GRB Inorganic Chemistry IIT JEE PDF

PREFACE
"Inorganic Chemistry for Competitions" has primarily, been written with the aim of meeting the needs and interests of
students seeking admission to professional courses especially in engineering and medical. This is an age oftough competition where
only the best survives. No doubt, the syllabus for various entrance tests is nearly the same as for intermediate or 10+2 examinations,
yet even good students fail to qualify as the standard of these tests is comparatively high and seats in engineering and medical
colleges are limited.
The present trend in competitive examinations is the stress on an objective rather than subjective treatment of the subject
matter. A critical scrutiny of the question papers of previous years of various entrance tests reveals that a variety of questions such as
very short answer type, short answer type, fill in the blanks, true and false, match the column, multiple choice, numerical type are
usually asked. In order to answer these questions, the students must be well equipped with thorough knowledge of the subject and its
application. With these objectives in mind, I have tried to present inorganic chemistry for competitions covering whole of the
syllabus of nearly all the competitions. The complete subject matter has been arranged in a systematic manner. Every topic has been
dealt precisely and to the point in a simple and understandable language. Things have been explained with proper reasoning
wherever possible. A good number of illustrations and solved problems based on structure and properties including numerical
problems have been provided to understand the theoretical aspect. Due emphasis has been given on group discussions of various
groups of periodic table. Flow-sheet diagrams have been provided to simplify the extraction of various metals, preparation of a
number of compounds and their properties. At the end of each chapter, a good number of questions of various types have been given
for self-assessment. It is my belief that students will be duly rewarded if they attempt these questions honestly and sincerely after
learning the particular topic. Necessary hints have been given whereverit is felt necessary.
Human efforts are never perfect. In spite of my best efforts, I am aware of the possible errors and omissions that have escaped
my notice. I shall, therefore, be extremely thankful to the learned teachers who will extend their cooperation by sending their
valuable criticism, suggestions and observations for further improvement of the book. I consider it my duty to pay thanks to the
authors and publishers ofthe books which I have consulted during the preparation of the manuscript.
My sincere thanks are due to Shri Manoj Kumar Bathla, Proprietor, MIs G.R. Bathla & Sons, Shri Shiv Charan Sohal (Artist) for
the whole-hearted cooperation in the preparation and publication of this book. I am also thankful to Dr. A.K. Virmani and Dr. A.S.
Singh for their encouragement, cooperation and guidance in the preparation ofthe manuscript ofthis book. Finally, I thank my wife
and children for the help they have extended in proof-reading.
June,20GO O.P.TANDON
( ,
CONTENTS-
Chapters Page No.
Classification of Elements and Periodicity in Properties 1~67
1.1 Introduction (1), 1.2 Earlier Attempts of Classification of Elements (2), 1.3 Mendeleev's Periodic Law and Original
Periodic Table (3),1.4 Modem Periodic Law and Modified Form of Mendeleev's Periodic Table (4),1.5 Naming the
Elements (9), 1.6 Electronic Configurations and the Periodic Table (11), Periodic Table ofthe Elements (Long Form-
Representing Electron Configurations) (14), 1.7 Extended or Long Form of Periodic Table (17), Periodic Table of the
Elements (Long Form) (18), 1.8 Position of an Element on the Basis of Electronic Configuration (22), 1.9 Atomic
Properties or Periodic Properties of Elements (23), 1.10 The Screening Effect or Shielding Effect (24), 1.11 Effective
Nuclear Charge (24), 1.12 Atomic Radius (24), 1.13 Ionic Radius (28), 1.14 Ionisation Enthalpy or Ionisation Potential
(29), 1.15 Electron Gain Enthalpy or Electron Affinity (31), 1.16 Electronegativity (33), 1.17 Some other Properties in
which Periodicity is Observed (34), Some Solved Problems (37), Summary and Important Points to Remember (41),
Practice Problems (44), Answers (48), Illustrations of Objective Questions (49), Objective Questions (51), Answers
(59), Objective Questions for lIT Aspirants (60), Answers (62), Matrix Matching Questions for lIT Aspirants (62),
Answers (63), Assertion-Reason :Type Questions (63), Answers (63), Thought Type Questions (64), Answers (66),
IntegefAnswer Type Questions (67), Answers (67).
Chemical Bonding 68-156

2.1 Introduction (68), 2.2 CllUse of Chemical
Combination (69), 2.3 LeWis Symbols of
Elements (70), 2.4 Electn)hic Theory of
Valency (70), 2.5 Electrovalenfor Ionic Bond
(70), 2.6 Determination ofLattke Energy (73),
2.7 Types oflons (74), 2.8 Method of Writing
Formula of an Ionic Co~pound (74),
2.9 Difference between Atornsand Ions (75),
2.10 General Characteristics'· of Electrovalent
Compounds (75), 2.11 Varia~l~ Electrovalency
(77),2.12 Covalent Bond (78),2.13 Covalency
(79), 2.14 Covalent Compounds (80),
2.15 Covalent Molecules of Elements (80),
2.16 Characteristics of Covalent Compounds
(80), 2.17 Comparison between Ionic and /
Covalent Bonds (81), 2.18 Comparison
between Ionic and Covalent Compounds
(81),2.19 Coordinate Bond (8l},2.20 Failure of Octet Rule (83), 2.21 Lewis Formulae for Molecules and Polyatomic
Ions (84), 2.22 Formal Charge (88), 2.23 Polarity ofCovruent Bond (89),2.24 Dipole Moment (90),2.25 Polarisation
(Change of Ionic Character ,to. Covalent Character) (92), 2.26 Hydrogen Bonding (93), 2.27 Modem Concept of
Covalent Bond (95),2.28 Hybridization (97), 2.29 Resonance (101),2.30 Prediction of Geometry (Shape) of Covalent
Molecules (102), 2.31 Valenc~ Shell Electron Pair Repulsion (VSEPR) Theory (104),2.32 Bond Characteristics (107),
2.33 Odd Electron Bonds (l09), 2.34 Molecular Orbital Theory (109), 2.35 Metallic Bonding (118), Some Solved
Problems (119), Summary and Important Points to Remember (123), Practice Problems (128), Answers (132),
Illustrations of Objective Questions (134), Objective Questions (136), Answers (148), Objective Questions for lIT
Aspirants (149), Answers (151);Matrix Matching Questions for lIT Aspirants (152), Answers (152), Assertion-Reason
Type Questions (152), Answers(153), Thought Type Questions (153), Answers (156), Integer Answer Type Questions
(156), Answers (156).
(x)
Acids and Bases 157-177

3.1 Introduction (157), 3.2 Arrhenius Concept (157), 3.3 Bronsted-LowryConcept (159), 3.4 Lewis Concept (161 ),3.5
The Lux-Flood Concept (163), 3.6 Usanovich Concept (163),3.7 Hard and Soft Acids and Bases (163), 3.8 Some
General Trends in Acidic and Basic Properties (164), Summary and Important Points to Remember (166), Practice
Problems (168), Answers (170), lllustrations of Objective Questions (171), Objective Questions (172), Answers (175),
Objective Questions for lIT Aspirants (175), Answers (175), Matrix Matching Questions for lIT Aspirants (176),
. Answers (176), Assertion-Reason Type Questions (176), Answers (176), Integer Answer Type Questions (177),
Answers (177).
General Principles of Extraction of Metals 178-208

4.1 Occurrence of Elements (178), 4.2 Occurrence of Metals (180), 4.3 Metallurgy (181),4.4 Concentration or
Dressing of the Ore (l81), 4.5 Extraction or Isolation of Crude Metals (183), 4.6 Thermodynamic Principles of
Metallurgy (186), 4.7 Applications of Elling ham Diagram in Pyrometallurgy (188), 4.8 Third Operation-Refining or
Purification (189),4.9 Furnaces (191), 4.10 Refractory Materials (192), Mineral Resources of India (193), Some
Solved Problems (193), Summary and Important Points to Remember (195), Practice Problems (198), Answers (199),
lllustrations of Objective Questions (200), Objective Questions (201), Answers (205), Objective Questions for lIT
Aspirants (206), Answers (206), Matrix Matching Questions for lIT Aspirants (206),Answers (207), Assertion-Reason
Type Questions (207),Answers (207), Integer Answer Type Questions (208), Answers (208).
.. Revision Exercisoe1 (Ch~pt'r 1 to 4) floe - 214.

6! '" .....' ,
Hydrogen and its Compounds (nai , 215-265

5.1 Position of Hydrogen in Periodic Table (216), 5.2 Discovery and
Occurrence (217),5.3 Preparation (217), 5.4 Manufacture of Hydrogen 17 18
(219), 5.5 Properties of Hydrogen (220), 5.6 IndustrialApplications (221),
5.6.1 Hydrogen Economy (222), 5.7 Hydrides (223), 5.8 Special Forms of 13 14 IS 16
Hydrogen (227), 5.9 Isotopes of Hydrogen (227),5.10 Heavy Hydrogen or
Deuterium, (228),5.11 Tritium (~H.or iT) (229), 5.12 Heavy Water or
Deuterium Oxide (D20) (230), 5.13 Water (231), 5.14 Hard and Soft Water
(234), 5.15 Hydrogen Peroxide (236), Summary and Important Points to
Remember (245), Practice Problems (248), Answers (250), Illustrations of
Objective Questions (251), Objective Questions (253), Answers (259),
Objective Questions for lIT Aspirants (260),· Answers (260), Matrix
Matching Questions for liT Aspirants (260), Answers (260), Assertion-
Reason Type Questions (261); Answers (261), Thought Type Questions
(261), Answers (263), Brain Storming Problems (263), Integer Answer
Type Questions (265), Answers (265).· ,
Alkali Metals and their Compounds (ClrouplAor1,na1, 266-315

6.1 Position of Alkali Metals in Periodic Table (266), 6.2 Abnormal
Behaviour of Lithium (272), 6.2.1 Diagonal Relationship : Similarities 13 14 IS 16 17 18
with Magnesium (272), 6.3 Lithium (273), 604 Sodium (276),
6.5 Compounds of Sodium (278), 6.6 Potassium (289), Summary and
Important Points to Remember (293), Practice Problems (296), Answers
(299), Illustrations of Objective Questions (300), Objective Questions
(302), Answers (308), Objective Questions for lIT Aspirants (309),
Answers (310), Matrix Matching Questions for liT Aspirants (311),
Answers (311), Assertion-Reason Type Questions (311), Answers (312),
Thought Type Questions (312), Answers (313), Brain Storming Pro\?lems
(313), Integer Answer Type Questions (315),Answers (315).
(xi)
Alkaline Earth Metals and their Compounds (Group IIAor2, nai,

7.1 Position of Alkaline Earth Metals in Periodic Table (316),
7.2 Solubility of Compounds of Alkaline Earth Metals (322), 13 14 15 16 17 18
7.3 Difference between Alkfl,line Earth Metals and Alkali Metals (323),
7.4 Abnormal BehaviouiofBeryllium (323), 7.5 Similarities (Diagonal
Relationship) between Beryllium and Aluminium (324), 7.6 Magnesium
(325),7.7 Calcium (329), 7J~ Compounds of Barium (334), Some Solved
Problems (335), Summary'hnd Important Points to Remember (337),
Practice Problems (340),fillswers (343), Illustrations of Objective
Questions (344), Objective Questions (346), Answers (351), Objective
Questions for lIT AspiraIl~ (352), Answers (353), Matrix Matching
Questions for ITT Aspirants (354), Answers (354), Assertion-Reason Type
Questions (354), Answers (J55), Thought Type Questions (355), Answers
(356), Integer Answer Type Questions (356), Answers (356).
• R,vl.lon 1".roill-2 (Chapter 5 to 7) 357 ..... 381
Elements of Group I~IA or 13 [Th. loron Family (nr np1)] 362'-407

(Ioron Ind Aluminium)
8.1 General Characteristics of Group lIlA or 13 Elements (362),
8.2 Abnormal Behaviour ofJ30ron (368), 8.3 Comparison of Boron and
Aluminium (368),8.4 Diag6pal Relationship of Boron and Silicon (370),
8.5 Boron (371),8.6 CompO,unds of Boron (372),8.7 Aluminium (378),
8.8 Compounds of Alunii,nium (382), 8.9 Goldschmidt's Alumino-
Thermic Process (384), Some Solved Problems (384), Summary and
Important Points to Remem~er (387), Practice Problems (390), Answers
(393), Illustrations of Objootive Questions (394), Objective Questions
(396), Answers (402), Objective Questions for lIT Aspirants (403),
Answers (404), Assertion-Reason Type Questions (404), Answers (405),
Thought Type Questions (405), Answers (406), Brain Stonriing Problems
(406), Integer Answer Type Questions (407),Answers.(407).
. ..'
Elements of Group IVA or 14 (EI.m.ntlofClrbon "Imlly, nrnpl) 408-460

9.1 Position in Periodict~ble (408), 9.2 Comparison of Carbon and
Silicon (412), 9.3 Compari~on of Tin and Lead (414),9.4 Carbon (415),
t
15 16 17 18
9.5 Compounds of Carbon (418), 9.6 Silicon (425),9.7 Compounds of
Silicon (426),9.8 Tin (430); 9.9 Compounds of Tin (431),9.10 Lead or
Plumbum: (433),9.11 CompOunds of Lead (435), Some Solved Problems
(437), Summary and In:J.portant Points to Remember (440), Practice
Problems (443), Answers (446), Illustrations of Objective Questions
(448), Objective Questions (449), Answers (455), Objective Questions for
lIT Aspirants (456), Answers (457), AssertioJ?-Reason Type Questions
(457), Answers (458), Th,ought Type Questions (458), Answers (459),
Brain Storming Problems (459), Integer Answer Type Questions (460),.
Answers (460). .'
(xii)
Elements of Group VA or 15 '46t--529

(Elements of Nitrogen aqd Phosphorus Family, ns'lnp3)
10.1 Position in Periodic Table (461), 10.2 Abnormal Behaviour of

Nitrogen (466), 10.3 Nitrogen.(N2) (467), 10.4 Important Compounds
of Nitrogen (469), 10.5 Nitrates (485), 10.6 Phosphorus (486),
10.7 Compounds of Phosphorus (489), 10.8 Arsenious Oxide or Arsenic
Trioxide (497), 10.9 Fertilizers (498), Some Solved Problems (501),
. Sununary and Important Poiqtsto Remember (504), Practice Problems
(509), Answers (513), Ilhisttations of ObjeCtive Questions (515),
Objective Questions (517), Answers (524), Objective Questions for IIT
Aspirants (524), Answers (525), Assertion-Reason Type Questions (526),
Answers (526), Thought Type Questions (526), Answers (528), Brain
Storming Problems (528), Integer Answer Type Questions (529), Answers
(529).
Elements of GrQup VIA or 16 (The Oxygen Family, ns'lnp4)

. .{
530-575
,f
11.1 Position in Periodic Table (530), 11.2 Abnormal Behaviour of

Oxygen (535), 11.3 Dissimilarities between Oxygen and Sulphur (535),
11.4 Oxygen (536), 11.5 Oxides (537), 11.6 Ozone (539), 11.7 Sulphur
(542), 11.8 Compounds of Sulphur (543), Some Solved Problems (555),
Sununary and Important Point~ to Remember (557), Practice Problems
(561), Answers (564), Ill1;lstfations of Objective Questions (565),
Objective Questions (567),Answers (571), Objective Questions for IIT
Aspirants (572), Answers (573);'Assertion-Reason Type Questions (573),
Answers (574), Thought Type:Questions (574), Answers (575), Integer
Answer Type Questions (575),A,nswers (575).
Elements of Group VilA or 17 (Halogens, ns'lnp5) 57'6-624
12.1 Position in Periodic Table (576), 12.2 Anomalous Behaviour of

Fluorine (580), 12.3 Fluorine (581), 12.4 Chlorine (582), 12.5 Bromine 18
(586), 12.6 Iodine (588), 12.7 Halogen Acids or Hydracids (591), 12.8
Oxides of Chlorine (595),12.9 Oxy-Acids of Chlorine (596), 12.10
Interhalogen Compounds (600), 12.11 Polyhalides (60 I), 12.12 Basic
Properties of Iodine (602),11.13 Pseudohalides and Pseudohalogens
(602), Some Solved Problems (602), Summary and Important Points to
Remember (605), Practice Pl;'o~lems (608), Answers (611), Illustrations
of Objective Questions (613); Objective Questions (615), Answers (620),
Objective Questions for IIT-Aspirants (620), Answers (621), Assertion-
Reason Type Questions (622),' Answers (622), Thought Type Questions
(622), Answers (623), IntegerAnswer Type Questions (624), Answers
(624).
(xiii)
The Elements of 18 or Zero Group (Inert Gases or Noble Gases, ns2np6) ·~25:r"644
18
13.1 Position in the Periodic Table (625), 13.2 Occurrence (627),
2 13 14 15 16 17
13.3 History of the Discovery of Noble Gases (627), 13.4 Isolation of ---i----,
Noble Gases from the Atmosphere (628), 13.5 Separation of Noble Gases
(629), 13.6 Uses of Noble Gases (630), 13.7 Compounds of Noble Gases
(631), 13.8 Importance of Noble Gases in Theoretical Chemistry (634),
13.9 Determination of Atomic Mass of a Noble Gas (635), Summary and
Important Points to Remember (635), Practice Problems (637), Answers
(638), Objective Questions (639), Answers (642), Objective Questions for
lIT Aspirants (642), Answers (642), Matrix Matching Questions for lIT
Aspirants (642), Answers (643), Assertion-Reason Type Questions (643),
Answers (644), Thought Type Questio~. (644), Answers (644), Integer
AnswerType Questions (644), Answers (644).
•:. Revision Exercise-3 (Chapter 8 to 13) 645-650
Transition Elements or d .. block Elements and foo block Elements '651~ 754
14.1 Introduction (651), 14.2 Electronic Configuration (652), 14.3 General Characteristics of Transition Elements
(654), 14.4 Chemistry of Chromium (661), 14.5 Potassium Dichromate, K2Cr207 (662), 14.6 Chemistry of Manganese
(663), 14.7 Potassium Permanganate, KMn04 (664), 14.8 Position of Iron in Periodic Table (666), 14.9 Extraction of
Iron (667), 14. 10 Types ofIron(669), 14.11 PassivityofIron(672), 14.12 Compounds ofIron (672),14.13 Corrosion of
Iron (674), 14.14 Position of Coinage Metals in Periodic Table (675), 14.15 Copper (678), 14.16 Compounds of Copper
(683), 14.17 Silver (687), 14.18 Compounds of Silver (690), 14.19 Gold (692), 14.20 Position of Zinc Family in
1 18
2 13 14 15 16 17
--+--i+--·d-bloCK Elements (Transition hlernen'ts)---.t--i---;--t--+--t-.....,
6 7 8 9 12
Cr Mn
(xiv)
Periodic Table (693), 14.21 Zinc (695),14.22 Compounds of Zinc (697), 14.23 Mercury (699), 14.24 Compounds of
Mercury (701), 14.25 Photography (703), 14.26fBlock Elements (704), 14.27 General Characteristics of Lanthanides
(705),14.28 General Characteristics of Actinides (707),14.29 Comparison of Lanthanides and Actinides (709), Some
Solved Problems (710), Summary and;lmportant Points to Remember (719), Practice Problems (723), Answers (726),
Questions Based on the Properties (728), Illustrations of Objective Questions (732), Objective Questions (734),
Answers (746), Objective Questions for lIT Aspirants (747), Answers (748), Matrix Matching Questions for lIT
Aspirants (749), Answers (749), Assertion-Reason Type Questions (750), Answers (750), Thought Type Questions
(750), Answers (752), Brain Storming Problems (753), Integer Answer Type Questions (754), Answers (754).
Coordination Compounds and Organometallics

15.1 Molecular or Addition CompouDds(755), 15.2 Terminology of Coordination Compounds (756), 15.3 Nomen-
clature of Coordination Compounds (760),15.4 Werner's Coordination Theory (762),15.5 Isomerism in Coordination
Compounds (764), 15.6 Bonding in Coordination Compounds (767), 15.7 Stability of Coordination Compounds in
Solutions (776),15.8 Preparation of Coordination Compounds (777), 15.9 Importance of Coordination Compounds
(777), 15.10 Organometallic Compounds (780), Some Solved Problems (782), Summary and Important Points to
Remember (786), Practice Problems (789), Answers (791), Illustrations of Objective Questions (792), Objective
Questions (794), Answers (801), Objective Questions for lIT Aspirants (801), Answers (803), Matrix Matching
Questions for lIT Aspirants (804), Answers (804), Assertion-Reason Type Questions (805), Answers (805), Thought
Type Questions (806), Answers (807), Brain Storming Problems (807), Integer Answer Type Questions (810), Answers
(810).
.. Rlvilion &)(lrOIII-4 (Chapter 14 to 15) 811- 818

Stoichiometry (CllauldoM ..ad on Chomlu' equation.)
16.1 Introduction (816), 16.2 Calculations Involving Mass-Mass Relationship (816), 16.3 Calculations Involving
Mass-Volume Relationship (820), 16.4 Calculations Involving Volume-Volume Relationship (821), Some
Miscellaneous Worked Problems (822), Practice Problems (with Hints and Answers) (828), Illustrations of OJ;>.jective
Questions (833), Objective Questions (835), Answers (839), Objective Questions for lIT Aspirants (839), Answers
(841), Thought Type Questions (841),Answers (841), IntegerAnswerTypeQuestions (842),Answers (842).
Volumetric Analysis
17.1 Introduction (843), 17.2 Methods of Expressing Concen-
trations of Solutions (844), 17.3 Types of Titrations (845),
17.4 Determination of Equivalent Mass (847), 17.5 Calculations of
Volumetric Analysis (849), 17.6 To Determine the Amount of
Sodium Hydroxide and Sodium Carbonate in a given Mixture
(854), 17.6.1 To Determine the Amount of Sodium Carbonate and
Bicarbonate ill a Mixture (854), 17.7 Kjeldahl's Process (856),
Some Miscellaneous Worked Problems (858), Practice Problems
(864), Answers (870), Illustrations of Objective Questions (871),
Objective Questions (873),Answers (878), Objective Questions for
lIT Aspirants (879), Answers (881), Matrix Matching Questions for
lIT Aspirants (881), Answers (881), Assertion-Reason Type
Questions (881), Answers (882), Thought Type Questions (882),
Answers (883), Integer Answer Type Questions (883), Answers.
(883).
(xv)
Qualitative Inorganic Analysis 884--920

'18.1 Introduction (884), 18.2 Identification of Acidic Radicals (884); 18.3 Identification of Acidic Radicals with
.Sodium Carbonate Extract (889), 18.4 Identification of Basic Radicals (890), 18.5 Chemical Reactions Involved in the
Tests of Basic Radicals (894), 18.6 Dry Tests (897), Some Solved Problems (899), Practice Problems (904), Answers
(908), Illustrations of Objective Questions (909), Objective Questions (910), Answers(915), Objective Questions for
lIT Aspirants (916), Answers (917), Matrix Matching Questions for lIT Aspirants (917), Answers (917), Assertion-
Reason Type Questions (918), Answers (918), Thought Type Questions (918), Answers (919), Brain Storming
~
Problems (919).
,';.
.:. RevisiOn ExerciallilB (Chaptof 18 to 18) 921 =026

Environmental Chemistry 927 .... 967
19.1 Introduction (927),19.2 Components of Environment (928),19.3 Environmental Pollution and Environmental
Pollutants (932), 19.4 Some Commonly used terms in Environmental Pollution (933), 19.5 Types of Pollution (933),
19.6 Air Pollution (934), 19.7 Acid Rain (941), 19.8 Smog (944), 19.9 Greenhouse Effect and Global Warming (946),
19.10 Ozone Layer and its Depletion (Stratospheric Pollution) (948), 19.11 Water Pollution (950), 19.12 Soil or Land
Pollution (953), 19.13 Strategies to Control Environmental Pollution (955),19.14 Green Chemistry as an Alternative
Tool for Reducing Pollution (956), Some Solved Problems (958), Practice Problems (960), Answers (962), Objective
Questions (963), Answers (965), Objective Questions for lIT Aspirants (966), Answers (966), Assertion-Reason Type
Questions (966), Answers (967), Thought Type Questions (967), Answers (967).
(xvi)
• Miscellaneous
Type 1 : Short and Very Short Questions
Type 2 : Matching of Columns
Type 3 : Multiple Choice-A
: Multiple Choice-B
Type 4 : Assertion·Reason Type
TypeS -: ThoughtTypeQuestions 99B
• Practice Papers (with Sol-utlons) 1000~f016
Classification of Elements
and Periodicity in Properties
, /f,~"",::~r
1,1?~ INTRODUCTION
Contents: Object and Need of Classification of Elements

1.1 Introduction Elements are the basic constituents of all types of matter. The
1.2 Earlier Attempts of Classification of discovery of chemical elements has been an ongoing process since
Elements ancient times. Certain elements, such as gold, appear in nature in
1.3 Mendeleev's Periodic Law and Original elemental form and were thus discovered thousands of years ago. In
Periodic Table contrast, some elements are radioactive and intrinsically unstable. The
1.4 Modern Periodic Law and Modified Form of majority of the elements although stable are dispersed widely in nature
Mendeleev's Periodic Table and incorporated in~o numerous compounds. For centuries, therefore,
1.5 Naming the Elements scientists were unaware of their existence. At the beginning of the
1.6 Electronic Configurations and the Periodic eighteenth century, only a few elements were known. During eighteenth
Table and early nineteenth century,. advances in chemistry made it easier to
1.7 Extended or Long Form of Periodic Table isolate elements from their compounds. As a result, the number of known
1.8 Position of an Element on the Basis of elements had more than doubled from 31 in 1800 to 63 by 1865. At
Electronic Configuration
present, 117 elements* are known. Out of these, recently discovered
1.9 Atomic Properties or Periodic Properties of
elements are not natural but synthetic, i.e., man-made and efforts are still
Elements
going on to synthesise new elements by artificial transmutation.
1.10 The Screening Effect or Shielding Effect
As the number of known elements increased, it became rather
1.11 Effective Nuclear Charge
impossible to study individually the chemistry of these elements and
1.12 Atomic Radius
their innumerable compounds and scientists began to investigate the
1.13 Ionic Radius
possibilities of classifying them in useful ways. The basic object and
1.14 Ionisation Enthalpy or Ionisation Potential
need of classification can be best stated in the words of Huxley, liThe
1.15 Electron Gain Enth,dpy or Electron Affinity
actual or ideal arrangement together of those which are alike and
1.16 Electronegativity separation of those which are unlike; the purpose of this arrangement
1.17 Some other Properties in which Periodicity being primarily to disclose the correlations, or laws of union, or
is Observed
properties, or circumstances and secondarily to facilitate the operation
*Recently, elements with atomic numbers 113, 114, 115, 116 and 118 have been reported.
2 G.R.B. Inorganic Chemistry for Competitions
of the mind in dearly receiving and then retaining in the DOBEREINER'S TRIADS
memory the characteristics of the objects in question." In
Mean of atomic masses of 1st
short, it can be stated that the basic object of classification Triads
and 3rd elements
is to arrange the facts regarding elements and their
Li Na K 7;39 ::: 23
compounds in such a way so that we may have greatest 7 23 39
control over their characteristics with least possible effort. Cl Br I
The best classification would be one which puts together 81.25
35.5 80 127
those elements which resemble in most respects and Ca Sr Ba ,,·~40+137'.
separates other. ' '. "'2; . ' = 88.5
40 88 . 137
Attempts were made to classify the elements according to S Se Te 32 + 127
= 79.5
one property or the other. The elements were classified into 32 79 127
metals and nonmetals; into electropositive and electro- P As Sb 31 + 120
75.5
negative. They were classed according to their valency as 31 75 120 2
monovalent, divalent, trivalent, etc. In these classifications, Fe Co Ni Nearly same atomic masses
the same element frequently appeared in more than one class Ru Rh Pd Nearly same atomic masses
and hence all these early classifications were considered as Os Ir Pt Nearly same atomic masses
rough classifications. After the establishment of Dalton's The main drawback of this classification was that the
atomic theory, the chemists took atomic mass as the concept was not applicable to all the known elements but
fundamental property of the element and tried to seek a only to a limited number of elements. However, one point
relationship between the properties of the elements and became clear that properties of the elements have some
their atomic masses. A number of classifications, taking relationship with their atomic masses.
atomic masses of the elements as the basis, were presented.
The best formulation resulted in the form of periodic table 2. De-Chancourtois Classification
in which elements have been arranged according to their (The Telluric Helix)
properties in a tabular form. The elements belonging to In 1862, A.E. de Chancourtois a French geologist, made
same vertical column constitute a chemical family having the next attempt to classify the elements on the basis of their
similar properties. atomic masses. He tooJ<a vertical cylinder with 16 equidistant
The arrangement of elements in order of increasing lines on the surface of the cylinder. The lines were parallel
atomic masses, with elements having similar properties in to the axis of the cylinder. A helix at 45° to the axis was
vertical cohunns, is kno'WIl as periodic table. The periodic drawn and the elements' in the increasing oider of their
classification (long or extended form of periodic table) of atomic masses were arranged on the helix. He observed that
eleIIlents ;hCis extremely simplified the study of such a large elements which differed from each other in atomic mass 16
number of elem~nts:
-
1~' EARLIER. ATrEMPTS OF CLASSIFICATION
or multiples of 16 fell in a vertical line fromthe centre of the
. spiral. The elements in a vertical line showed nearly the same
properties. However, this classification was not accepted.
OFJ=LEMENTS (Brief HistoricaLDevel()pment 3. Newland's Law of Octaves
()f the Periodic Table)
The first attempt to classify all the known elements was
Some of the earlier classifications based' on atomic masses made by Newl<ind in 1864. He presented the law of octaves.
of the elements are described below: According to this law, the elements when arranged in
order of their increasing atomi( masses, the. eighth
1. Dobereiner's Law of Triads· succeeding element was the repetition of the first one like
Dobereiner between 1815 and 1829 gave his la~ of triads. 8th note of the musical. scale, i.e./after a difference of seven,
According to which in certain tfi~ds (groups of three elements with similar characteristics were observed. The
elements which possessed similar chemical properties) the following are the three horizontal rows of the Newland's
. atomic mass of the central element was merely the arithmetic classification:
mean ofthe atomic masses of the other two elements and the Musical scale: Sa. Re. Ga Ma· Pa Dha Ne
pr6perties of the middle element were in between thos~ of 1 2 3 4 ·5 6 7
the end members. These families.of three elements became 1st H Li Be B C N: 0
knoWnas Dobereirier's' Triads. But in some triads, all the 2nd F Na Mg Al Si P S
three elementS possessed nearly the same atomIc masses, 3rd CI K Ca Cr Ti Mn Fe
hence the law was rejected. . The system worked quite well for the lighter elements. For
example, H,F and Cl show similar properties and similarly
Classification of Elements and Periodicity in Properties 3
. ..'
Li, Na and K exhibit same characteristics. The system, When he plotted theseatornic"olumes agairlst corres-
however, fails in the case of heavier elements as manganese ponding atomic. masses, a curve takil}g the form of sQarp
has been placed along with nitrogen and phosphorus or peaks and broad minima was obtained (Fig. 1.1) .
iron has been placed along with oxygen and sulphur, i.e., . Lother Meyer pointro.out that elements having siInilar
dissimilar elements have been grouped which is against the properties occupy similar positions on the curve such as,
aim of classification. This clearly shows that in the classi- 0) Alkali metals, having the largest atomic volumes,
fication, the properties of the elements were not taken into occupy the maxima of the curve ..
account and only the elements were arranged in order of (ii) The alkaline earth metals (Mg, Ca, Sr, Ba) occupy
ascending atomic masses. No space was left for the elements positions at about the mid-points on the descending portions
which were unknown at that time and many elements were of the curve.
provided wrong positions on account of wrong values of (iii) The halogens (p, CI, Br, D occupy positions on the
atomic masses in this classification. Thus, Newland's c1assi"': ascending portions of the curve.
fication was not accepted as an appropriate arrangement. (iv) The transition elements occupy minima of the curve.
However, his work was recognised by Royal Chemical On the basis of above observations Lother Meyer proposed
Sodety, London, and was awarded Davy Medal in' that, the physical properties of the elements are a periodic
1887. . function of their atomic masses..
[Later on when atomic numbers of the elements were
4. Lother Meyer's Curve plotted in place of atomic masses, the general pattern of the
Lother Meyer in Germany and Mendeleev in Russia curve remained the same.]
quite independently evolved, in 1869, identical classifications It was an ideal classification but lacked in practical utility
of elements. Both these classifications emphasised the as it was not easy to keep in mind the various portions of
periodicity of the properties of the elements with their atomic the curve.
masses. While Mendeleev's classification was based
largely on considerations of chemical properties of the 1.3,t~ MENDELEEV'S PERIODIC LAW
elements, that of Lother Meyer emphasised physical AND ORIGINAL PERIODIC TABLE
characteristics of the elements. Lother Meyer presented the Mendeleev put forward the periodic law which forms the
classification in the form of curve while Mendeleev in the basis of modern classification of elements in the form of a
form of a table. table, known as the periodic table. The periodic law can be
Lother Meyer calculated the atomic volumes of the known stated as, "If the elements are arranged in order of
elements by applying formula, increasing atomic masses, their properties vary in definite
. 1· Atomic mass manner from member to member of the series, but return .
AtOllUC vo ume = D 'tyenSl more orless nearly to same value at certain fixed points in
the series". In other words the properties of the elements
80!r-.--r~~r-~.--.-.--.-'--.-.--.-.-~ are a periodic function of their atomic masses. This was an
75~+-~-+~--~~~~--~+-~-+--bC~s+-~ impressive version of law of octaves. The main points of
7o~+-~-+~--~~~~--~+-~-+--~+-~i periodic law as stated by Mendeleev in his original paper
65~+-~-+~--~~~~--~~-r-+--Hr+-~! are reproduced below:
1. The elements, if arranged according to their
atomic weights exhibit an evident periodicity of properties.
2. Elements whichaie similar as regards their chemical
properties have atomic weights which either are of nearly
same value, e.g., Fe, Co, Ni or increase regularly, e.g., K, Rb,
Cs.
3. The arrangement of elements/or groups of elements in
the order of their atomic weights corresponds to their so
called "valencies" as well as their distinctive properties.
4. The elements which are most widely distributed in
nature have small atomic weights and possess shaq"lly
defined properties.
5. The magnitude of .atomic weight determines the
character of the element.
o 10 20 30 40 50 60 70 80 90 100110120130140150 6. Many yet unknown elements may be discovered.
Atomic mass,amu . 7. The atomic weight of an element may sometimes be
Fig. 1.1 Lother Meyer's curve corrected with the aid of the knowledge of the atomic weights
of the adjacent elements.
8. Certain characteristic properties of elements can be properties, i.e., he laid emphasis on the properties of the
foretold from their atomic weights. elements rather than their atomic masses. For example, iodine
Mendeleev's original table prepared in the light of the having lower atomic mass than tellurium was placed ahead
above statements arranged similar elements in horizontal of tellurium because iodine showed similarities with fluorine,
rows but subsequently he modified the original table chlorine and bromine.
arranging similar elements in vertical columns. The original When Mendeleev presented the periodic table, oilly 63
modified periodic table, is shown in Fig. 1.2. elements were' known. Thus, a number of gaps for
A tabular arr~gement of elements' in rows and unknown elements were left in the table and the properties
columns, highlighting the regular repetition of properties of these unknown elements were predicted on the basis of
of elements is called a periodic table. periodic law. These predicted properties helped the
Mendeleev arranged the elements between hydrogen future scientists in the discovery of unknown elements. For
and uranium, providing 90 spaces between these two example, gallium and germanium were not known when
elements, in order of increasing atomic masses. Elements Mendeleev presented the periodic table. These elements
with similar properties were present in vertical columns were named eka-aluminium and eka-silicon. Their properties
called groups. The horizontal rows were called periods. were predicted by Mendeleev and these. properties actually
Mendeleev violated his periodic law at certain places to give matched the properties of elements when discovered.
appropriate position to the few elements on the basis of their
Mendeleev's Original Periodic Table of Elements
Series Group I Group II Group III Group IV Group V Group VI Group VII Group VIII
RzO RO R Z0 3 RO z /RH 4 RH3 /RzOs RHz /R0 3 RH/R z0 7 R0 4
1. H =1
2. Li = 7 Be 9.4 B 11 C = 12 N 14 0=16 F = 19
3. Na = 23 Mg 24 Al = 27.3 Si = 28 P 31 S 32 Cl = 35.5
4. K = 39 Ca 40 ... 44 Ti = 48 V 51 Cr = 52 Mn=55 Fe 56, Co = 59
Ni 59, Cu = 63
5. (Cu = 63) =68 ... = 72. As 75 Se 78 Br = 80
6. Rb = 85 "Yt = 88 Zr=90 Nb 94 Mo=96 .;. = 100 Ru = 104, Rh = 104
Pd = 106, Ag 108
7. (Ag = 108) Cd 112 In 113 Sn = 118 Sb 122 Te = 128 1= 127
8. Cs = 133 Ba 137 "Di = 138 "ee = 140 - -
9. - - - - -
10. - "Er 178 "La = 180 Ta 182 W = 184 - Os = 195, Ir = 197,
Pt 198
11. (Au = 199) Hg 200 Tl 204 Pb = 207 Bi = 208
12. - - - Th = 231 U 240 - -
Fig. 1~2 Mendeleev's Periodic Table (Published in 1872)
The table given below gives a comparative idea about the The original periodic table consisted eight vertical
predicted and· actually observed some of the properties' of columns called groups (Fig. 1.2), Each group consisted
these elements. elements· having similar properties, especially the same.
valency. This table consisted a number of defects such as
Property Eka-aluminium Gallium Eka-silicon Germanium
(Predicted) (Observed) (Predicted) (Observed)
anomalous pairs, position of isotopes, position of
lanthanides and actinides, etc. Some of these defects do not
Atomic mass ~ ro n n~
exist in modern Mendeleev periodic table .
Densi7, .5.9 .5.94 5.5 5.36
(g!cm )
Formula of
oxide
EO z GeOz 1.41 MODERN PERIODIC LAW AND MODIFIED
FORM OF MENDELEEV'S PERIODIC TABLE
Formula of GaC~ GeClt
chloride' As the physical and chemical properties of an element
*Atomic weight is now referred as atomic mass .. depend on the number of electrons and their arrangement in
various energy shells of the atom, the atomic number (the modified the periodic law by saying. that physical and
number of positive charges on the nucleus or number of chemical. properties of ~e elements are periodic function
electrons in energy shells) is thus the fundamental property of their atomic numbers. When the elements are arranged
of the element. The change in atomic number always changes in order of their increasing atomic numbers, the same table
the fat~ of the element, i.e., a new element comes into as presented by Mendeleev, is obtained. The table based on
existence. Moseley, thus, suggested that basis of classifi- atomic numbers of the elements is called modem
cation of elements should be the atomic numbers of the Mendeleev's periodic table (Fig. 1.3). In modern periodic
elements rather than the atomic I;llasses of the elements. He table, similar properties recur after the intervals of 2, 8, 8, 18,
Modern (Modified) Mendeleev's Periodic Table
~
I II III IV V VI VII VIII 0
A B A B A B A B A B A B A B
PERIOD
1 1 H
1
H
1
He
2
2 U Be B C N 0 F Ne
3 4 5 6 7 8 9 10
3 Na Mg AI Si P S Cl AI
11 12 13 14 15 16 17 18
K Ca Sc Ti V Cr Mn Fe Co Ni
19 20 21 22 23 24 25 26 27 28 Kr
4 Cu Zn Ga Ge As Se Br 36
29 30 31 32 33 34 35
Rb Sr Y 'ZI Nb M:l Tc Ru Rh Pd
37 38 39 40 41 42 43 44 45 46 Xe
5 Ag Cd In Sn Sb Te I 54
47 48 49 50 51 52 53
Cs Ba La* Hf Ta W Re Os Ir Pt
55 56 57-71 72 73 74 75 76 77 78 Rn
6 Au Hg TI Ph Bi Po At 86
79 80 81 82 83 84 85
Fr Ra Act Ku(Rf) Ha Unh(Sg) Uns(Bh) Uno Une Uun

87 88 89-103 104 105 106 107 (Hs) (Mt)
7 Uuu Uub Uut Uuq, Uup Uuh 108 109 110 Uuo
111 112 113 114 115 116 - 118
~------ - - - Inner Transition Elements - - - - - - - - - ----7
*Lanthanide Ce Pr Nd Pm Sm Eu Gd 1b Dy Ho Er Tm Yb Lu
series 58 59 .60 61 62 63 64 65 66 67 68 69 70 71
tActinide Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
series 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Fig. 1.3 Modem Mendeleev's Periodic Table

18 and 32 elements, i.e., if the elements are arranged in the elements are known as rare-earths or lanthanides (from At.
increasfug atomic numbers, the properties of the elements no. 58 to 71) and are separately arranged below the table in
reappear after definite regular intervals. With the a horizontal row.
replacement of atomic mass by atomic number as the basis The last period consists of 28 elements, out of which 14
of classification, two main defects of original table based on elements from atomic number 90 to 103 are separately
atomic masses disappear. These defects are: arranged like lanthanides below the table in a horizontal
(i) Anomalous pairs: The original periodic law based row. These elements are called actinides.
. on atomic masses is violated in case of four pairs of elements (iii) Every period starts from a member of alkali group and
in order to give them positions on the basis of properties. The ends with a member ofzero group. The first period, however,
elements having higher atomic masses have been assigned starts with hydrogen.
positions before the elements having lower a.tomic masses at .
four places as shown below: 1st element I Last element I Total elements
Period
At. no. At. no. in the· period
At. mass
(a) Ar· K
40 39
(b) Co
59
Nt (c) Te
58.6 127.5 127
(d) Th
232
Pa
231
1st period H (l)}. He (2) 2
At. No. 18 19 . 27 28 52 53 90 91 2nd p<riod Li OJ 2) Ne (10) 8
N~
Ar (18) 8
This defect disappears, if the elements are arranged in
order of increasing atomic numbers.
(ii) Position of isotopes: Isotopes are atoms of the same
: : : :::: 8}8}18 I<r (36) 18
element having different atomic masses but same atomic

18
number. The isotopes of the same element will be given
different positions, if atomic mass is taken as a basis. This
shall disturb the symmetry of the table. In modem table, one
: : : ::: }'}8 :::: 32
position is fixed for one atomic number and since all the 32
. 7th period Fr(87) Uuo(118) Incomplete
isotopes of an element have the same atomic number, these 31 till today
are assigned orily one position. I
The difference in the atomic numbers of subsequent alkali
• Description of the Modern Periodic Table metals indicates that similar properties recur after the
intervals of 2, 8, 8, 18, 18 and 32.
The main characteristics of the modem periodic table are, (iv) There is.a gradual change in properties of the elements,
(i) The modem periodic tabie consists of nine vertical when we move in a period from one end to the other end.
columns called 'groups' and seven horizontal rows called Some examples are given below to justify this gradual
'periods'. The nine groups are marked from 0 to VIII. The change.
groups I to VII are divided each into subgroups A and B. (a) Valency: Valency of the elements increases from 1
The groups I to VII are termed normal groups. In the VIIT to 7 from left to right if oxygen is taken as standard. The
group in one place, there are three similar elements placed valency of the elements with respect to hydrogen increases
together which are known as transition triads-Fe, Co and from 1 to 4 and then decreases from 4 to 1 in a period.
Ni; Ru, Rh and Pd; Os, Ir and Pt; Hs(Vno), Mt (Vne) and Vun. Group I II III IV V VI VII
(ii) Starting from hydrogen to the heaviest element,
. uranium, there are 92 elements which are arranged in Valency with respect 1 2 3 4 5 6 7
to oxygen
different periods as follows:
Formula of the oxide R20 RO R20 3 R02 R20 S R03 R20 7
First period 2 elements (very shott period) Valency with respect 1 2 3 4 3 2 1
Second period 8 elements (short period) to hydrogen
Third period 8 elements (short period) Formula of the hydride RH RH2 RH3 RRt RH3 RHz RH
Fourth period 18 elements (long period)
. Fifth period 18 elements (long period) This trend is observed in every period. Considering the
Sixth period 32 elements (very long period) .members of third period,
Seventh period 6 elements upto (very long period, incom-
Na Mg AI Si P S CI
at. no. 92 plete period)
Oxide NazO MgO Al 20 3 Si02 P 20 S S03 Cl20 7
The IV, V and VI periods possess two horizontal rows Valency 1 2 3 4 5 6 7
each, which are termed even and odd series. In the 6th period,
fifteen elements from lanthanum (At. no. 57) to lutetium (At. Thus, group number signifies the valency of the elements
no. 71) are given only one position in third group. These belonging to that group if oxygen is taken as a standard.
Classification of Elements andPeriodidtjr in Properties 7
(b) Metallic nature: In a period from left to right ~ef~llic Be
.nature decreases while ,non-metallic characlerindeases.'· I
, ·M·.'·
3r~~riod ·Na
~
.Mg
Metals
Al
Metalloid
.Si P sq.
'--:---v-----'
Non-metals
./g~. Bridge element .
Ca Zn
. Non-metallic·· natUre ·u{in~reasing' ~rd~; I .1.
MetaIlicnatuI'e. in decreasing order· .) Group
IIA
rrBa d
9
Hg
Group
lIB
(c) Electropositive I Electronegative character·: The I 1
electropositive ,character decreases in a ,period frem left to ~a· 'Uub
right or electronegative character increases.. '
(vii) Diagonal relationship: The first three members of
2nd period Li Be B·C N O·p second period (Li, Be and B) not only show· siinilarities with
~------~----~--------,--~--~
Electronegative na):Ure ,in ,increasing order the members of their own groups but show similarities with
or the·elements diagonally placed in the higher groups. This
Electropositive nature in decreasing order resemblance is termed diagonal relationship. .
(d) Oxidising and reducing nature: In a period, from GrouP. I II. III IV
left to right, th$? reducing naturedeereases while oxidiSing 2nd period Li Be B .. ' C
Na~Mg ~AI~Si
nature increases.
3rd period Na Al Si P S Cl 3rd period
------------=
Strong reducing Strong. oxidisirig Lithium shows similarities with magnesium; beryllium
. agents agents with aluminium and boron with silicon.
(e) Nature of oxides: In a period, from left to rIght the (viii) The elements belonging to the same subgroup exhibit
basic nature of the oxides decreases while acidic nature· of either same properties or a regular gradation in properties
the oxides increases. from top to bottom. Some examples are given below:
(aHn the case of elements of IA group (ti, Na, K, Rb, Cs)!
3rd period Na Mg Al Si P S CI
the eiectropositive character· or reactivity increases as the
Oxide Na20 MgO AJ203 Si02 PzOS 503 020,
atomic number increases. An the members show· memO-
Basic in na~ Ampl;toteric . Addic oxides
valency and are never found in free state. The oxides are basic
Acidic nature in and form strong alkalies. .
increasing order
(b) In IVA group, the metallic character increases
Na20 is mqre basic than MgO and MgO is more basic than gradually:
Al20:3; .
C Si G e S n Pb
(v) Typical elements: . The elements ofsecond and third Non-metals Metalloid Metals
periods are called typical elements as they summarise the
.. The acidic nature of the oxides decreases 'from top to
properties of their respective groups ..
bottom. CO2 is acidic while Pb02 is basic in nature.
Groups 11 III IV V VI VII (c) In VIlA group, the reactivity of theha:logens decreases
2nd period. Li Be B C N. 0 F from topto bottom. These ate electronegative ahd this'nature
3rd period. Na. Mg Al Si .p S CI decreases from top to bottom. Their hydrides are acidic in
Li andNa are typical elements of 1st group while Be and nature and acidic natUre increases as the atomic number
Mg are typical elements of 2nd group and sO'on. increases.
(vi) ,Bridge elements : The typical· elements of third F Cl Br I
. )
period are also called bridge elements as the division Electronegative nature decreases
between two subgroups A andB starts from these elements.
In second group,Mg acts as a bridge element. The properties HF HCl HBr HI
of bridge element are somewhat mixed properties of the Acidic nature incre.ases
.elements of two subgroups as magnesium shows similarities (ix) the elements of the same subgroup resemble, quite
with alkaline earth metals alA) on one hand and with zinc closely to each other but there is hardly any resemblance
metals (lIB) on the other. between the elements of two subgroups A and B. For example,
in the firSt group, the subgroup A consists of alkali metals
(Li, Na, K, Rb, Cs) and subgroup B consists of coinage metals equivalent mass was known to be 4.55. It was thought that
(Cu, Ag, Au) but there appears hardly any resemblance the element possessed valency 3 as its oxide was iso-
between the members of these two subgroups except all show morphous with alumina (AI20 3). Thus, the atomic mass of
monovalency. Some properties are given below to justify this this element came out to be ·3 x 4.55 =13.65. On the basis of
statement: this value of atomic mass, it should have been given
IA (alkali metals) IB (coinage metals) position after carbon (At. wt. 12) but Mendeleev assigned
(Li, Na,K, Rb, Cs) (Cu, Ag, Au) position to beryllium in second group, i.e., he considered
beryllium as bivalent. The atomic mass of beryllium was
(i) Soft metals . (i) Hard metals
given the value 4.55 x 2 =9.10. This value of atomic mass
(ii) Low densities (ii) High densities
(iii) Low melting points (iii) High melting points
justified its position in second group along with Mg, Ca, Sr,
(iv) Highly reactive (iv) Less reactive, noble metals etc. In the modem periodic table the atomic masses of all the
(v) Never found free in (v) Found mainly free in nature elements have been corrected.
nature Thus, the (ii) and (iii) points are of only historical
(vi) Decompose water (vi) Do not decompose water importance because all the unknown elements have already
readily been discovered and the atomic masses of the elements have
already been corrected.
The difference in properties of two subgroups is maximum
in the first group and decreases from first to fourth group. • Defects of Modern Periodic Table
The difference again becomes maximum in the seventh
Inspite of its great usefulness in the study of various
group.
elements, the modem periodic table suffers from the
• Applications or Advantages of the following defects:
(i) Position of hydrogen: On account of the dual nature
Modern Periodic Table
of hydrogen as it shows resemblance with alkali metals
(i) Classification of elements: There is no doubt that and also with halogens, its position in periodic table is
the Mende1eev's periodic system is far superior to the all uncertain. It is sometimes placed in the first group and
earlier classifications of elements. The periodic table has sometimes in the seventh group. However, the symmetry of
reduced the study of 117 known elements into the study of the periodic table is not disturbed whether it is accommo-
few groups. If we know the properties of a single member of dated in the first group or in seventh group. It is, therefore,
a group, we can have good approximation of the properties difficult even at present, to decide to where it should correctly
of other members of this group without individually studying be placed.
them. (ii) Similar elements separated : Certain elements
(ii) Discovery of new elements: A number of gaps were which show similar properties have been separated in the
left in Mendeleev's periodic table for unknown elements. periodic table. For example, Ba and Pb resemble each other
Mendeleev even predicted the properties of these unknown in so many respects but have been placed in second and
elements. These properties helped the workers to discover the fourth groups, respectively. Similarly Ag and Tl having
unknown elements more readily and accurately. Thus, the similar properties have been separated, Ag placed in the first
periodic system hastened the discovery of many new group and Tl in the third group.
elements. In modem periodic table, no gap is present, i.e., all (iii) Dissimilar elements placed together in the same
the unknown elements upto 112 have been discovered. group : Elements showing marked dissimilarities are
Recently, the elements with atomic numbers 113 to 116 and placed in one group. For example, coinage metals (Cu, Ag
118 have been reported. Element with atomic number 117 is and Au) have been placed with alkali metals in the first
still to be discovered.k> complete the last, i.e., 7th period of group. Manganese has been placed in seventh group along
the periodic table. with halogens with which it shows little resemblance.
(iii) Correction of atomic mass: Atomic mass of an . (iv) Metals and nonmetals: No attempt has been made
element is related with equivalent mass of the element by the to place metals and nonmetals separately in the periodic
follOWing formula: table. Most of the groups are mixed groups consisting of
Atomic mass = Equivalent mass x valency .metals, nonmetals and metalloids.
(v) Position of vm group: There are twelve ele-
Valency of the element can be known from its position in ments in this group and they are accommodated in only
the periodic table. This formula was utilised in the correction four available positions. This group is present between
of atomic mass of many elements. For example, when seventh and zero groups which is not justified.
Mendeleev presented the periodic table, the atomic mass of (vi) Positions of transition elements : Mendeleev
beryllium was not correctly known. However, its regarded only the three triads of VIU group as the only
transition elements but modem studies have confirmed 1J~ NAMING THE ELEMENTS
that there are 40 (upto At. no. 112) transition elements. These
Every element has been given a definite name and· for
similar elements are scattered in whole of the periodic
covenience a nick name which in chemical language is called
table. These elements are present in every group except zero
a symbol. When a new element is discovered, the discoverer
group.
usually gets the opportunity to suggest a name for the ele-
(vii) Position of lanthanides and actinides: Inspite of
ment, which is then approved by The International Union
the fact that members of lanthanide series and actinide series
of Pure and Applied Chemistry-IUPAC.
have different atomic numbers, these have not been given
Symbols have been derived either by taking the first
individual places in the periodic table. The 14 members of
alphabet of the name of the element or by taking the first
lanthanide series have been placed along with lanthanum
alphabet and one more alphabet from the name of the
in the third group and sixth period and similarly 14
element (for example, C for carbon; N for nitrogen; 0 for
members of the actinide series have been placed along with
oxygen; Ca for calcium; Al for aluminium, etc.) but there are
actinium in third group and seventh period. The justification
quite number of elements for which the derivation of the
for assigning one place to these elements has been given on
symbol is not quite so obvious .~ for example, Na for sodium;
the basis of their similar properties. The properties are so
Pb for lead; Ag for silver; Fe for iron, etc. Such anomalies occur
similar that the fifteen elements from La to Lu can be
because of the way, the elements were originally named. Some
considered as equivalent to one element. In case, these
of the elements were given names in other languages such
elements ·are assigned different positions, i.e., arranged in
as Latin, German, etc.
order of their increasing atomic numbers, the symmetry of
Of all the elements on the periodic table, C,s, Fe, Cu, As, Ag,
the whole arrangement would be disrupted. The same
Sn, Sb, Au, Hg, Ph and Bi were known to ancient civilisations
explanation can be given in the case of actinides.
so the date of their 'discovery' is not known. Of these, Fe, Cu,
SCIENTISTIPERSONS. AFTER WHOM ELEMENTS HAVE BEEN NAMED

Name Brief biography Element named
1. Vasilii Yefrafovich von Chief of staff of the Russian Corps of Mining samarium, Sm
Samarski-Bykhovets (1803-1870) Engineers (element 62)
2. lohan Gadolin Finnish chemist; first person to isolate a gadolinium, Gd
(1760-1852) lanthanide element (element 64)
3. Pierre Curie (1859-1906) and Husband and wife scientific team; Pierre curium, Cm
Marie Curie (1867-1934) French and Marie Polish by birth; jointly won the Nobel Prize in physics in 1903 (element 96)
4. Albert Einstein Most famous scientist of the twentieth century; einsteinium, Es
(1879-1955) German by birth; won the NObel Prize in physics in 1921 (element 99)
5. Enrico Fermi (1901-1954) Italian physicist; made great advances in the study of nuclear fermium,Fm
reactions; won the Nobel Prize in physics in 1938 (element 100)
6. DmitriMendeleev Russian chemist; renowned for the mendelevium,Md
(1834-1907) development of the periodic table (element 101)
7. Alfred Nobel (1833-1896) Swedish inventor of dynamite an patron of the Nobel Prizes nobelium, No
(element 102)
8. Ernest Lawrence American inventor of the cyclotron; won the . lawrencium, Lr
(1901-1958) Nobel Prize in physics in 1939 (element 103)
9. Ernest Rutherford New Zealand physicist! chemist; made seminal rutherfordium, Rf
(1871-1937) contributions to understanding the structure of (element 104)
the atom; won the Nobel Prize in chemistry in 1908
10. Glenn Seaborg American chemist; first prepared many of the elements beyond uranium seaborgium, Sg
(1912-1999) in the periodic table; won the Nobel Prize in chemiStry in 1951 (element 106)
11. Niels Bohr (1885-1962) Danish physicist; studied electronic energy levels within atoms, w Wch help bohrium,Bh
our understanding of the atom; won the Nobel Prize in physics in 1922 (element 107)
12. Lise Meitner (1878-1968) Austrian physicist; made discoveries concerning meitnerium, Mt
nuclear fission; controversially never awarded a Nobel Prize (element 109)
13. Wilhelm Rontgen German physicist; discoverer of X-rays; won rontgenium, Rg
(1845-1923 ) the Nobel Prize in in 1901 (element 111)
G.R.B. Inorganic Chemistry for Competitions
Ag, Sn, Sb, Au, Hg and Pb are the abbreviations for the Latin , Abbtevlation
names ferrum, cuprum, argentum, stannum, stibium, aurum,
o ,nil n
hydragyrum andplumbum. The earliestknown discovery of an
1 un u
element was that ofphosphorus, P:It was isolated in 1669 by
2 bi b
Hennig Brand from, the distillation of u,:dne (he }Vas appar-
3 tri
eittly try;U:g t9 m~ke silv~r orgold~unsuccessfully,of course!)
4; quad" q
and was 'named cifterthe Greek.W()rd.phosphpro~,.me~ng
pent p
'bringer of light', as theele~entglows in the da~k, E'iements
6 hex h
have been named after countries (germanium, francium, am-
7 sept' s
ericium, polonium) and even after the places they were first
8 ,oct 0
discovered; the Svvedish town ofYtterby has the distin$Qnof
9 'enn, e'
having four elements (E1rbium,Eri ytterbium, Ybi yttrium, Y; , ,
and terbium, Th)na,med after it/as these were found in depos- 2. In certain cases the names areshortened. For example,
its close tQthe town. Surprisingly few elements have been 'biium' and 'triiumi are sftortened to 'bium' and' 'trlum' and
named after people; at present, only·14 peOple have been 'ennnil' .is shortened' to 'ennii'. '
immortalised on the periodic table, and they are listed in table , 3. The symbol for the elementis made up from thefirst
given on page 9. letters from the rootswhlchmake up the names. The
" mixture of Latin arid Greek roots has' been chosen to eitsure
• Nomenc,latureofElements that the symbols are all different.
with Atomic Numbers> 100 IUPAC Nomenclature for the Super Heavy-Elements
The elements coming after uranium which do not exist Atomic
naturally, are named transuranic or transurani~m elements. Name of the element Symbol
The elements with Z 104-116 and 118 have been reported 101 Unnilunium, Un"':nil- ium (Unu)
recently and are called transactinidesbr super-heavy To
102 'Unnilbium Un - nil- bi - urn (Unb)
elements. These are synthetic, i.e., man-made elements. The T02
production of synthetic elements requires binuclear reactions 103 Unniltrium Un -nil-tri-um (Uilt)
between two positive nuclei that must be fused together T03
Un - nil- quad - ium
against the force of electrical repulsion. Nuclear accelerators' 104 Unnilquadium T o -4- (Unq)
are used for this' purpose. There are currently two major 105 Unnilpentium (Unp)
groups working on producing super-heq,vy elements, one in , 106 Unnilhexium, . (Unh)
California, USA and the other at Dubna near Moscow, 107 Unnilseptium (Uns)
Russia. By convention, the workers who discover· a new 108 Unniloctium (Uno)
109 Urinilennium . (Une)
element have the right to name it. However, in recent years, no Ununnilium (Uun)
on account of competitive spirit disputes have arisen over . 111 Unununium Un- un -nu -ium (Uuu)
the names of the newly discovered elements. For example, TTT
112 Ununbhim Un - un - bi - urn (Uub)
both American and Russian scientists claimed credit for the TT2
discovery of the' element 104. The Americans named it Un- -tri-um
113 Ununtrium
T 3 (Uut)
Rutherfordium whereas Russians named it Kurchatovium.
Un un - quad ium
To avoid such problems, the IUPAC suggested that until the 114 Ununquadium T T -4- (Uuq)
discovery of the new element is proved and its name is 115 Ununpentium -un- pent -ium (Uup)
T -S-
officially recognised, a systematic nomenclature based on the
116 Ununhexium Un - un - hex-ium (Uuh)
atomic number of the element be followed. The following are' TTT
the points of the nomenclature of the element having atomic 118 Ununoctium Un un - oct ium (Uuo)
numbers> 100.
TTs
120 Unbinilium Un - bi - nil-fum (Dbn)
1. The names are derived by using the numerical roots for' T20
three digits in the atomic number of the element and adding
the ending -ium: The roots for the numbers are: At pr~sent 117 elements have been discovered. These are
the elements with atomic numbers upto 116 and 118. Element
with atomic number 117 is yet to be discovered. Official In the periodic table, the elements have been arranged in
IUPAC names for the elements upto 111 have been approved order of increasing atomic number, i.e., increased number of
by the Commission on Nomenclature of Inorganic orbital electrons. Thus, each element contains one more
Chemistry (CNIC). orbital electron. than the preceeding element Each period
Thus, the newly discovered element is first given a starts with ns1 configuration and ends with a noble gas (He,
temporary name on the basis of atomic number and later on ls 2, in the first period and ninp6 configuration with rest of
a permanent name with symbol is alloted by the consent of the elements). The sequence in which the various energy
IUPAC representatives. - levels are filled determines the number of elements.
Nomenclature of Elements with 1st period Is 2 elements in .this period
Atomic Number above 100 2nd period 2s 2P 8 elements in. this period ,
3rd period 35 3P 8 elements in this period
Atomic Name on the basis Official IUPAC 4th period 45 3d 4p 18 elements in this period
number of atomic number name Symbol 5th period 55 4d 5p 18 elements, in this period
(Temporary) (Permanent)
6th period 65 4f 5d 6p. ' 32 elements in this period
101 Unnilunium Mendelevium Md 7th period 75 5f 6d 7p 32 elements in this period
102 Unnilbium Nobelium No The ground state electronic configurations oithe elements
103 Unniltrium Lawrencium Lr are given in the following table. For the sake of simplicity,
104 Unnilquadium Rutherfordium Rf condensed electronic configurations of the elements are
105 Unnilpentium Dubnium Db given. In writing condensed electronic configuration of an
106 Unnilhexium Seaborgium Sg, element, the electronic configuration of the nearest noble gas
107 Unnilseptium Bohrium Bh oflower atomic number is represented by its chemical symbol
108 Unniloctium Hassium Hs in square bracket. For example, the condensed electronic
109 Unnilerinium Meitnerium Mt configuration of sodium can be written as l
110 Ununnilium Darmstadtium Ds
[Ne] 3s1
111 Unununium Rontgenium Rg
112 Ununbium* - - Electronic Structures of the Elements
113 Ununtrium*
114 Umlnquadium* - z Element Symbol Structure
115 Ununpentium* - - , ~p,
Period -1
116 Ununhexium* - - ' . Hydrogen H lSI
118 Ununoctium* - - 2 Helium He 152
*OfficiallUPAC name yet to be announced.
3 Lithium Li [Hel ~1
1.6J~ ELECTRONIC CONFIGURATIONS 4 , Beryllium Be [He) '252
- AND THE PERIODIC TABLE 5 Boron B [Hel U 2pl

6 Carbon C [He] 252 2p2
The au'fbau principle and electronic configuration of the 7 Nitrogen N [Hel252 2p3
8 Oxygen 0 [He) 252 2l
atoms of elements provide a theoretical foundation for the 9 Fluorine F [He] 2s2 2p5
classification of elements. It is now recognised that the 10 Neon Ne [He] 252 2p6
periodic table is essentially the consequence of the periodic Period - 3
variation in electronic configuration of the atoms of the 11 Sodium Na [Ne]'3s1
elements which determine the physical and chemical 12 Magnesium Mg [Ne] 3;
properties of the elements and their compounds. The elements 13 Aluminium Al [Ne) 352 3pl
in a vertical column,i.e., in a group of the periodic table 14 Silicon Si [Ne] 3; 3p2
15 Phosphorus P [Ne] 3; 3p3
exhibit similar-chemical behaviour.·This is due to the' fact 3p4
16 Sulphur S [Ne)3i
that these elements have same number and same distribution 17 Chlorine CI [Ne] 3; 3p5
of electrons in their outermost orbitals, i.e., in the valency 18 Argon Ar [Ne) 3; 3p6
shell. For example, the group lA elements (alkali metals) Period 4
which show same chemical behaviour possess same valence 19 Potassium K [Ar] 4s1
shell configuration, i.e., ns1. Similarly, the group VIlA 20 Calcium Ca [Ar] 4;
elements (halogens) which are similar in chemical properties 21 Scandium Sc [Ar] 3i 452
possess same valence shell configuration, ns 2np5. 22 Titanium Ti [Ar] 3i 45 2
23 Vanadium V [Ar] 3j 45 2
..
Z Element Symbol Structure Z Structure

5 1
24 Chromium Cr [Ar] 3d 45 76 Osmium . Os [Xe] 414 ·Sd6 6i
2S Manganese Mn [Ar]3d5 45 2 77 Iridium lr [Xe] 414 Sd
7
65 2
26 Iron Fe [Ar] 3a6 4s2 78 Platinum Pt [Xe] 414 Sd 9 651
27 Cobalt Co [Ar] 3d7 45 2 79 Gold Au [Xe] 4l4. Sd W 65 1
28 Nickel Ni [Ar] 3dB 4s 2
80 Mercury Hg [Xe] 414 Sd w 6s 2
29 Copper. Cu [Ar] 3aI D 45 1
[Ar] 3dlO 452 81 Thallium Tl [Xe] 4fH Sd 1D 68 2 6pl
30 Zinc Zn .
82 Lead Pb [Xe] 414 Sd lD 6s 2 6l
31 Gallium Ga [Ar] 3dlO 4s 2 4pl
83 Bismuth Bi [Xe] 414 Sd lO 6s 2 6p3
32 Germanium Ge [Ar] 3dlO 4s
2 4p2
84 Polonium Po [Xe] 414 Sd lD 6s 2 6p4
33 Arsenic As [Ar] 3dlO 4s 2 4p3
8S Astatine At [Xe] 414 Sd lD 6s2 6p5
34 Selenium Se [Ar] 3dlO 4i 4p4
3S Bromine Br [Arl 3aI° 4i 4p5 86 . Radon Rn [Xe] 414 Sd lD 6i 6 p6
36 Krypton Kr [Ar] 3dlD 4s2 4p6 Period - 7

Period - 5 87 Francium Fr [Rnl 751
37 Rubidium Rb [Krl SSI 88 Radium Ril [Rn17i
38 Strontium Sr [Krl si
89 Actinium Ac [Rn] 6d 1 7s 2
1
39 Yttrium Y [Kr] 4d si 90 Thorium Th [Rnl 6d 2 7i
40 Zirconium Zr [Kr] 4d2 sl 91 Protactinium Pa [Rnl sl 6d 1 75 2
[Kr] 4a4 Ssl
41 Niobium Nb 92 Uranium U [Rnl Sf3 6d 1 78 2
42 Molybdenum 1\10 [Kr] 4d5 S5 1
93 Neptunium Np [Rn]S( 6d 1 75 2
43 Technetium [Kr] 4a5 Ss2
{ Tc 1 94 Plutonium Pu [Rn]S! 6dO 752
Tc [Kr] 4a6 5s
9S Americium Am [Rn]S{ 6do 7s 2
44 Ruthenium Ru [Krl 4d7 S5 1
45 Rhodium Rh [Krl ~ Ssl 96 Curium Cm [RnIS{ 6d 1 7i

46 Palladium Pd [Krl 4d1O Sso 97 Berkelium
{Bk [Rri] 5l 6do 7i
47 Silver Ag [Krl 4d1O S5 1 Bk [Rn]Sr 6d 1 7i
48 Cadmium Cd [Kr] 4aI° S5 2 98 Californium Cf [Rn] slo 6do
99 Einsteinium Es [Rnl Sfll 6do 7s 2
49 Indium In [Krl 4d1O sl 5pl
100 Fermium Fm [Rnl Sl2 6do 7s 2
SO Tin Sn [Kr14d1O S82 5p2
S1 Antimony Sb [Krl 4dlO S82 5t 101 Mendelevium Md [Rnl Sf13 6dO 78 2
52 Tellurium Te [Krl 4d1O sl Sp4 102 Nobelium No [Rnl Sl4 6do 7s 2
53 Iodine I [Krl 4d1O 582 Sp5 103 Lawrencium Lr [Rnl Sl4 6d 1 7s 2
54 Xenon Xe [Kr] 4d1O sl Sp6
104 Rutherfordium Rf [RnlSfl4 6d 2
Period 6 105 Dubnium Db [RnlSfl4 6d3 752
SS Caesium Cs [Xel6s1 106 Seaborgium Sg [RnlSl4 6d 4 75 2
S6 Barium Ba . [Xel 6s2 107 Bohrium Bh [RnlSl4 6d 5 752
Lanthanum La [Xe] Sd1
108 Hassnium Hs [RnlSl4 6d 6
S7 6l 7
109 Meitnerium Mt [RnlSf14 6d
S8 Cerium Ce [Xel 4fl Sd 1 6s 2 110 Darmstadtium Ds [RnISfH 6ds
S9 Praseodymium Pr [Xe] 4l Sd o 6s2 111 Rontgenium Rg [Rnl SfH 6d 9 75 2
60 Neodymium Nd [Xe]4( Sdo 6s2 112 Ununbium Uub [Rnl Sl4 6d lD 75 2
61 Promethium Pm [Xe]4l Sd O 6i 113 Ununtrium Uut [Rn] Sl4 6d lO 75 2 7pl
62 Samarium Sm [Xe] 4f' Sdo 6s2 114 Ununquaclium Uuq [Rn] Sl4 6d lO 75 2 7p2
63 Europium Eu [XeI4{ Sd o 6s2 l1S Ununpentium Uup [Rn] Sl4 6d lO 78 2 7p3
64 Gadolinium Gd [XeI4{ Sd 1 6i 116 Ununhexium Uuh [Rn] Sl4 6d 1o 7l 7p4
6S Terbium Tb [Xel4l Sd o 6s 2 118 Ununoctium Uuo [Rnl Sl4 6d 1O 7l 7p6
66 Dysprosium Dy [Xel 4flo Sd o 6i
67
68
Holmium
Erbium
Ho
Er
[Xel 4fll
[Xel 4f12
Sdo 6i
SdO 65 2 • Classification of Elements on the
Basis of Electronic Configurations
69 Thulium Tm [Xel 41 3 Sdo 6i
70 Ytterbium Yb [Xel 4fH Sdo 6i 1. Bohr's Classification
71 Lutetium Lu [Xel 4fH Sd 1 6i
The classification proposed by Bohr is based on complete
72 Hafnium Hf [Xe] 4f14 Sd2 682 and incomplete energy shells. The elements have been
73 Tantalum Ta [Xe]4r Sd 3 6s 2
grouped into four types:
74 Tungsten W [Xel4r Sd 4 652
(i) Inert gases : In the atoms of these elements, the
7S Rhenium Re [Xe14l 4 Sd5 652
s-and p-subshells of the outermost shell ar~ completely filled.
With the exception of helium which has ls2 configuration, Each series consists of 14 elements, i.e., in the lanthanides,
all other have ns2np6 configuration. Because of stable 4f is gradually filled up while in actinides, Sf is gradually
configuration, these elements do not show chemical activity filled up. The properties of these elements are similar to
under normal conditions. These are all gases under normal transition elements. The members of actinide series are
conditions and thus, termed as inert gases. Under special radioactive and majority of them are not found in nature. The
conditions, the higher members do form some compounds elem.ents from atomic number 93 onwards are called
with other elements and hence, the name has been changed transuranic elements and have been discovered by artificial
to noble gases. Seven elements He, Ne, AI, Kr, Xe, Rn and means.
Uuo belong to this group. This group was unknown at the In this classification, the elements Zn, Cd and Hg have
time when Mendeleev presented the periodic table. These not been included in any of the four groups of elements. The
elements are the end members of the respective periods of elements Lu and Lr of the inner~transitiongroup have
the periodic table, respectively. (n -2)f shell complete consisting of 14 electrons, hence their
(ii) Representative or Normal elements : In these inclusion in this group is not justified.
elements atoms have all shells complete except outermost
shell which is incomplete. The number of electrons in the 2. Differentiating Electron Classifications.
outermost shell varies from 1 to 7, i.e., the configuration of (Division of elements into S-, P-, d-, f-Blocks)
the outermost shell varies from ns1 to ni np5. These elements This classification divides the elements into four types, i.e.,
comprise of some metals, all non-metals and metalloids. s-, po, d- and f-block elements depending on the nature of the
These are the elements which are found in· nature in atomic shell into which the last electron enters. The last
abundance and active in nature. On account of this, these electron is called as differentiating electron. This classi-
elements are called representative elements. All the three fication is most rational and is now commonly in use. The
types of valencies are observed in the case of these elements. energy shell into which the last electron enters is of highest
These elements have one of the follOWing configurations in energy. This may not always belong to the outermost energy
their outermost shell: shell. In generat it can be said that aufbau principle is follow-
nsl, ns2, ns 2 np1, ns2 np2, ni np3, ni np4, ni np5 ed in filling of various energy shells with few exceptions.
123 4 5 6 7
~
Os-block elements
The number of electrons present in the outermost shell
signify the group to which these elements belong. o p-block elements
(iii) Transition elements: ... In the atoms of these elements II .0 d-block elements ?p
'(i
o fblock elements
I~;
the outermost shell and the penultimate shell (next to the ip
outermost) are incomplete. These elements have the general
3~ 4p
configuration (n 1)dl - 9 nsO or 1 or 2 either in the ground state
II ~
I Ii ip
or in excited state. These elements are present in fourth, fifth, .. 5~ 6p
sixth· and seventh periods of periodic table and are called tis
transition elements. The elements showing horizontal ~:s ** 6~ 'p
relationship as well as vertical relationship are termed
transition elements. There ~ four transition series, eVery
series consists of 9 elements each; Each series starts with a
member of third group and ends with a member of first group.
l± 4f
5f
.. Fig. 1.4 Periodic table, illustrating division of elements

1st series Sc 21 to eu
29 3d 1-94l
into s-, p-, d-, t- Blocks
2nd series Y 39 to Ag 47 4d 1-9552
3rd series La 57 to Au 79 5d 1-9652
[The elements from Ce (58) • (i) ..Block Elements
to Lu (71) are notincludedl
4th series Ac 89, Rf (104), Db (lOS)
In these elements, the last electron enters the ns energy
and 106 to 111 [The elements froD;l Th (90) shell. The maximum capacity of ns energy shelUs of two
to Lr (l03) are not included] electrons, thus, these elements have valency shell confi-
The elements belonging to this group are all metals. gurationeither ns1 or ns2.
(iv) Inner-transition elements: Atoms of these ele- The members of this block lie on the extreme left of the
ments have three outermost shells incomplete. The general periodic table. The elements having ns 1 configuration are
configuration is (n -2)f 1-14 (n - l)d O or 1 ni; There are two called. alkali metals (Group IA elements) while those having
series of elements, ns2configuration are called alkaline earth metals (Group IIA
(a) Lanthanides or rare-earths from Ce (58) to Lu (71) elements). The elements of s-block are also called as Reactive
(b) Actinides from Th (90) to Lr (103). m.etals.
Periodic Table of the Elements (Long Form)
" (Representing Electron, Configurations)
Main-Group Elements Main-Group Elements • _ _ _ -to>
"""iI-------....... , - - -,- - p-subshell is gradually filled up:
s-subshell is filled up
~ IA O(Zero)
G
Period 1 2
~1 H He
IIA Atomo ""mb" lilA IVA VA VIA VilA lS2
ls'
3 ,4 H Symbol ' 5 6 7 8 9 10
2 Li Be 1s' Valence-shell configuration B C N 0 F Ne

2s' 2s2
2
28 2p' '2s?2;1 2
28 2'; 2
28 2p· 2822p5 2822p6'
11 ,12 r+- Transition Elements ,+ 13 14 15 16 17 18
- - - - - - - - - - - - - - d-subshell is gradually filled up
3 Na Mg VIllB AI 5i P 5 CI Ar
Ss' ss2 IIIB IVB VB VIB VIIB r ..A..
""") IB liB 2
35 sp' 2
, 35 S;I 352Sp3 2
35 Sp' 3523 pS I 3823p6
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34' 35 36
4 K Ca 5c Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As 5e Br Kr
4.' 4r 3d'4s2 sif4s2 3cf4s2 3cf4s' 3cf'4s2 3cf'4s2 3d7 4s2 3cf'4s2 ,0
3d 4s' 3d,04s2 48 24p' ," 4824;1 4824p3 4824p· 4824 p5 4824p6
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb r V Zr Nb Mo Tc Ru Rh Pd Ag Cd In 5n 5b Te ,
I Xe
5s' 51 4d'5s2 4if5s2 4d'5s 1 4cf5s' 4cf'5s2 4d7 5s' 4Jl5s' 4d'o 4d 05s
'
4d 05s2
' SS25p' SS25;1 SS2 5p3 5s25p· SS25'; SS2Sp6
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir i
I
Pt Au Hg TI Pb Bi Po At Rn
as' as2 5d1es2 I st:I6s2 scfes2 5~SS2 5d5ss2 5d6ss2
7
5d as2 5dllss' 5d'Oas' 5d'Oas2 68"pl 68";1 68"p3 ss"p· SS"p5, 68",!
87 88 89 I 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
7 Fr Ra ACi.. Rf Db 5g Bh Hs Mt Os Rg Uub Uut Uuq Uup Uuh

1
Uuo
7s1 7r I
ad'7SL I echs2 sns2 ad'7s2 &f7s2 6d'7s2 7
Sd 7s2 ed'7s2 6d'7SL 6d'~s2 7s 27pl 7S2S;I 7s 2ep3 7s 27P' 7s 27p6
I
I
Inner·Transition Elements
I
I """iI----~------------ -f-subshell is gradually filled up-----------------
-- .......
I
I
I 58 59 60 61 62 63 64 65 66 67 68 69 70 71
I
;Gmh-;nid-:
Ce Pr Nd Pm 5m Eu Gd Tb Dy Ho Er Tm Vb Lu
4f5d'W 4FW 4"W 4,sW 4rw 4f7W 4f5d'w 4rw 4f1OW 4f"W 4f'2aSL 4f'36s2 4f146fl 7r 45d'w
90 91 92 93 94 95 96 97 98 99 100 101 102 103
"Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
w7s2 5f 26d'7s2 5f
3
6d'7s2 5f
46d'7s2 5f67 s2 5f 77s2 Sf7 6d'7SL 5f97s2 6f'~s2 5f11 7 s2 5f'27 s2 5f,37 s2 5f,47 s2 5f46d'7SL
Fig. 1.5 A Modern Form of the Periodic Table (Long Form)

(Representing valence-shell qonfigurations of the elements)
C4ssificap,on of .Elements ,and Periodicity in Properties 15
(ix) With exception of Be and Mg, they decompose water

ns 1
Elements Group IA Alkali metals and readily evolve hydrogen.
• (ii) p-Block Elements

H 1 lsI or 151
2
Li 3 15 , 2s1 or [He] 2s1
In the atoms of these elements,the last electron enters the
Na 11 Ii, 2i2p6, 3s 1 or [Ne]3s1
p-supshell 'of the outermost shell~ In these elements np-
K 19 2, 8; 8,45 1 , or lAr) 451 subshell is gradually 'filled, up. The valency shell '
Rb 37
'
2, 8, 18, 8, 55
1
or [Kr) SsI configuration varies from ni npl tons 2 np6.
Cs 55 2,,8, 18, 18, 8, 6s1 or [Xe) 651 , OJ,"de.r. nil npl ni np2 ns 2 np3 ns2 np4 ns 2 np5 ni np6
Fr 87 '2, 8, 18, 32, 18, 8, 75 1 or [Rn] 75 1 of the (IUrd (IVth\ (Vth (VIth (VIlth (Zero
period group) group) t group) group) group) group)
;', .>
Group'IIA
A 'A A A A
ns 2 Elements Group I1A Alkaline earth metals
2 ' , ' " ' n=2 B C N 0 F, Ne
152
..
He 2 Is (Actually belongs to zero group) or
2l,2pl 2s2 2p2 , 2s2 2p3 2s2 2p4 2s2 2p5 2l2p6
Be 4 ls2, 2s2 or [Hel 2s2
n=3 Al Si ' P S CI Ar
Mg 12 1i,2s22p6, 3s2 or [Ne]3i
3l' 3pt 352 3p'- 3s2 3p3 2
, 3s 3p4 35 2 3p5 3i 3p6
Ca 20 2, 8, 8, 482 or [Ar) 4s2
n=4 Ga Ge As Se Br Kr
Sr 38 2, 8, 18, 8, 5l or [Kr) 5i :
2
45 4p1 4i 4p2 4s2 4p3 4i 4p4 4i 4p5 4s2 4p6
Ba 56 2, 8, 18, 18, 8, 6s2 , or [Xe)6s2
Ra 88 2, 8, 18, 32, 18, 8, 7l or [Rn] 75
2 n 5 In Sn Sb Te I Xe
552 5p1 5i 5p2 5s2 5p3 5i 5p4 5ispS 5p6
General Characteristics ofs-Block Elements:
n 6 Tl Pb Bi Po At Rn
The general characteristics of alkali metals (Li, Na, K, Rb, 6i 6pl 6l6l 682 6l 6l6p4 6s2 6p5 6s2 6p6
Cs and FrY and alkaline earth metals'(Be, Mg, Ca, Sr, Ba and
Ra), i.e., s-block elements are the following: , n 7 Uut Uuq Uup Uuh Uuo
2
7s 7pl 7i 7p3 2
7s 7p4 7s2 7p6
(i) They are soft 'metals, possess low melting and boiling 7;7l
points, have the largest atomic radii'in *eir corresporiding Group Group Group Group' Group Group
periods and. are good conductors of heat and electricity. , 13 14 15 16 17 18
(ii) They have low values of ionisation energies and hence
highly electropositive. , , ," . [These elementS belong to subgroup A in the extended
(iii) They Me very reactive 'and. ieadily form' ionic ., form of periodic ,"table except zero group' in which no
compounds. They show a fixed valency which depends on subgroup is presenf.] These elements include some metals,
th~ number of electrons present in ~e outermost shell. The all non-metals and metalloids. s-block and p-block elements'
alkali metals show monovalency while alkaline earth metals, are collectively called normal or representative elements
show divalency. They are never found in free state in nature, (except zero group elements). Each period ends with a
due to their reactive
. -
nature.
- ',-:,
", member of zero group (18th group), i.e., a noble gas with a
"
(iv) On account of low ionisation energies and highly closed.sheU ns2np6 configuration. Prior to noble gas group,
negative electrode potentials, they act, as strong reducing there are two chemically important groups of non-metals.
agents., The alkali and alkaline .earth metals cannot be ' These are halogens (group 17) and chalcogens (group 16).
prepared by doing electrolysis of aqueous solutions of their
salts. General Characteristics of p-Block Elements
, (v) Except Be and Mgi they impart a characteristic colour (i) p-block consists of the elements of six groups, viz.,IIIA, ,
to the flame. IVA, VA, VIA, VIlA and zero group. The number of electrons
(vi) The compounds of s-block elements are predomi- in the oute,rmost shell, varies from .3 to 8, i.e., they have
nently ionic and colourless. However, lithium and beryllium .,..general ~onfiguration, nlnpl:.t,. The number.of electrons in
compounds are covalent in nature. the p~nultimate shell is either 2 or 8 or 18.
(vii) They have great affinity for oxygen and nonmetals. (ii)', Except F and inert gases, p-block elements show a
The oxideS are basic. The hydroxides are strong alkalies. number of oxidation states from +n to (n -, 8) where nis the
, (viii) They displace hydrogen from acids and form number of electrons f'resent in the outermost shell. '
corresponding salts. ,,'
1.6 G.R.B. Inorganic Chemistry for Competitions
Group iliA IVA VA VIA VIlA of 3d, 4d, 5d and 6d subshells of third, fourth, fifth and sixth
Oxid. states +3 +4 to-4 +5 to -3 +6 to -2 +7 to-1 energy shells, respectively. Each series starts with a member
[Oxygen is an exception. However, it can show -2, of third group. Every series consists 10 elements each. The
-l,-1/2(K02),-1 /3(K03) and +1/2(02PtF6) oxidation states.] end members of 3d, 4d, 5d and 6d series are the members of
(iii) The p-block elements generally show covalency but second group. The expected configurations of these elements
higher members can show electrovalency. The highly are tabulated in Fig. 1.6. The elements marked with asterisk
electronegative elements like halogens, 0, 5, N, etc., show (*) have different actual configurations.
electrovalencyby accepting electrons and forming anions. 3Id group 2nd group
Some of the elements show coordinate valency also. l 2
3d series Sc (21) [Ar) 3d 45 to Zn (30) [Ar) 3io4i
(iv) In the period from left to right, there is regular increase
Ost transi-
in nonmetallic character. However, nonmetallic character tion &eries)
decreases in the groups from top to bottom. 4d series Y (39) [Kr) 4dl~ to Cd (48) [Kr) 4d1°552
(v) Ionisation energies increase from left to right in a (2nd transi-
tion series)
period while decrease in a group from top to bottom. The
*5d series La (57) [Xe) 5d16s 2 to Hg (80) [Xe) 4f145d106s2
members of V group and zero group have exceptionally high (3rd transi-
values of ionisation energies on account of half filled and tion series)
fully filled orbitals in the valency shell. t6d series Ac (89) [Rn] 6d17s 2 to Unb (112) [Rn) 5fl46dl~i
(vi) In every period, reducing nature decreases from left (4th transi-
to right while oxidising nature increases. Reducing nature tion series)
increases in a group from top to bottom. Halogens are strong *The elements from Ce (58) to Lu (71) are not included.
oxidising agents. tThe elements from Th (90) to Lr (03) are not included.
(vii) Most of them are highly electronegative. The
electronegativity increases in a period from left to right and General Characteristics of d-Block Elements
decreases in a group from top to bottom.
(viii) Most of them form acidic oxides. The general characteristics of d-block elements are :
(i) They are all metals having high melting and boiling
(ix) No member of p-block series or the salts imparts a
characteristic colour to the flame. points. They are hard in nature and good conductors of heat
(x) Chemical properties change from group to group. It is and electricity. They are malleable, ductile and possess high
difficult to summarise them. tensile strength. They have high densities.
(xi) A number of elements of p-block series show the phe-
(ii) The ionisation energies of most of d-block elements lie
nomenon of allotropy. Carbon, silicon, phosphorus, sulphur, in between those of sand p-block elements. They are less
boron, germanium, tin, arsenic, etc., show this property. electropositive than s-block elements and more electro-
(xii) Catenation property is shown by many elements of positive than p-block elements. The members of 5d series
p-block series such as carbon, silicon, germanium, nitrogen, such as Pt, Au, Hg, etc., are inert under ordinary conditions.
oxygen, sulphur, etc. They are called noble metals.
(iii) d-block elements show variable valency. However,
• (iii) d-Block Elements (Transition Elements) members of TIB group (Zn, Cd and Hg) do not show variable
valency.
The d-block elements are also called transition metals. In (iv) Most of the compounds formed byd-block elements
these elements, the last electron enters (n - l)d-subshell (d- are coloured in the solid state or in solution.
orbitals of the penultimate orbit), i.e., (n -1) d-subshell is (v) Paramagnetism is common in d-block elements. This
gradually filled up. The configuration varies from (n - 1)i is due to the presence of unpaired electrons in (n -1)d orbitals.
ns2 to (n _1)d 10 ns2. At certain places, the configurations are (vi) Most of the transition elements and their compounds
different than expected. The general configuration of these act as good catalysts.
(vii) They have high tendency to form complex
elements can be represented as (n - 1)d 1-10 nsO or 1 or 2, The
compounds.
elements of IIIB, NB, VB, VIB, VIIB, VIII, IB and lIB belong to (viii) They have high tendency to form alloys with other
this block. These elements are also called transition elements metals.
as their properties are· intermediate between s- an<;l p-block (ix) They form both ionic and covalent compounds.
elements. Transition elements must have incomplete
penultimate d-subshell, either in the neutral atom or in any • (iv) f-Block Elements (Inner-Transition Elements)
one of its stable oxidation states. All the transition elements In these elements the last electron enters the (n - 2)f
are metals. These elements are classified into four series, i.e., energy shell [I-orbitals of the (n - 2) main she1l], i.e., (n - 2) f
3d, 4d,5d and 6d series corresponding to the filling of orbitals subshell is gradually filled up. The configuration varies
3d-series Configuration 4d-series Configuration 5d-series Configuration 6d-series Configuration

1. Sc (21) [Ar] 3d 1 4i Y (39) [Kr] 4d 1Si La (S7) [Xe] Sd 16s 2 Ac (89) [Rn] 6d 17i
2. Ti (22) [Ar] 3d 24i Zr (40) [Kr] 4d 2Si Hf (72) [Xe] 4f14 Sd 26s 2 Rf (104) [Rn] Sf 146d27i
3. V (23) [Ar] 3d 34i *Nb (41) [Kr] 4d 3Si Ta (73) [Xe] 4f14Sd36i Db (10S) [Rn] Sf 14 6d 37i
or
[Kr] 4d 4Ss 1
4. *Cr (24) [Ar]3d 44i *Mo (42) [Kr] 4d 4Si W (74) [Xe] 4f14Sd46i Unh (106) [Rn] Sf 146d47i
or or (Sg)
[Ar] 3,-i.:"4s 1 [Kr] 4d 5Ss 1
[Ar] 3d 54i
~K'l 4d's,' [Xe] 4f 14 Sd 56 i [Rn] Sf 14 6d 57s 2
0., 0., 0., 0.,
5. Mn (2S) ;::l Tc (43) ;::l Re (7S) ;::l Uns (107) ;::l
"0 "0 "0 "0
or (Bh)
~
~
~ ;::::I ~
!.::i !.::i [Kr] 4d 6Ss 1 !.::i !.::i
>. >. >. >.
6. Fe (26) ~;::l [Ar] 3d 6 4i *Ru(44) ~ [Kr] 4d 6 si as (76) ~ [Xe] 4f 14 Sd 6 6 i Uno (108) ~ [~] Sf 14 6d 67i
.g
~
;::l
"0 "0
...
CIS CIS or ...
CIS (Hs)
OIl 5"JJ
[Kr] 4d 7Ss 1 OIl 6h
.~ .~ .~ .~
~ ~ ~ ~
7. Co (27) <'l [Ar]3d 74i *Rh (4S) "<t [Kr] 4d 7 Si Ir (77) It") [Xe] 4f 14Sd76i Une (109) \0 [Rn] Sf 146d77s2
or (Mt)
[Kr] 4d 8Ss 1
8. Ni (28) [Ar]3d 84i *Pd (46) [Kr] 4d 8Si *Pt (78) [Xe] 4f 14Sd86s2 Uun (110) [Rn] Sf 146d87s2
or or (Ds)
[Kr] 4d lO SsO [Xe] 4f 14Sd9 6s 1
9. *Cu (29) [Ar] 3d 94i *Ag (47) [Kr] 4d 9Si *Au (79) [Xe]4f 14 S d9 6i Uuu (111) [Rn] Sf 14 6d 97i
or or or (Rg) or
[Ar] 3d10 4s 1 [Kr] 4dlO Ss 1 [Xe] 4f 14Sd106s1 [Rn] Sf14611107s
10. Zn (30) [Ar] 3d104i Cd (48) [Kr] 4d 1Osi Hg (80) [Xe] 4f 14Sd106i Uub (112) [Rn]Sf 146d107i
Fig. 1.6 d-block elements

from (n - 2)f 1 (n - 1)d 1 ns 2 to (n - 2)f 14 (n - 1)d 1 ns 2 . At General Characteristics of '-Block Elements
some places the actual configurations are somewhat The characteristics of f-block elements are similar' to transi-
different than the expected configurations. Thus, the tion metals, i.e., d-block elements. The important charac-
general Lonfiguration can be represented as (n - 2)f O-14, teristics are given below:
(i) All are metals.
(n - l)do, 1 or 2 ns2 . All f-block elements belong to 3rd group. (ii) They show variable valency. +3 is the most important
The f-block elements are of two types: oxidation state. Few elements show +2 and +4 oxidation states.
(a) 4f-series (Lanthanides): This series has 14 elements (iii)· They are paramagnetic in nature.
from Ce (58) to Lu (71). In these elements 4f-energy shell is (iv) They form coloured compounds.
gradually filled up. (v) They have tendency to form complexes.
(b) 5f-series (Actinides) : This series also has 14 (vi) Chemically lanthanides are very similar. It is difficult
elements from Th (90) to Lr (103). In these elements Sf-energy to separate them from a mixture by application of a chemical
shell is gradually filled up. These elements are also called property. The members of the actinide series are also similar
inner transition elements. All the elements are acco- in chemical properties.
mmodated in 3rd group but separately written in two (vii) The members of actinide series are radioactive in
horizontal rows below periodic table. nature. Elements above atomic number 92 are not found in
nature. These are man-made elements. These are called
4f- Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu transuranic elements.
elements 58 59 60 61 62 63 64 65 66 67 68 69 70 71
5f- Th Pa U Np Pu Am em Bk Cf Es Fm Md No Lr 1.7r~ EXTENDED OR LONG FORM
elements 90 91 92 93 94 95 96 97 98 99 100 101 102 103 c"" OF PERIODIC TABLE
Note: Lanthanum (57La) and actinium (89Ac) ate d-block In order to remove the defects of Mendeleev's periodic table,
elements. They are very similar in properties with a number of tables have been presented for the classification
lanthanides and actinides respectively and are usually of elements. The best table out of these is the extended or long
studied along with them.
form of periodic table which has been shown in Fig. 1.7.
Periodic Table of the Elements (Long Form)
s-Block
.....--------
Elements
....... _.- - - - - - p-Block Elements - - - - - -_
-
Group
r:II!!I_~1fGi1
New Notation - - - - - - - - - - - - - - - - - - - - : 1...17
.......- - - - - - - - - - - - - - - - - - - - - CAS Version - - - - - - - - - - - - - - - - -.......Y
r-~~--::--r;;;]
18
Atomic
number
Symbol
Name
Not found in nature []] Atomic
mass
- - - - - - - - - - - - - - d-Block Elements (Transition Metals) - - - - - - - - - - - - - -
8 10
Key
Metals
o Metalloids
Nonmetals
Fig. 1.7 A Modern form of the Periodic Table

fI!Iote : (1) The new IUPAC format numbers the group from 1 to 18. The previous IUPAC numbering system and the system used by Chemical Abstracts Service (CAS) are also shown. For radioactive elements that
do not occur in nature, the mass number ofthe most stable isotope is given in brackets with the longest half-life.
(2) The symbols for elements 104-111 used in this table are those proposed by the American Chemical Society and 112-118 proposed by IUPAC.
(3) There is no general agreement on the metallOids. Almost every list includes 5i, Ge, As, Sb and Te but some also include B, At and Po in the list.
The credit for this table cannot be given to any single 4f-~rbitals, the energies of 4d and 4f orbitals are higher than
person but it incorporates the modifications suggested by Ss orbital. Thus, 4s and 4p-orbitals are filled. However in
many scientists, especially Rang, Werner, Bohr, Bury, etc. between 4s and 4p-orbitals, five 3d-orbitals are also filled as
The table is most widely used these days and is also referred their energies lie in between those orbitals. Hence, nine
to as Bohr's table, since it follows the Bohr scheme of the orbitals, one 4s, five 3d and three 4p-orbitals are filled. The
arrangement of elements into four types based on electronic fourth period contains18 elements from potassium (4s 1) to
configuration of the elements. This table is just a graphical krypton (3a1°4i4p6). This period, therefore, includes first
representation of the aufbau principle.
d-block series from scandium (Z = 21, 3a14i) to Zinc (Z =
• Structural Features of the Long Form 30, 3a1°4i). Two s-block elements, ten d-block elements and
of the Periodic Table six p-block elements are present.
5th period: Like fourth period, it also accommodates 18
Like Mendeleev's periodic table, the long form of the
elements as nine orbitals, one Ss, five 4d and three Sp orbitals
periodic table consists of horizontal rows called periods and
vertical columns called groups. These are described below: are filled. It includes elements from rubidium (Ssl) to xenon
(4d lO SiSp6). This period, therefore, contains second d-block
PERIODS: series from yttrium (Z = 39, 4d lOSi) to cadmium (Z = 48,
Periods are numbered as 1,2,3,4, S, 6, and 7 from top to 4a1°Si). Two s-block, ten d-block and six p-block elements
bottom. The period number corresponds to the value of are present in this period.
n, i.e., principal quantum number for the outermost or valence 6th period: The 6s, 4f, Sd and bp-orbitals (i.e., sixteen
shell of the atoms of the elements belonging to that period. orbitals) are filled accommodating 32 elements from caesium
Number of elements in each period is twice of the atomic (6s 1) to radon (4l 4Sd 10 6i6p6 ). This period includes third
orbitals available in the energy level that are being filled. d-block series from lanthanum (Z = S7, sa16i-Here aufbau
1st Period: In the first period, the first main energy shell
principle is violated) to mercury (4f14Sd106i). The filling of
(K shell i.e., n = 1) is filled. As it has only one orbital which
can accommodate only two electrons, i.e., only two elements 4f-orbitals begins from cerium (Z = S8, 4f1 sa16i) and ends
are present. The first period consists of hydrogen (1s1) and up at lutetium (Z = 71, 4f14 Sd 1 6i). These fourteen elements
helium (1s 2). '. constitute 4f-series (Lanthanides). As the period can
2nd Period: In the second period, the second energy accommodate to the maximum of 18 elements, these 14
shell (L-shell i.e., n = 2) is completed. This energy shell has elements of 4f-series are separately placed in a horizontal
four orbitals, one 2s and three 2p orbitals, which can row below the periodic table.
accommodate eight electrons and therefore, second period 7th period: Like sixth period, seventh period is also
has eight elements from Li (2s1) to Ne (2i2p6). expected to accommodate 32 elements corresponding to
3rd period: This period corresponds to the filling of filling of sixteen orbitals, i.e., one 7s, seven Sf, five 6d and
third energy shell, i.e., n = 3. There are nine orbitals, one 3s, three 7p orbitals. However, at present this period is
three 3p and five 3d-orbitals in this shell. However, on the incomplete consisting 31 elements. One element of p-block
basis of aufbau principle, the 3d orbitals are higher in energy bearing atomic numbers 117 is to be discovered to complete
than 4s orbital. Thus, 3d orbitals are filled after filling of 4s this period. The period includes two s-block elements,
orbital. Hence, only four orbitals, one 3s and three 3p orbitals lOd-block elements, 14f-block elements and five p-block
are filled in this period. Consequently, this period, contains elements at present. 14 members of Sf-series (actinides) are
8 elements from Na (3s 1) to Ar (3i3p 6). also separately accommodated in a horizontal row below the
4th period: The fourth period corresponds to the filling periodic table like 4f-series.
of fourth energy shell, i.e., n = 4. Out of 4s, 4p, 4d and The number of elements and the corresponding orbitals
being filled are given in the following table:
Energy level Orbitals being First Last Total number of electrons or
Period
being filled filled member member elements in the period
n =1 Is H (Z = 1) He (Z = 2) 2 =2
2 n =2 2s 2p Li (Z = 3) Ne (Z = 10) 2 + 6 =8
3 n=3 3s 3p Na (Z = 11) AT (Z = 18) 2 + 6 =8
4 n =4 4s 3d 4p K (Z = 19) Kr (Z = 36) 2 + 10 + 6 = 18
5 n =5 5s 4d 5p Rb (Z = 37) Xe (Z = 54) 2 + 10 + 6 = 18
6 n=6 6s 4f 5d 6p Cs (Z = 55) Rn (Z = 86) 2 + 14 + 10 + 6 = 32
7 n=7 7s Sf 6d 7p Fr (Z = 87) Duo (Z = 118)* 2 + 14 + 10+ 6 = 32*
At present 31 elements are known. Element with atomic numbers 117 is yet to be discovered.
They are p-block elements and their number is quite low. Six (iii) The completion of each period is more logical. In a
of the nonmetals carbon, boron, phosphorus, sulphur, period as the atomic number increases, the energy shells are
selenium and iodine are solids. Bromine is the only liquid gradually filled up until an inert gas configuration is
nonmetal at room temperature. The remaining nonmetals-- reached. It eliminates the even and odd series of IV, V and
nitrogen, oxygen, fluorine, chlorine, hydrogen and noble VI periods of Mendeleev's periodic table.
gases are gas~s. Nonmetals are generally (i) brittle (i~) The position of VIII group is appropriate in this table.
(ii) nonlust!))Us'(iii) have low melting and boiling points All the transition elements have been brought in the middle
(carbona'hd boron are exceptions) (iv) nonconductors of as the prop~rties of transition elements are intermediate
heat (v) capable of forming acidic oxides (vi) do not evolve' between s- and p-block elements.
hydrogen from acids. (v) Due to separation' of two subgroups, dissimilar
elements do not fall together. One vertical column acco-
o Reactive Metals 0 Metalloids
mmodates elements with same electronic configuration
o Transition Metals 0 Nonmetals 17 18
thereby showing same properties.
2 . 0 Inner-Transition Metals 13 14 15 16
o Poor Metals (vi) In this table a complete separation between metals and
nonmetals has been achieved. The'nonmetals are present in
upper right comer of the periodic table.
(vii) There is a gradual change in properties of theele-
ments with increase in their atomic numbers, i.e., periodicity
of properties can be easily visualised. The same properties
of recurrence in properties occur after the intervals of 2, 8, 8,
18, 18 and 32 elements which indicates the capacity' of
Reactive
Metalloids
various periods of the table.
Metals
*r-,-,-,-,-,--,-,-,-,-,-,,-.-.-. (viii) This arrangement of elements is easy to remember
4{ and reproduce.
Iriner-Transition Metals -+-+-+-t--1f--i
** 5f
• Defects of Long Form of Periodic Table
Fig. 1.10 Blocks of elements representing similar
The long form of periodic table has following defects:
properties in the periodic table
(i) Position of hydrogen: The position of hydrogen is
Metalloids : not fixed in this table also. It is placed either in IA or in VIlA
There are some elements which do not fit completely into· group.
. (ii) Position of lanthanides and actinides : No
either metal or nonmetal class. Elements which have mixed
properties of metals and nonmetals both are called semi- individual places have been assigned to these 28 elements
metals or metalloids. Silicon, germanium, arsenic, antimony in the periodic table.
(iii) This table does not reflect the exact distribution of
and tellurium are metalloids. But some scientists include
boron, polonium and astatine also in the list of metalloids. electrons among all. the orbitals of the atoms of all the
In most respects, metalloids behave as non-metals, both elements.
chemically and physically. However, in their most important
physical property, the electrical conductivity, they somewhat t.it POSITION OF AN ELEMENT ON THE
resemble metals. Metalloids tend to be semiconductors; they " BASIS OF ELECTRONIC CONFIGURATION
conduct electricity, but not nearly so well as metals. This The block, period and group of an element can be easily
property, particularly found in silicon and germanium, is decided from its electronic configuration of the element
responsible for the remarkable progress made during the last (Fig. 1.4).
fifty years in the field of solid-state electronics. The operations
(i) The block of the element is decided on the basis of the
of every computer, audio system, TV receiver, DVD or CD
type of the orbital on which the last electron is acco-
player relies on transistors made from semiconductors.
mmodated. If the last electron enters into s-subshell or
In periodic table, the metallic character increases from
top to bottom in a group while metallic character decreases p-subshell or d-subshell or f-subshell, then the element
from left to right along a period. belongs to s-block or p-block or d-block or /-block respectively.
(ii) The period to which an element belongs depends on
• Superiority of the Long Form of the Table the total number of orbits (shells) on which electrons are
over Mendeleev's Periodic Table present.
(i) This table is based on a more fundamental property, or
i.e., atomic number. The serial number of the period corresponds to the
(ii) It correlates the position of the element with its principal quantum number (p.q.no.) of the outermost shell
electronic configuration more dearly. on which the electrons are present.
CI 17 2,8,7 !Nel belongs to enthalpy, valency, screening effect, effective nuclear charge
Three orbits p.q.no. 3 3rd period and electronegativity are the properties of individual atoms
Pb 82 2, 8, 18, 32, 18, 4, [Xel 4f145d lO6s26p2 belongs to . and 9.irectly dependent on their electronic configurations.
Six orbits p.q.no. 6 6th period (ii) Properties of group of atoms: Properties such as
melting point, boiling point, heat of fusion, heat of vapo-
(iii) To decide about the group number (IUPAC), the rization, density, atomic volume, etc., are the properties of
number of electrons present on the outermost shell or / and group of atoms together and are indirectly related to their
penultimate shell [next to the outermost, i.e., (n - 1) shell] are electronic configurations.
counted. All these properties which are directly or indirectly
(a) If the last orbit contains 1 or 2 electrons, the group dependent on the electronic configuration of the elements
number is 1 or 2 respectively (Helium is an exception which are called atomic properties.
belongs to group 18). There should not be any d-orbital in Since electronic configurations of the elements are periodic
the penultimate shell, i.e., in the penultimate shell either 2 function of atomic numbers of the elements, therefore, these
electrons [(n -l)i] or 8 electrons [(n l)ip6 ] electrons are a
atomic properties are also periodic function of atomic
present. numbers of the elements. On account of this, atomic properties
ns1 ---') 1st group ns2 ---') 2nd group are also called periodic properties.
K 19 2,8,8, III [Arl 481 Group 1 • Periodicity in Properties
Sr 38 2,8, 18,8, [KrISi Group 2
The rigid meaning of the word periodic is that a particular
Be 4 2, ~ [He] 152 Group 2 property is repeated in a system at regular intervals. The term
Li 3 2, OJ •
[Hel 151 Group 1 periodicity in properties in the classification of elements
means that same properties of the elements reappear at
(b) If the last orbit has 3 or more electrons, then the group definite intervals when the elements are arrangt-'! in the
number is the sum of electrons in the last orbit plus 10. Such order of their increasing atomic numbers. In modern periodic
an element belongs to p-block. table, these intervals are 2, 8, 8, '18, 18 and 32, i.e., similar
S 16 2,8,6 [Nel 3h p4 6 + 10 = 16 properties are observed with elements belonging to the same
i.e., 16th group subgroup which have been arranged in subgroups after the
Ge 32 2,8,18,4 [Arl 3i°4s24p2 4 + 10 = 14 difference of either 2 or 8 or 18 or 32 in atomic numbers as
i.e., 14th group similar valency-shell electronic configurations recur after
Xe 54 2,8, 18,18, 8 [Kr] 4dlOSS?Sp6 10 + 8= 18 certain regular intervals of atomic number. This is the cause
i.e., 18th group of periodicity in properties.
At 85 2,8, 18,32, 18, 7 [Xe] 4P45dl06s26p5 10 + 7:= 17 The real meaning of the word periodic in any classifi-
i.e., 17th group cation of elements is that when the elements are arranged in
(c) If the last orbit contains 1 or 2 electrons and order of their increasing atomic numbers in the same period
(n l)d-orbitals where electrons are present, then group or a group, there is gradual change (i.e., increase or decrease)
number is equal to the sum of electrons in the last orbit and in a particular property. In a period, the gradual change is
(n - l)d-orbitals. Such an element belongs to d-block.
due to the gradual change of electronic configuration from
member to member. Some of the properties which depend on
Cr 24 2,8,8 +S,1 [Ar] 3d 54s1 5 + 1 6 electronic configuration of elements such as screening effect,
i.e., 6th group effective atomic number, atomic radii, ionic radii, ionisation
Cu 29 2,8,8 +10,1 [Ar] 3d104s1 10 + 1 11 potential, electron affinity, electronegativity, etc., follow the
i.e., 11th group
general trend of periodicity.
Ru 44 2,8, 18, 8 + 7, 1 [Krl 4d7Si 7 + 1 8
In a group, the chemical properties of the elements remain
i.e., 8th group
nearly the same due to same valence shell configuration.
Hf72 2,8, 18, 32, 8 + 2,2 [Xel 4l4Sd26s2 2 + 2 4
There is gradual change in physical properties due to
i.e., 4th group
gradual change in the size of atoms due to start of new energy
1 ATOMIC PROPERTIES OR PERIODIC shell.
We shall discuss now the periodicity or periodic trends
PROPERTIES OF ELEMENTS
in some of the properties such as screening effect, effective
The physical properties of the elements can be divided into nuclear charge, atomic and ionic radii, ionisation enthalpy,
two categories : electron gain enthalpy, electronegativity, etc. We shall restrict
(i) Properties of individual atoms: Properties such as our study especially in the case of s- and p-block (i.e., normal
atomic and ionic radii t ionisation enthalpy, electron gain or representative) elements.
1.1 o~l THE SCREENING EFFECT OR B 2, 3 :::: 2 x 0.35 +2 x O.~ = 2.40

No, SHIELDING EFFECT C 2, 4 = 3 x 0.35 +2 x 0.85 2.75
N 2,5 4 x 0.35 +2 x 0.85 = 3.10
In a multielectron atom, the electrons of the valency shell
(outermost shell) are attracted towards the nucleus and also
o 2, 6 :::: 5 x 0.35 +2 x 0.85 = 3.45
these electrons are repelled by the electrons present in the F 2, 7 6 x 0.35 +2 x 0.85 =: 3.80
'j inner shells. On account of this, the actual force of attraction Ne 2, 8 = 7 x 0.35 +2 x 0.85 ::: 4.15
\ ,
between the nucleus and the valency electrons is somewhat Example 3. Calculation of screening constants in zinc (a)
decreased by the repulsive forces acting in opposite for a 4s-electron (b) for a 3d-electron.
direction. This decrease in the force of attraction exerted (a) The electronic configuratlol1 of zinc (30) is,
by the nucleus on the valency electrons due to the presence
Os)2 (25 2p)8 (3s 3p)8 (3d)10?<ld
. of electrons in the inner shells, is called screening effect or
shielding effect. The magnitude of the screening effect . a = 10 x 1.0 + 18 x 0.85 + 1 x 0.35 = 25.65
depends upon the number of inner electrons, i.e., higher the (b) For 3d-electron,
number of inner electrons, greater shall be the value of a =: 18 x 1.0 + 9 x 0.35 = 21.15
screening effect. The screening effect constant is represented It is clear from the examples (1) and (2) thatthe magnitude
by the symbol a. The magnitude of 'a' is determined by the of screening constant in the case .of s- and p-block elements
Slater's rules. The contribution of inner electrons to the increases in a period as well as in a group as the atomic
magnitude of 'a' is calculated in the following ways: number increases.
From the example (3), it is evident that the electrons in
• For ns or np Orbital Electrons different orbitals are differently affected by the same
(i) Write the electronic configuration of the element in the nuclear charge depending upon their proximity to the
following order and group them as, nucleus.
(1s), (2s 2p), (3s 3p), (3d), (4s 4p), (4d 4f), (5s 5p), .,~
(5d Sf), (6s 6p), etc, 1.11~1 EFFECTIVE NUCLEAR CHARGE

(ii) Electrons to the right of the (ns, np) group are not Due to screening effect the valency electron experiences less
effective in shielding the ns or np electrons and contribute attraction towards nucleus. This brings decrease in the
nothing to a. nuclear charge (Z) actually present on the nucleus. The
(iii) All other electrons in the (ns, np) group contribute to reduced nuclear charge is termed effective nuclear charge
the extent of 0.35 each to the screening constant (except for and is represented by Z*. Itis related to actual nuclear charge
Is for which the value is 0.30). (Z) by the following formula:
(iv) All the electrons in the (n 1)th shell contribute 0.85 Z * = (Z a), where a is screening constant.
each to the screening constant.
(v) All the electrons in the (n - 2)th shell or lower contri- It is observed that magnitude of effective nuclear charge
bute 1.0 each to the sCrt",ening constant. , increases in a period when we move from left to right.
IT period Li Be B C N 0 F Ne
• For cI- or '-electrons Z 3 4 5 6 7 8 9 10
cr 1.7 2.05 2.40 2.75 3.10,3.45 3.80 4.15
Rules (i) to (iii) remain the same but rules (iv) and (v) get Z* (Z - cr) 1.3 1.95 2.60 3.25 3.90 4.55 5.20 5.85
replaced by the rule (vi).
(vi) All the electrons in the groups lying left to (nd, nf) In a subgroup of nonnal elements the magnitude of
group contribute 1.0 each to the screening effect. . effective nuclear charge remains almost the same.
Alkali group Li Na K Rb Cs
Example 1. Calculation of screening constants of alkali Z 3 11 19 37 55
metals for valency electrons. cr 1.7 8.8 16.8 34.8 52.8
U ~1=2xQ~ = 1.7 Z* (Z cr) 1.3 2.2 2.2 2.2 2.2
Na 2, 8,....L.;;;;;...Sx 0.85 + 2 x 1 = 8.8 ITA group Be Mg Ca Sr Ba
K 2, 8, 8, 1 8 x 0.85 + 10 x 1 = 16.8 Z 4 12 20 38 56
cr 2.05 9.15 17.15 35.15 53.15
Rb 2, 8, 18, 8, 1 = 8 x 0.85 + 28 x 1 = 34.8 = (2 cr) 1.95 2.85 2.85 2.85 2.85
Cs 2, 8, 18, 18, 8, 1 8 x O.~ + 46 x 1 52.8
Example 2. Calculation of screening constants of members 1.1 ATOMIC RADIUS
of second period for valency electrons. An atom is assumed to be spherical in shape and, thus, the
U 2,1 =: 2 x O.~ :::: 1.7 size of atom is generally given in terms of radius of the
Be 2, 2 =: 0.35 + 2 x 0.85 :::: 2.05 sphere and is called atomic radius. It is usually defined as
the distance between the centre of the nucleus and outer- dCl--c1 1.98
:. Covalent radius of chlorine ---=-- 0.99 A
most shell where electron or electrons are present. The exact 2 2
measure of atomic radius is not easy due to following reasons: (c) Bond length (dc--c) in diamond is 1.54A.
(i) The atom does not have well defined boundary. The
probability of finding the electron is never zero even at large :. Covalent radius of carbon dc- c -_ 1.54 -- 0.77 A'
2
distances from the nucleus.
(d) Bond length (dSi--c) in carborundum is 1.93A.
(ii) It is not possible to get an isolated atom. The electron
•• dSi--c = fSi + fC
density around an' atom is affected by the presence of
or 1.93 = fSi + 0.77 C' rc = 0.77A)
neighbouring atoms, i.e., the size of the atom changes in
or rSi 1.93 - 0.77 = 1.16A
going from one set of environment to another.
(e) Bond length (dc--Cl) in CC4 is 1.76A.
(iii) The size of an atom is very small, of the order of about
o -10 •. dC--C1 = rc + fCI
1.2A, i.e., 1.2 x 10 m. or 1.76 = fC + 0.99 (.: fCI = o.99A)
An estimate of the size of the atom can,.however, be made or fC = 1.76 - 0.99 = 0.77A
by knowing the distance between the atoms in the combined Note : Elements may have. multiple bonds in compounds
state. The distance between the atoms, i.e., bond lengths are which are always shorter than single bonds.
generally measured by the application of techniques such as c-c C=C, c==c
1.54A' 1.33A 120 A
X-ray diffraction, electron diffraction, infrared spectroscopy,
The double and triple bond radii are calculated in the similar
nuclear magnetic resonance spectroscopy, etc. However, fashion as single covalent radius. 0
bond lengths change with different type of bonding. Three Double bond radius of carbon = 1.33/2 = 0.665A
types of radius are commonly used, i.e., (a) covalent radius Triple bond radius of carbon· 1.20/2 = 0.60A
(b) crystal radius (c) van der Waals' radius.
The double and triple bond radii of an atom are approxi-
(a) Covalent radius: Covalent radius is defined as half mately 0)17 and 0.78 times the single bond radius respectively.
of the distance between two nuclei of two like atoms (b) Crystal Radius: It is used for metal atoms which
bonded together by a single are a~~Llmed to be closely packed spheres in the metallic
covalent bond. Consider a homo- crystal, i.e., atoms are supposed to touch one another: It is
nuclear diatomic molecule A 2, defined as one half the distance between the nuclei of two
bonded together by single covalent adjacent metal atoms in the metallic closed packed crystal
bond. It is assumed that electron lattice in which the metal exhibits a coordination number
clouds of each atom touch each of 12. It is also called metallic radius.
other. Let the bond length be Fig. 1.11 For example, the distance between the two adjacent
dA- A · Then dA- A = fA + fA = 2rA· potassium atoms in solid potassium is 4.62A. 1perefore, the
dA-A metallic radius of potassium is 4.62/2 = 2.31 A.
So fA =-2-
.A metallic radius is always longer than covalent radius.
In a hetero-nuclear diatomic AB molecule if both atoms
are linked by a single covalent bond and have nearly same Metal Covalent radius (A) Crystal radius ~A)
electronegativity, the bond length dA - B is equal to sum of Sodium 1.54 1.86
covalent radius of the two atoms. Potassium 2.03 2.31
Copper 1.17 1.28
dA- B fA + fB Barium L98 2.22
Knowing the bond length and covalent radius of one of Aluminium 1.20 1.43
the atoms, the radius of the other atom can be determined. Atomic radius is expressed either in nanometre (1 nm = 10 9 m) or
Covalent radius is used for non-metals. in angstrom (1 A = 10-10 m) or in picometre (1 pm = 10-12 m).
[When there is large difference in the electronegativity of (C) van der Waals' radius: It is half of the distance
two elements A and B, the bond between A and B will have between the nuclei of two non-bonded neighbouring atoms
somewhat ionic character and the bond length dA- B will be of two adjacent molecules in solid state.
shorter than expected. In such cases, the following relation- r (covalent)
ship should be used : i+"-+j
dA - B = fA + fB 0.09(XA - XB) : I
X A and XB are the electronegativities of elements A and I

I
I I
I
I 'II I
8.]
.. --f..J+-~
For example, 0 I I I
I
(a) Bond length (d H- H) in hydrogen molecule is 0.74A. I
. d - 0.74 ,
:. Covalent radius of hydrogen = H H 0.37 A
(b) Bond length (dCl-d in chlorine molecule is 1.98A. r (van dar Waals')
Fig.1.12 Comparison of covalent and van der Waals' radius
The m~gnitude of the van der Waals' radius depends the periodicity in atomic radii (covalent radii) of repre-
upon the packing of molecules of the element in solid state. sentative elements. The radii are in angstroms.
For example, the distance between adjacent chlorine atoms
Period/Group--7 I II III IV V VI VII
of the two neighbouring molecules in solid state is 3.6A. t 1 H
Therefore, the van der Waals' radius of chlorine is 0.37
3.6/2 = 1.8 A. 2 Be
U B C N 0 F
van der Waals' radius of an elementis always larger than
1.23 0.89 0.80 0.77 0.75 0.73 0.72
its covalent radius. If)
A comparison of three types of radius shows that covalent 3 Na Mg Al Si P S CI <l>

!I)
<Ii
radius of an atom is shortest while van der Waals' radius is 1.54 1.36 1.20 1.17 1.10 1.04 0.99 <l>
....
u
the longest. 4 K Ca Ga Ge As Se Br ,Ei
van der Waals' radius> Crystal radius> Covalent radius 2.03 1.74 1.26 1.22 1.20 1.16 1.14
van der Waals' forces are weak, thus the distances 5 Rb Sr In Sn Sb Te
between the atoms held by these forces are much larger than 2.16 1.91 1.44 1.41 1.40 1.36 1.33 .
held by covalent bonding. A covalent bond is formed by
6 Cs Ba Tl Pb Bi Po
overlap of two half filled atomic orbitals, thus a part of the
2.35 1.98 1.48 1.47 1.46 1.46
electron cloud becomes common between two atoms. Due
to these reasons van der Waals' radius is always higher than Decreases
covalent radius. In case of a crystal, the valence electrons of
The atoms of zero group elements do not form chemical
the atoms are mobile, therefore, they are only weakly
bonds. Hence, their vander Waals' radii are considered
attracted. The metallic forces are thus weaker than covalent
which are always larger than covalent radii of halogens.
forces. On account of this, crystal (metallic) radius is larger
than 4j:ovalent radius. He Ne AT Kr Xe
[van der Waals' forces < Metallic forces < Covalent forces] van der Waals' radii (A) L20 1.60 1.91 2.00 2.20
Note ; For simplicity, we may use the term atomic radius for both
covalent or crystal (metallic) radius depending on whether the element is
The decrease in the size of transition elements is small
a non-metal or a metal. However, the atomic radii of inert gases are since the differentiating electrons enter into inner 'd' levels.
usually expressed in terms of van der Waals' radii as they do not form The additional electrons into (n - l)d levels effectively screen
chemical compounds. much of increased nuclear charge on the outer ns electrons
and therefore, size remains almost constant.
• Variation of Atomic Radii
Element Sc Ii V Cr Mn Fe Co. Ni Cu
(a) Variation in a Period: As we move from left to right
Atomic radius A 1.44 1.32 1.22 1.18 1.17 1.17 1.16 1.15 1.17
across a period, there is regular decrease in atomic radii of
(Covalent)
the representative elements. This is due to the fact that
number of energy shells remain the same in a period but However, in vertical columns of transition elements, there
nuclear charge increases gradually as the atomic number is an increase in size from first member to second member as
increases. This increases the force of attraction towards expected but from second member to third member, there is
nucleus which brings contraction in size. This can also be
explained on the basis of effective nuclear charge which
1.4
increases gradually in a period, i.e., electron cloud is attracted
1.3
more strongly towards nucleus as the effective nuclear charge
becomes more and more as we move in a period. The 1 1.2
increased force of attraction brings contraction in size. '$1.1
!!l 1.0
'd
A tOmIC ra 'lUS oc --1 (Zeff. Z )
(J '6
~ 0.9
Zeff. u
.~ 0.8
Zeff. = Effective nuclear charge; Z = Atomic number; F(0.72)
(J = Shielding effect < 0.7
2nd period u ~ B C N 0 F 0.6
Zeff. =0 (Z - cr) (3-1.7) (4-2.05) (5-2.40) (6-2.75) (7-3.1O) (8-3.45) (9-3.80)
1.3 = 1.95 2.60 =3.25 3.90 4.55 =5.20 Atomic number ( Z ) -
Atomic 1.23 0.89 0.80 0.77 0.75 0.73 0.72
radius (A) Fig. 1.13 Variation of atomic radii (covalent) in a period
(b) Variation in a Group: Atomic radii in a group
increase as the atomic number increases. The increase in very small change in size and sometimes sizes are same. This
size is due to extra energy shells which outWeigh the effect is dueto Lanthanide contraction (in the lanthanide elements
of increased nuclear charge. The following table illustrates
differentiating electrons enter into 4f levels. Since these

electrons do not effectively screen the valency electrons from 3.00
the increased nuclear charge, the size gradually decreases.
This decrease is termed lanthanide contraction). 2.50
Rb 1 8
i ~ \\ \ I
0« 2.00 ~
tJ)
,g 1.50 ~i \Na 1\ ,., Jl.J\\ I'
\ ~ I\.....
~ V ....1 V
J
u
1.00
\... F CI
I...... Br
0.50
10 20 30 40 50 60 70 80 90
. Atomic number - -
Atomic number ( Z ) -
Fig.1.15 Variation in atomic radii in periods
Fig.1.14 Variation of atomic radius (covalent) down a group (Metallic radii for metals and covalent radii for non-metals)
Element Ce Pr Nd Pm Sm Tb Lu
Atomic radius A 1.65 1.65 1.64 1.63 1.62 1.59 1.56
(Covalent)
The increase in size that arises due to period change in second and third transition series is almost compensated by the
lanthanide contraction.
1st Tr. series Se Ti V Cr Cu
At. radius A (Covalent) 1.4.4 1.32 1.22 1.17 1.17
2nd Tr. series Y Zr Nb Mo Ag
At. radius A (Covalent) 1.62 1.45 1.34 1.29 1.34
3rd Tr. series La Hf Ta W Au
At. radius" A (Covalent) 1.69 1.45 1.34 1.30 1.34
The follOWing table illustrates the metallic radii (Crystal radii) in angstroms:
Li Be
1.52 1.12
Na Mg Al Si P
1.86 1.60 1.43 1.32 1.28
K Ca Se Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As
2.31 1.97 1.64 1.47 1.35 1.29 1.37 1.26 1.25 1.25 1.28 1.37 1.23 1.37 1.39
Rb Sr Y Zr Nb Mo Te Ru Rh Pd Ag Cd In Sn . Sb
2.48 2.15 1.82 1.60 1.47 1.40 1.35 1.34 1.34 1.37 1.44" 1.52 1.67 1.62 1.59
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi
2.65 2.22 1.87 1.59 1.47 1.41 1.37 1.35 1.36 1.39 1.44 1.57 1.70 1.75 1.70
Conclusions (v) In 4f-series, there is continuous decrease in size with

increase in atomic number. This decrease is termed Lantha-
(i) The alkali metals which are present at the extreme left
nide contraction.
of the periodic table have the largest size in a period.
(vi) In a group of normal elements, there is continuous
(ii) The halogens which are present at the extreme right
increase in size with increase in atomic number.
of the periodic table have the smallest size.
(vii) In a group of transition elements, there is an increase
(iii) The sizes of the atoms of inert gases are, however,
in size from first member to second member as expected but
larger than those of preceding halogens because in inert gases
from second member to third member, there is very small
van der Waals' radii are taken into consideration.
change in size and sometimes sizes are same. This is due to
(iv) In transition series, the decrease in size is small as
Lanthanide contraction.
the additional electrons in (n l)d levels effectively screen
much of the nuclear charge on the ns electrons.
28 G.R. B. Inorganic Chemistry for Competitions
1.13~ IONIC RADIUS

~.:_w.
Comparative Sizes of Atoms and their Anions
Ionic radii are related to the ions present in ionic (crystalline) Atomic radii Corresponding Ionic radii
Atom
solids. Ions are formed when neutral atoms lose one or more (covalent, A) anions (A)
electrons or gain one or more electrons. A positive ion results F 0.72 F 1.36
when a neutral atom loses one or more electrons. A positive Cl 0.99 Cl- 1.81
ion is called cation. A negative ion is formed when a neutral Br 1.14 Br- 1.96
atom gains one or more electrons. The negative ion is termed 0 0.73 0 2- 1.40
anion. The effective size of these "ions is termed ionic radius. S2-
S 1.04 1.84
It is defined as the distance between the nucleus and N3-
N 0.75 1.71
outermost shell of an ion or it is the distance between the p3-
P 1.10 2.12
nucleus and the point where the nucleus exerts its influence
on the electron cloud. In· any particular group, the ions (cations or anions)
Like atomic radii, the accurate measurement of ionic radii increase in size on moving from top to bottom. This is due
is also not easy. However, the internuclear distance between to an increase in the number of shells. For example,
two oppositely charged ions in a crystal can be taken as the Li+ < Na+ < K+ < Rb+ < Cs+
sum of the radius of cation and radius of the anion by 0.59A 0.99A 1.33A 1.48A 1.69A
assuming spherical shapes of the ions and both are touching F < Cl- < Br- < r
each other. X-ray technique is used to measure the 1.36A 1.81A 1.96A 2.20A
internuclear distances. Knowing the radius of one ion, the
The size of the cations of the same element decreases with
radius of the other ion can be calculated.
For example, in NaCI crystal, the internuclear distance of the increase of positive charge. For example, Pb4+ is smaller
two ions is 2.76A.. The radius of Na+ ion is 0.9sA (Pauling in size than Pb 2+; Sn4+ is smaller in size than Sn2+; Fe3+ is
theoretical method). Therefore, the radius of Cl- ion is smaller in size than Fe2+.
2.76 - 0.95 = 1.81A.. Cu 2 + 0.72 Co3+ 0.64
0.67 A
0.82 A Cu+ 0.96 Co2+ 0.82
• Comparison of the Ionic Radii with
Corresponding Atomic Radii This can be explained on the basis of Z/ e ratio
(a) The radius of the cation is always smaller than the Nuclear charge)
( No. of electrons . Whenever Z/ e ratio increases, the size
atomic radius of its parent atom. This is due to the fact that
nuclear charge in the case of a cation is acting on a lesser decreases and when Z/ e ratio decreases, the size increases.
number of electrons and pulls them closer, i.e., effective Na Na+ Cl cr Fe2+ Fe3+
nuclear charge of a cation is always greater than the neutral 11 11 17 17 26
atom and thus, electron cloud contracts. Z/e IT = 1.0; 10 1.1;
17
1.0; 18 = 0.95; = 1.08; 23
1.13
(b) The radius of the anion is always larger than the So Na+ < Na cr> Cl Fe3+ < Fe2+
atomic ra4ius of its parent atom. In an anion as electron or Isoelectronic species (ions or atoms) are those which have
electrons are added to the neutral atom, the nuclear charge same number of electrons. For such species the size decreases
acts on more electrons so that each electron is held less tightly with an increase of atomic number. This is illustrated in the
and thereby the electron cloud expands, i.e., effective nuclear following table:
charge of an anion is always smaller than the neutral atom
and thus, electron cloud expands. Atomic No. of
Atom or Ion
numberZ electrons e
Zle ratio Size in A
Comparative Sizes of Atoms and their Cations
6 10 0.6 2.60
Atom Atomic radii Corresponding Ionic radii N3- 7 10 0.7 1.71
(crystal, A) cations (A)
0 2- 8 10 0.8 1.40
Li 1.52 Li+ 0.59 F 9 10 0.9 1.36
Na 1.86 Na+ 0.99 Ne 10 10 1.0 1.12
K 2.31 K+ . 1.33 Na+ 11 10 1.1 0.99
Mg 1.60 Mg2+ 0.65 Mg2+ 12 10 1.2 0.65
Ba 2.22 Ba 2+ 1.35
Al3 + 13 10 1.3 0.50
Al 1.43 AI3+ 0.50
Pb 1.75 Pb2+ 1.32
H+ and Cs+ are the smallest and largest cations respec- or
tively. Ionisation enthalpy is also called as ionisation potential
H- and r are the smallest and largest anions respectively. as it is the minimum potential difference in a discharge
Conclusions tube required to remove the most loosely bound electron
from an isolated gaseous atom to form gaseous cation.
(i) The radius of cation (positive ion) is always smaller
Ionisation enthalpy (or potential) is expressed either in
than that of the parent atom.
terms of electron volts per atom (eV I atom) or kilocalories
(ii) The radius of anion (negative ion) is always larger
per mole (kcal morl ) or kllojoules per mole (kJ mol-I).
than that of the parent atom.
1 electron volt (eV) per atom
(iii) The ionic radii in a particular group increase in
moving from top to bottom. = 3.83 x 10-20 cal per atom = 1.602 x 10-19 J per atom
(iv) In a set of species having the same number of electrons 3.83 x 10-20 x 6.023 x 1023 cal mor l
l
(isoelectronic), the size decreases as the charge on the = 23.06 kcal mor
nucleus increases. = 1.602 x 10- x 6.023 x 1023 J mol-l
19
(v) The size of the cations of the same element decreases 96.49 kJ morl
with the increase of positive charge.
:. 1 eV per atom = 23.06 kcal morl = 96.49 kJ mor1
1. IONISATION ENTHALPY OR Like the removal of first electron from isolated gaseous
atom, it is possible to remove second, third and successive
IONISATION POTENTIAL electrons from positive ions one after the other. The amounts
The electrons in an atom are attracted by the positive charge of energies required are termed second, third, fourth ...... .
present on the nucleus. To remove an electron from an atom, ionisation enthalpies respectively. These processes can be
energy has to be supplied to overcome the force of attraction shown as:
towards nucleus. A quantitative measure of the tendency of ~(g) + ,1#2 or IE2 =M2+(g) + e
an atom of an elementto lose electron is given by its ionisation M2+(g) + ,1#3 or 1E3 = M 3+(g) + e
enthalpy. It is defined as the minimum amount of energy
M 3+(g) + ~H4 or 1E4 M 4+(g) + e
required to remove most loosely bound electron from an
It is observed that ,1#2(1E2) has higher value than
isolated atom in the gaseous state of an element so as to
,1#l(1E l ). ,1#3 is higher than ,1#2 and so on, i.e.,
convert it into gaseous monovalent positive ion. It is also
known as first ionisation enthalpy or energy. The process ,1#1 < ,1#2< ,1#3 < ,1#4
can be represented as : The successive ionisation enthalpies of first ten elements
+energy are given in the following table:
M(g) ) M+(g)+e
Successive Ionisation Energies of the First Ten Elements (kJ/mol)**
Element Electronic First Second Third Fourth Fifth Sixth Seventh
H 1312
He Ii 2372 5250
Li 1l, 151 520
Be 152, 282 899 21,006
B 182, 2s22pl 801 2427 25,025 32,826
C Ii, 2i2p2 1086 2353 4620 6222 37,829
N 152, 2;2p3 1402 2857 4578 7475 9445 64,358
0 Ii, 2s22p4 1314 33/38 5300 7469 10,989 15,160
F Ii, 2s~p5 1681 3374 6020 8407 11,022 17,867
Ne 1l, 2s 22p6 2081 3952 6122 9370 12,177 15,238 19,998
**Ionisationenergies to the right of a vertical line correspond to .removal of electrons from the core of th., atom.
The increase in the values of successive ionisation increases. This requires higher energy to remove the electron
enthalpies can be explained on the basis that effective nuclear from the cation in comparison to neutral atom. The energy
charge increases from M(g) to Mn+(g), i.e., electrostatic increases as the charge on the cation increases gradually.
attraction between the nucleus and the remaining electrons Thus, successive ionisation enthalpies have higher values.
in the cation (especially the outermost electron in the cation)
*H represents enthalpy and AH, change in enthalpy. It is given positive sign if energy is required and negative sign if it is released.
an endoergic process and will be given a positive sign. From the table, the following trends are observed:
Similarly, higher electron gain enthalpies are positive. For (i) The electron gain enthalpies, in general, become less
example, when an electron is added to an oxygen atom to negative in going down from top to bottom in a group. This
form 0- ion, energy is released. However, when second is due to increase in size on moving down a group. This
electron is added to 0- ion to form 0 2- ion, energy is absorbed. factor is predominant in comparison to other factor, i.e.,
increase in nuclear charge.
O(g) + e~ O-(g); 1st AReg -141 kJ mol-1
(Energy released) Na > K > Rb > Cs
O-(g) + e ----7 02-(g); 2nd AReg == +780 kJ mol-1 . -53 -48 -47 -46kJ mOrl
(Energy absorbed) Cl Br I At
-349 -325 -295 -270 kJ morl
Similarly for sulphur atom, the second electron gain
enthalpy is positive. (ii) The electron gain enthalpies of oxygen and fluorine,
the members of the second period, have less negative values
S(g) + e ----7 S-(g) ; 1st AReg -200 kJ mol-1 than the elements sulphur and chlorine of the third period.
S-(g) + e ----7 S2-(g) ; 2nd AReg == +590 kJ mol-1 This is due to small size of the atoms of oxygen and
fluorine. As a result, there is a strong inter-electronic
The magnitude of electron affinity depends on a number
repulsion when extra electron is added to these atoms, i.e.,
of factors such as:
electron density is high and the addition of electron is not
(i) Siie of the atom: Smaller the size of the atom,
easy. Thus, the electron gain enthalpies of third period
stronger is the attraction for the added electron towards
elements, sulphur and chlorine, have more negative values
nucleus. Thus, smaller the size of atom, greater is the electron
than corresponding elements oxygen and fluorine.
affinity.
(il) Nuclear charge: Greater the nuclear charge, stronger o -141 kJ moI-1 F -328 kJ morI
is the attraction for the added electron towards nucleus. S -200 kJ moI-1 CI -349 kJ mor l
Thus, electron affinity increases as nuclear charge increases.
Similar trend is observed in nitrogen and phosphorus.
(iii) Electronic configuration: The elements having
stable configuration (half filled or fully filled valence N +31 kJ morl
subshells) have very little or no tendency to accept additional P -74 kJ mort
electron; hence, electron affinities are low or zero in thE;!se (iii) In general, electron gain enthalpy becomes more and
cases. more negative from left to right in a period. This is due to
decrease in size and increase in nuclear charge as the atomic
• Variation of Electron Gain number increases in a period. Both these factors favour the
Enthalpies in Periodic Table addition of an extra electron due to higher force of attraction
In general, the electron gain enthalpy becomes less by the nucleus for the incoming electron. .
negative in going from top to bottom in a group and more (iv) Electron gain enthalpies of some of the members of
negative in going from left to right in a period. However, alkaline earth metals, noble gases and nitrogen are positive.
electron gain enthalpy does not show a regular trend along This is because they have stable configurations. Alkaline
a period or a group. The electron gain enthalpies of normal earth metals have stable configurations due to completely
elements are given in the following table in kJ morl : filled ns orbital while nitrogen has extra stability due to half
filled p-orbitals oi, 2s 2 2p~ 2p~ 2p~), i.e., symmetrical
Period J, 1 2 13 14 15 16 17 18 configuration. These atoms resist the addition of extra
electron as they do not want to disturb their stability.
1 H He Noble gases have ninp6 configuration, i.e., no place for
-73 +48 incoming electron. In case the extra electron is to be
2 Li Be B C N 0 F Ne accommodated, it will occupy its position on a new principal
-60 +66 -83 -122 +31 -141 -328 +116 shell, i.e., it will be weakly attracted towards nucleus. Such
3 Na Mg Al Si P S CI Ar anion will be extremely unstable. Helium has also a stable
-53 +67 -50 -119 -74 -200 -349 +96 li configuration and cannot accommodate the incoming
4 K Ca Ga Ge As Se Br Kr electron.
-48 -36 -116 -77 -195 -325 +96 (v) Halogens have highest negative electron gain enthal-
5 Rb Sr In Sn Sb Te Xe pies. FollOWing two factors are responsible for this:
-47 -29 -120 -101 -190 -295 +77 (a) Small atomic size and high nuclear charge of halo-
6 Cs Ba TI Pb Bi Po At Rn gens in a period.
-46 -30 -101 -110 -174 -270 +68
(b) Halogens have the general electronic configuration. of isolated gaseous atom while electronegativity is concerned
ns'Lnp5, i.e., one electron less th<;m stable noble gas (nlnp6) with the atom in combination. Electronegativity concept
configuration. was introduced by Pauling in 1932. An arbitrary value of
Thus, halogens have a very strong tendency to accept an 4.0 has been assigned to fluorine (I)\ost electronegative
additional electron and their electron gain enthalpies are, element) and the electronegativitles of other elements have
therefore, high. been calculated against this standard by the application of
follOWing formula:
II Importance of Electron Gain Enthalpy 1 !
Certain properties of the elements can be predicted on the XA XB =0.208 [EA-B - 2(EA~A + EB-B)) 2
basis of values of electron gain enthalpies. where XA and XB are the electronegativities of two atomS A
(i) The elements having high negative values of electron and Band EA- B, EA- A and E8-B are bond energies of
gain enthalpy are capable of accepting electron easily. They molecules A - B, Az and Bz, respectively in kcal morl Or
form anions and thus form ionic (electrovalent) compounds. 1 !
These elements are electronegative in nature. X A - XB = 0.102 [E A- B - 2(EA-A + E8-B»)2, if the bond
(ii) The elements having high negative electron gain energies are taken in kJ morl.
enthalpies act as strong oxidising agents, for example, F, CI, Mulliken regarded electronegativity as" the average
Br,O, S, etc. value of ionisation potential and electron gain enthalpy of
On the basis of the general trend of ionisation enthalpy an atom when both are taken in electron volts.
and electron gain enthalpy, the following properties can be .. IP+EA
predicted: EleCtronegatiVlty = 2
(i) Metallic nature decreases in a period while non-
[IP Ionisation enthalpy; EA = Electron gain enthalpy]
metallic nature increases. Metallic nature increases in a group
while non-metallic nature decreases. The arrow (J,) represents However, it was found that Mulliken values were 2.8 times
a group and (~) represents a period. greater than Pauling values.
Metallic
Metallic
~, Decreases ; Non-metallic
(Electro +ve) ~, .
Increases
(Electro -ve)
+
Non-metallic
Increases
. Decreases
Thus, electronegativity in Pauling scale
IP+EA
2x2.8
IP+.EA
5.6
(ii) Stability of metal increases while activity of the metal Electronegativity of an atom on Pauling scale if the values
decreases in a period and in a group stability decreases . IP+EA
while activity increases. are taken in kcals per mole
2x2.8x23.06
Stability of the metal
Stability--L
of the metal ~'
Increases.;
Decreases
Activity of
the metal
-+
Activity of the metal
Increases
Decreases
Electroriegativity of an atom on Mulliken scale if the
. . -1 IP+EA
values of IP and EA are taken in kJ mol =2x96.48
Thus,electronegativity of an atom on Pauling scale

This trend is observed especially in IA, IIA and IllA IP+EA IP+EA
elements. =
2x96.48x2.8 540
(iii) The basic nature of the oxides decreases in a period
while acidic nature increases. In a group, basic nature On Allred and Rochow scale, the electronegativity is
increases while acidic nature decreases. calculated by applying the following formula,
Basic nature
of oxides
+
Basic nature of oxides
Increases
Acidic nature of oxides
,Decreases; Acidic nature
of oxides
--L~.
Increases
Decreases
X A =0.744+ 0.359 Z;ffective
r
where Zeffective = Effective nuclear charge at periphery
of elementA. .
1.t&! ELECTRONEGATIVITY r radius of the element A in A.
This is the property of a bonded atom. The relative tendency In general, the electronegativity values are high for
of an atom to attract the shared electron pair towards smallest elements and low for bigger atoms.
itself is called electronegativity. Electron gain enthalpy and The electronegativity values of representative elements on
electronegativity both measure the power of attracting the pauling scale are given in the follOWing table:
electrons but electron gain enthalpy is concerned with an'
1 2 13 14 15 16 17 electronegativity are non-metals. Fluorine with highest

Group -+ IA IIA lIlA IV A VA VIA VIlA electronegativity is the most non-metallic and caesium with
I period H lowest electronegativity is the most metallic element of the
2.1 periodic table.
IT period Li Be B C N 0 F (iii) (Xo - XA) difference predicts the nature of the oxides
1.0 1.5 2.0 2.5 3.0 3.5 4.0 formed by the element A. Xo is electronegativity of oxygen.
ill period Na Mg Al 5i P 5 Cl
Xo - XA is large, the oxide shows basic nature (e.g., Na20).
Xo - XA is small, the oxide shows acidic nature (e.g., S02)'
0.9 1.2 1.5 1.8 2.1 2.5 3.0
IV period K Ca Ga Ge As Se Br Difference·between Electron Gain Enthalpy
0.8 1.0 . 1.6 1.8 2.0 2.4 2.8 and Electronegativity
V period Rb 5r In 5n Sb Te I
<J) Electron Gain Enthalpy Electronegativity
0.8 1.0 1.7 1.8 1.9 2.01 2.5 0.>
<J)
VI perio<;! Cs Ba Tl Pb Bi Po At ...'u"
OJ 1. It is the tendency of an isolated It is the tendency of an atom in a
0.7 0.9 1.8 1.9 1.9 1.76 2.2 0.>
Q atom to attract electron. combined state, i.e., in a molecule
) Increases to attract· the shared .pair of
electrons.
In a period from left· to right, the value of electro- 2. It can be measured experi- It is a relative number and cannot
negativity increases while in a group from top to bottom, mentally. be determined experimentally.
the value of electronegativity decreases. 3. Its units are electron volts per It has no units but merely a
The electronegativity of any given element is not constant atom or kilojoules per mole or number.
but is dependent on the following factors: kilocalories per mole.
(i) State of hybridization: For example, in the case of 4. It is a constant quantity for a Electronegativity of an element is
carbon, electronega.tivity decreases from sp state to sp3 state. particular elerr.ent. not constant. It depends on a
number of factors such as hybri-
. sp > sp2 > sp3 dised state, oxidation state, etc.
electronegativity decreases 5. Its periodicity is not. regular in The periodicity is regular in a
(ii) Oxidation state of the element: With increase of a period or a group. period but not so regular in groups.
oxidation state, electronegativity increases. Fe3+ (EN 1.96)
has higher electronegativity than Fe2+ (EN 1.83). 1.11~ SOME OTHER PROPERTIES IN WHICH
.. PERIODICITY IS OBSERVED
"" Importance of Electronegativity
(i) Atomic volume: Atomic volume increases in a group
The following predictions can be made from values of from top to bottom. The increase is due to the increase in
electronegativity: the number of energy shells.
(i) Nature of the bond between two atoms can be predic- In a period from left to right, atomic volume varies
ted by the electronegativity difference of the two atoms. cyclically, i.e., it decreases at first for some elements, becomes
(a) When difference XA - XB = 0, i.e., X A = XB, the bond is minimum in the middle and then increases. The foUowing
purely covalent. For example, H 2, Cl2, O 2 and N2 molecules two factors explain this trend:
are purely covalent and non-polar. (a) Atomic radii decrease due to increase of nuclear
(b~ The difference XA - XB is small, i.e., XA > XB, the bond
charge.
is polar covalent. (b) The number ofvalency electrons increases in a period.
(c) The difference XA XB is 1.9, the bond is 50% covalent As to accommodate all the valency electrons, the volume
and 50% ionic.
increases. These two factors oppose each other. The effect of
(d) The difference XA - XB is very high, the bond is more
first factor is more on the left hand side and that of the seCond
ionic and less covalent. The molecule will be represented in factor is more on the right hand side.
such case as BA(B+A-).
Be B C N 0 F Ne
r
Percentage ionic character may be calculated as: 13 5 5 5 14 11 15 17
Percentage of ionic character
.
=16 (X A X B) + 3.5 (XA - XB)
where XA and XB represent electronegativity of bonded
2
Na
24
K
46
Mg
14
Ca
26
AI
10
Ga
12
5i
12
.Ge
13
P
17
As
16
5
16
5e
16
CI
19
Br
23
Ar
24
Kr
33
II
]
'" "
atoms A and B.
This relation was given by A.L. Allred (1961). The maximum value of atomic volume (87) is observed in
(iil,The elements having low values of electronegativity the case of francium (last member of alkali group).
(ii) Density: The density of the elements in solid state
are ~~~als while the elements having high values of
varies periodically with their atomic numbers. At first, the
density increases gradually in a period and becomes • Periodicity in Chemical Properties
maximum somewhere for the central members and then
starts decreasing afterwards gradually. (I) VALENCY
Li Be B C N 0 F The combining capacity of an element is termed the

0.5 1.8 2.3 2.2 valency. The valency of an element is linked with the number
Na Mg Al Si P S Cl of electrons present in the outermost energy shell of the atom.
1.0 1.7 2.7 2.3 1.8 2.1 The electrons present in the outermost shell are, therefore,
K . Se Br termed as Valence electrons.
0.9 4.8 3.1
In the case of representative elements, the valency is
Rb Te I
1.5 6.2 4.9 generally equal to either the number of valence electrons or
Cs equal to eight minus number of valence electrons. However,
1.9 the transition elements show variable valency involving
In solids, osmium has the highest density (22.6) and in valence electrons and 4 electrons of the penultimate
liquids, Hg has the highest density (13.6), energy shell. The common valence of transition metals are
(iii) Melting and boiling points: The melting points of either 2 or 3.
the elements exhibit some periodicity with rise of atomic Variation in a period: In the case of representative
number. It is observed that elements with low values of elements, the number of valence electrons increases from 1
atomic volumes have high melting points while elements to 8 from left to right in a period.
with high values of atomic volumes have low melting points.
Group 2 13 14 15 16 17 18
.In general, melting points of elements in any period at first
Number of 2 3 4 5 6 7 8
increase and become maximum somewhere in the centre .valence electrons
and thereafter begins to decrease. The melting points of the
Valence on 2 3 4 3 2 1 0
elements of second and third periods are given in the table:
hydrogen scale
Li & B C N 0 F ~
M.pt.(K) 454 1550 2303· 4000 63 54 53 24 Valence·on 1 2 3 4 5 6 7 0
scale
Na Mg Al Si P S CI Ar
M.pt.(K) 370.8 924 .933 1693 317 392 172 83.6 On hydrogen scale, the valency increases from 1 to 4
The boiling points of the elements also show similar and then decreases from 4 to 0, while on oxygen scale, it
trends, however, the regularities are not striking as noted increases from 1 to 7.
in the melting points. The boiling points of the elements of 1 2 13 14 15 16 17
third period are given below:
3rd period NaH MgHZ AlH3 SiH4 PH 3 HzS HCl
Na Mg Al Si P S Cl Ar
B.pt.(K) 1165 1396 2075 2815 557 717.6 238 87 1 2 3 4 3 2
•
In moving down the group, the melting and boiling points NazO MgO Al203 Si02 P20S S03 C12~
do show regular gradation, however, the pattern of variation 1 '2 3 4 5 6 7
is different in different groups. For example, in alkali group, .
Variation in a group: In a group, all the elements have
the melting and boiling points decrease in moving {rom top
same number of valence electrons and hence, all the elements
to bottom but among halogens, there is increase in moving
show same valency. For example, the elements of group 1
from top to bottom.
(alkali metals) show monovalency while the elements of
Element Li Na K Rb Cs group 2 (alkaline earth metals) show divalency.
M.pt.(K) 454 370.8 335 312 302
B.pt.(K) 1609 1165 1063 973 943
(II) NATURE OF OXIDES
Element F CI Bf I
M.pt.(K) 53 172 266 386 In a period, the nature of the oxides varies from basic to
B.pt.(K) 85 238 332 456 acidic as stated earlier.
Tungsten has the maximum melting point (3683K)
amongst metals and carbon has the highest melting point Strongly Basic Amphoteric Weakly Acidic Strongly Strongly
(4000K) amongst non-metals. Helium has the lowest melting basic acidic acidic acidic
point (3K). The metals Cs, Ga and Hg are known in liquid
In a group, basic nature increases or acidic nature
state at 303K
decreases. Oxides of the metals are generally basic and oxides
of the non-metals are acidic. The oxides of the metalloids are Chlorine forms a number of oxy-acids:
amphoteric. The oxides of Al, Zn, Sn, As and Sb are
HClO HCI0 2 HCI03 HCI04
amphoteric. We can summarise that as the electronegativity --------~---~) Strength increases
of element increases, acidic character of oxides increases. ------------~) Stability increases
When an element forms a number of oxides, the acidic ------------~ Oxidising nature
nature increases as the pe~centage of oxygen increases. decreases
N 20
NO
N,o,
NO z I':.~
Neutral
}i.
Neutral PPl
p,o,
PzOs
Ii
;ij
'0,5
~
l"
! ~
:g ,5~
,):I
I~ Mn20 3
MnOz
Mn03
Basic
Basic
Neutral
Acidic
G~eater is the oxidation state of central atom; more will be
the acidic strength.
(IV) NATURE OF HYDRIDES

(J~ ..:
NzOs :0
'0'
6 ..: Mn207 Acidi~
The nature of the hydrides changes from basic to acidic
..:
in a period from left to right.
CO, N 20, NO. and H20 are neutral oxides. The· oxides
NH3 H20 HF
COz, N 20s, P20s, P 20 S, S02, S03, Cl20 7, etc., are called Weak base Neutral Weak acid
acid anhydrides as these combine with water to form oxy-
PH3 H 2S HCI
acids. Very weak base Weak acid Strong acid
C02~H2C03 P203~H~03 Ina group, the acidic nature of the hydrides of non-metals
S03~H2S04 N20s~HN03 increases. The reducing nature also increases but stability
decreases from top to bottom.
P20s~H3P04 Cl2~~ HCl04
HF HCl HBr HI
N203~HNOz S02 --'-t H2S03 Strength of the acid increases
Stability decreases
(III) NATURE OF OXY-ACIDS
Reducing nature increases
In a period, the strength of the oxy-adds formed by non-
metals increases from left to right. (V) ANOMALOUS BEHAVIOUR OF THE
ELEMENTS OF SECOND PERIOD
II period H 3B03 ~2C03 HN0 3
-...,..-----Y------~) Strength increases It has been observed 'that in the case of representative
I
elements, the first element in each group, i.e., lithium in the
III period H2Si03 H3P$r H2S04 ~lffCI04 .
I- i i .1 ; : ! ) Strenph mcreases first group, beryllium in the second group and boron to
fluorine in the groups 13 to 17, differ in many respects from·
In a group, the E{tre,th\ of~halPrr1acids of!non-metals
decreases. i I
the other members of their respective groups. The anomalous
behaviour of the first member of each group is attributed to
HiAs04 following reasons:
) Strength decreases (a) small atomic radius of the atom and ionic radius of its
Vilgroup HCI04 HBr04 HI04 ion.
) Strength decreases (b) high electronegativity.
If a non-metal forms a number of oxy-acids, the strength (c) non-availability of d-orbitals in their valence shell.
increases with the increase of percentage of oxygen. (d) tendency to form multiple bonds by carbon, nitrogen
.and oxygen.
Sulphur forms two oxy~acids H 2S03 and H2S04.H2S04 is
. (e) high charge/radius ratio.
stronger acid than H 2S03.
The abnormal properties will be discussed in detail in
respective groups.
..
Problem 1. The diagram given below is a part of the (x) Alkali metals ,belong to firstgroup. Thus, elements
periodic table. Study the table and answer the questions that with atomic number 3, 11 and 19 are alkali metals.·
follow: (xi) The element-35 is a halogen, its valency is one and
the valency of element-20 (calcium) is two. Thus, one atom
2 2 of element-20 combines with two atoms of element-35.
He (xii) The atomic number of an inert gas is 36 (Kr).
3 4 5 6 7 8 9 10 Problem 2. Among the elements with atomic numbers
Be 0 9, 12 and 36, identify by atomic number of an element which is:
11 12 13 14 15 16 17 18 (a) highly electronegative
(b) an inert gaS
26H~
Si S
19 20 21 22 23 24 25 29 30 31 32 33 34 35 36 (c) highly electropositive and give reasons for your choice.
Solution:
Ca Cr Kr
The electronic configuration of the elements with atomic
(z) Name two elements in the same group of the periodic table. numbers 9, 12 and 36 are: -
(ii) Name a transition metal. Atomic number 9; 2, 7
(iii) Name an element whose oxide is basic. Atomic number 12; 2, 8, 2
(tv) Name an element whose oxide has a very low melting point. Atomicnumber 36; 2,8,18,8
(v) Name an element which reacts vigorously with water. The element with atomic number 9 can accept one more
(vi) Name an element which forms a colourless solid chloride electron to have 8 electrons in the outermost orbit, !l,us it is
XCI 21 where X = the element. an electronegative element.
(vii) Name the element which is gaseous at room temperature. The element with atomic number 12 loses two electrons
(viii) Name a metallic element which has a high melting point. to acquire inert gas configuration, thus it is electropositive
(ix) Name two elements which would react with each other to in nature.
form a single compound. The element with atomic number 36 has 8 electrons in the
(x) Give the atomic number of an element which is an alkali outermost orbit, hence it has no tendency either to lose or
metal. accept electrons. Thus, it is an inert gas.
(xi) How many atoms of element-35 can combine with an atom Problem 3. Two elements A and B have atomic number 16
of element-20? and 19, respectively.
(xii) Give the atomic number olan element which is inert. (i) Write down the electronic configurations of A and B in terms
Solution: of s, p, dand f.
(i) The elements' placed vertically one below another (ii) Which element belongs to s-block of modern periodic table?
belong to the same subgroup. Thus, Be and Ca belong to the (iii) Which-element belongs to p-block?
same subgroup. (iv) Which element is a powerful reducing agent?
(ti) First transition series starts fromelement-21 and ends (v) Write down the formula of compound formed between A and
at element-30. Thus, chromium-24 is a transition metal. B.
(iii) The oxides formed by the elements on left hand side Solution:
of the periodic table are basic. Thus, calcium forms basic (i)A= 1s2,2s22p6,3s23p4 (six electrons ill valency shell).
oxide. B = 1s2,2s 22p6,3s23p6,4s 1 (one electron in valency shell).
(iv) Sulphur forms a gaseous oxide whose melting point (ii) B belongs to s-block as the last electron is accommo-
is low. dated on ns.
(v) Alkali and alkaline earth metals react vigorously with (iii) A belongs to p-block as the last electron is accommo-
water. Thus, calcium reacts vigorously with water. dated on np.
(vi) Calcium belongs to second group. It shows divalency (iv) B has a tendency to lose valency electron easily, thus
and forms solid chloride of the type XCl 2. it acts as a powerful reducing agent.
(vii) Oxygen is known in gaseous state at room (v) The valency of B is 1 and that of A is 2. Thus, the
temperature. formula of the compound formed is B2A.
(viii) Transition metals have highmeltirig points. Thus, _Problem 4. An element A has an atomic number 11.
chromium possesses high melting point. (i) Represent its electronic configuration.
(ix) Be and oxygen react together to. form one oxide, BeO. (ii) To which group of periodic table does it belong?
(iii) What is its valency? The energy absorbed in (ii) step is more than. the energy
(iv) Write the formult; of its oxide. released in the (i) step. Hence, the formation of 0 2- from 0 is
Solution: endothermic in nature.
(i) Electronic configuration = Is2, 2s 2 2p6, 3s 1.
Problem 8. (a) Why chlorine has higher negative electron gain
(ii) As one electron is present in the outermost energy
enthalpy than F?
shell, it belongs to first group of the periodic table.
(b) Why N has higher 1st ionisation enthalpy than O-atom?
(iii) Its valency is 1.
(c) Why Mg has higher 1st ionisation enthalpy than
(iv) The formula of its oxide is A 20.
AI-atom?
Problem 5. Name the groups and periods of the elements Solution:
having atomic number 18 and 26. What are the possible valencies (a) The size of fluorine atom is small and thus electron
of the above elements? [M.L.N.R. 1990] density is high. This resists the addition of electron, hence
Solution: electron gain enthalpy of fluorine is less.
Electronic configurations of the elements are: (b) The electronic configurations of nitrogen and oxygen
(A) At. no. 18 2, 8, 8 3s2 3p6 are as follows:
(B) At. no. 26 2,8,8 + 6, 2 3d 6 , 4s 2 N : Is2, 2s2 2p; 2p~ 2p~
A belongs to third period and zero group.
B belongs to fourth period and eighth group.
o : Is2, 2s2 2p~ 2p~ 2P:
A is an inert gas, its valency is zero while B is a transition In N, p-orbitals are half filled and hence, its structure is
metal. It can show 'Variable valency. Its possible valencies are stable. It requires more energy to remove an electron. Hence,
2,3 and 6. the IE of nitrogen is higher than oxygen atom which has a
less stable structure.
Problem 6. The first ionisation energy of carbon atom is.
greater than that of boron atom, whereas reverse is true for the (c) The electronic configurations of Mg and AI are as
second ionisation energy. Explain. follows:
Solution: Mg : Is2, 2s2 2p6, 3s2
The electronic configtrrations of carbon and boron are as Al : Is2, 2s2 2p6, 3s2 3p1
follows: It is difficult to remove an electron from 3s in comparison
C : Is2, 2s2 2p; 2p~ ; B: Is2, 2s2 2p; to 3p (3s paired and 3p singly occupied). Hence, IE of Mg is
Due to higher nuclear charge in carbon, the force of higher than AI.
attraction towards valency electron is more in carbon atom Problem 9. The elements with atomic numbers 117 and 120
and hence the first ionisation energy is greater than boron are yet to be discovered. In which family/group would you place
atom. After loss of one electron, the monoval~nt cations have these elements when discovered? Give their expected electronic
the configurations as follows: configurations of the outermost shells and IUP AC names.
B+ : Is2, 2s2 ; C+: Is2, 2s2 2p} Solution:
The B+ configuration is a stable one and hence the removal Atomic Electronic
Name Symbol Group/family
of electron is difficult in comparison to C+. Hence, second number configuration
ionisation potential of boron is higher than carbon. 117 Ununseptium Uus 7s 27 p5 17/Halogen
2
Problem 7. The formation of F- (g) from F(g) is exothermic 120 Unbinilium Ubn 85 2nd/ Alkaline
whereas that of d-(g) from O(g) is endothermic. Explain. earth metals
Solution:
Problem 10. Which of the following species will have the
The addition of an electron to a neutral atom is an exoergic
largest and smallest size?
process. Mg, Mg2+, AI, A13+
F + e ---7 F- + energy Solution:
o + e ---7 0- + energy ... (i) Mg and AI, both belong to same period.
The addition of second electron to a monovalent anion
Mg Al
0-, as to make it d- is difficult because both have the same Atomic number 12 13
charge and experience a lot of repulsion. Thus, the addition Atomic size decreases from left to right across the period.
of an electron to 0- requires energy to overcome the force of Thus, Mg atom is larger in size than Al atom.
repulsion. . Cation is smaller than its neutral atom. Mi+
ion is smaller
a- + e + energy ---7 d- ...(ii) 3
than Mg atom and A1 + ion is smaller than AI atom. Thus,
Al3+ ion is smallest and Mg atom is largest in size among ponding to 32 elements. Upto the end of sixth period 86
the given species. elements have been accommodated. Thus, the present long
Problem 11. Arrange the following in order of increasing form of periodic table can accommodate 86 + 32 118
radii: elements.
(z) l,r,r (ii) C, N, Si, P (ii) Elements with atomic number higher than 100 having
(iii) (j2-, F-, Ne, Mg!-+ (iv) Fe, Fe2+, Fe3+ high densities are called superheavy elements.
(iii) The names and symbols of the elements with atomic
Solution:
(i) 1+ < 1<1-
numbers 126, 134 and 150 are:
Z Name Symbol
z/e 535353 z/e decreases, hence size increases. 126 Unbihexium Ubh
525354
(ii) N < C < P < 5i (a) Effective nuclear charge in 134 Untriquadium Utq
nitrogen is higher than in 150 Unpentnilium Upn
carbon, hence N « C. Problem 14. Which of the elements Na, Mg, Si and P would
(b) Effective nuclear charge in have the greatest difference between the first and second ionisation
phosphor.us is higher than in enthalpies? Explain.
silicon, hence P < 5i. Solution:
(c) C and 5i both belong to same Among these elements, sodium is an alkali metal and has
group. the electronic configuration, 1s2, 2S2 2p6, 3s1. Due to the
C 1s2, 2S22p2 (Two orbits) presence of only one electron ill the valence shell the first
5i 1s2, 2s22p6, 3s23~ (Three ionisation enthalpy is very low. After the removal of this
orbits) C < 5i electron, the Na+ ion has inert gas configuration, i.e., 1s2,2s2
(iii) Mi+ < Ne < F- < 0 2- 2p6. To remove the electron from this configuration, It cry high
energy is required. Therefore, the second ionisation enthalpy
z / e 12
10 10 9 10
10 10 8 z / e d ecreases, h "
ence SIze mcreases. is expected to be very high. Consequently, the difference
between first and second ionisation enthalpies would be
(iv) Fe3 + < Fe2+ < Fe greatest in sodium atom.
z/ e ~ ~: ~~ z/ e decreases, hence size increases. Problem 15. The ionisation enthalpy of lithium is 520
kJmol-1.Calculate the amount of energy required to convert 140
Problem 12. Give the formula of a species that will be
mg of lithium atoms in gaseous state into Li+ ion.
isoelectronic with the following atoms or ions:
Solution:
(l) Ar (ii) F- (ii!) K+ (iv) sy2+
Mass of lithium :::; 140 mg
Solution:
140 x 10-3 g
Isoelectronic species are those which have same number
of electrons.
= 14 x 10-2 g
(i) AI has 18 electrons. Therefore, the species p3-,
Cl-, K+, Ca2+, etc., are isoelectronic to Ar.
No. of moles of lithium :::; 14 x O-
2
i
(ii) F- has 10 electrons; Therefore, the species N3-, = 2 x 10-2 mole
(j2-, Ne, Na+, Mi+, etc., are isoelectroruc to F-.
Energy required to convert 2 x 10-2 mole atoms of lithium
(iii) K+ has 18 electrons. Therefore, the species p3-, 52-, CI-
into Li+ ions :::; 520 x 2 x 10-2 10.4 kJ
, Ar, Ca2+, etc., are isoelectronic to K+.
(Iv) 5r2+ has 36 electrons. Therefore, the species Br-, Kr, Problem 16. The amount of energy when million atoms of
iodine are completely converted into r ions in the vapour state
Rb+, etc., are isoelectronic to 5r2+.
according to the equation,
Problem 13. Answer the following: . leg) + e ---') leg) is 4,9 x 10-13 J.
(i) How many elements can be accommodated in the present set Calculate the electron gain enthalpy of iodine In terms of
up of the long form of periodi.c table? kJ mol-1 and eV per atom.
(ii) What are superheavy elements? Solution:
(iii) What would be lUPAC names and symbols with atomic The electron gain enthalpy of iodine is equal to the energy
numbers 126, 134 and ISO? ' released when 1 mole of iodine atoms in vapour state are
Solution: converted into I:" ions
(i) There are seven periods in the present long form of 13 23
periodic table. In the last period 7s, Sf, 6d and6p orbitals are :::; 4.9 x 10- x 6.023 x 10 29.5 x 10 4 J:::; 295 kJ
106
to be filled, i.e., it can accommodate 32 electrons corres-
Thus electron gain enthalpy of iodine = -295 kJmor1 is 3.0 in all nitrogen compounds is not correct as. electro-
We know that 1 eV per atom = 96.49 kJ mol-1 negativity of any atom is not a constant quantity. It varies
:. Electron gain enthalpy of iodine in eV per atom with state of hybridization and the oxidation state of the
295 . element.
=-96.49 3.06
Problem 21. Answer the following:
Problem 17. Assign the position of the element having outer (a) Why do elements in a group show similar chemical
electronic configuration properties? .
(i) ns2np4 for n = 3 ..
(b) Alkali metals have very high second ionisation enthalpy
(ii) (n - l)d2ns2 for n = 4
values. Why?
(ii1) (n - 2)f(n --:-)dJ:.ns2 for n = 6
Solution:
in the periodic table. (a) In a group, all the elements have same number of
Solution': electrons in the valence shell and the chemical properties
(i) The element belongs to 3rd period (n 3) and group 16
mainly depend on the valence electrons. Therefore, the
(10 + 2 + 4 = 16).
elements belonging to the same group show similar chemical
(ii) The element belongs to 4th period and group 4 (2 + 2
properties.
= 4).
(b) The general electronic configuration ofalkali metals is
(iii) The element belongs to 6th period and group 3. It is a
ns1. By losing this electron, they acquire the configuration of
member of lanthanide series and placed with lanthanum. the nearest noble gas element. It is a stable configuration and
Problem 18. The first and second ionisation enthalpies (k] to remove the electron from this configuration is difficult, i.e.,
mol-I) of three elements I, II and III are given below; requires a large amount of energy. Therefore, the second
I II III ionisation enthalpy values of alkali metals are high.
403 549 1142 Problem 22. In terms of period and group, where would you
2640 1060 2080 locate the element with 2 = 113? Give the IUPAC name and
Identify the element which is likely to be: symbol of the element.
(a) non-metal (b) an alkali metal Solution:
(c) an alkaline earth metal. The last member of 6th period is radon (2 = 86). In 7th
Solution: period, 7s, 5f, 6d and 7p subshells are filled. The maximum.
(a) Element (ill) is a non-metal because its ~H1 is highest capacity of these subshells is 2, 14, 10 and 6 respectively.
among the three. Atomic number difference with radon is = 113 - 86
(b) Element (I) is an alkali metal as its first ionisation =27
enthalpy is lowest and second ionisation enthalpy is very Thus, the electronic configuration of the element, Z = 113,
high. . is
(c) Element (II) is an alkaline earth metal because its first 7s2 5f14 6io 7p1
ionisation enthalpy is near to enthalpy of element (I) and It, therefore, belongs to 7th period and group 13 of the
second ionisation enthalpy is not very high. periodic table. Its !UPAC name is Ununtrium and symbol is
Problem 19.· How would you justify the presence of 18 Uut.
elements in the 5th period of the periodic table? Problem 23. What are the main factors due to which the
Solution: ionisation enthalpy of the main group elements tend to decrease
. Each period in the periodic table starts with the filling of
down the group?
a principal energy shell, i.e., 5th period begins with the filling
Solution:
of 5s-orbital. Each period is completed by filling of·
The ionisation enthalpy of the elements decreases down
np-orbitals, i.e., 5th period is completed when 5p-orbitals
the group due to follOwing two factors:
attain 6 electrons. Between 5s and 5p-orbitals, 4d-orbitals
(i) There is increase in the number of main energy shell
are also filled as their energies are higher than 5s and
in moving from element to element, i.e., atomic size
lower than 5p-orbitals. Therefore, in fifth period the electrons
increases gradually at each succeeding element, thereby the
can be filled only in 5s, 4d and 5p-orbitals, i.e., 9 orbitals
force of attraction of the nucleus towards valence electrons
are filled accommodating 18 electrons. Hence, 5th period
decreases.
has 18 elements.
(ii) There is increase in the magnitude of the screening
. Problem 20. How would you react to the statement that effect on account of increase in the inner electrons from one
electronegativity of N on Pauling scale is 3.0 in all the nitrogen member to another and thus, the force of attraction of the
compounds? nucleus towards valence electrons decreases and hence, the
. Solution: ionisation enthalpy decreases.
The statement that electronegativity of N on Pauling scale
'i SUMMARY AND IMPORTANT POINTS TO REMEMBER' 1

1. Mendeleev's periodic table was based on atomic masses of elements, i.e., 28 f-block elements are present in periodic
the elements. When Mendeleev presented the periodic table, table. The elements in first row are termed 4f-elernents or
only 63 elements were known. He left 29 places in the table rare earths or lanthanides while the elements of second row
for unknown elements. are termed 5f-elements or actinides.
2. Modern Mendeleev periodic table is based on atomic 5. The elements are broadly divided into three' types :
numbers of the elements. The modern periodic law is: (i) Metals comprise more than 78% of the known ele-
liThe physical and chemical properties of the elements are ments. s-block, d-block and f-blOCk elements are metals.
periodic function of their atomic numbers." The higher members of p-block are' also metals.
The horizontal row in the periodic table is called a period (ii) Non-metals are less than twenty. (C, N, P, 0, 5, Se, H,
and vertical column is called a group, There are seven P, Q, Br, I, He, Ne, Ar, Kr, Xe, Rn and Uuo are non-
periods and nine groups in the modern Mendeleev periodic metals)
table. (iii) Elements which lie in the border line between metals
3. The long or extended form of periodic table consists of and non-metals are called semimetals or metalloids. B,
seven periods and eighteen vertical columns (groups or Si,Ge, As, Sb, Te, Po and At are regarded metalloids.
families). The elements in a period have same number of 6. !UPAC has given a new scheme for assigning a temporary
energy shells, i.e., principal quantum number (n). These are name to theriewly discovered elements. The name is derived
nUmbered 1 to 7. . directly from the atomic number of the element. However,
1st· period Is orbital filled 2 elements !UPAC has accepted the following names of the elements
2nd period 2s2p orbitals filled 8 elements from atomic numbers 104 to no.
3rd· period 3s3p orbitals filled 8 elements Rutherfordium (Rf), Dubnium (Db), Seaborgium (Sg),
4th' period 4s3d4p orbitals filled 18 elements 104 105 106
5th period 5s4d5p orbitals filled 18 elements Bohrium (Bh), Hassium (Hs), Meitnerium (Mt),
6th period 6s4f5d6p orbitals filled 32 elements 107 108 109
Darmstadtium (Os)·
7th period 7s5f6d7p orbitals filled 32 elements
no
Total *U8 elements The temporary names of the elements discovered recently
At present 117 elements are known. are:
In a vertical column (group), the elements have similar Unununium (Uuu), Ununbium (Uub),
valence shell electronic configuration and therefore exhibit 111 112
similar chemical properties.
Ununtrium (UuO, Ununquadium (Uuq),
4. There are four blocks of elements : s-, p-, d- and I-blocks
depending on the orbital which gets the last electron. The 113 1.14
general electronic configuration of these blocks are: Ununpentium (Uup), Ununhexium (Uub),
s-block : [Noble gas]ns1 or 2. However, hydrogen has lSI
115 116
configuration.
Ununoctium (Uuo)
p-block : [Noble gas]ninpl-6
d-block : [Noble gas] (n _ 1)d1":IO ns1 or 2 118
I-block : [Noble gas] (n - 2)f1-14(n l)d o or Ins2 7. The recurrence of similar properties of the elements after
s-block elements occupy lA(t) and IIA(2) groups, i.e., extreme certain definite intervals when the elements are arranged
left portion of the periodic table. in the order of increasing atomic numbers in the periodic
p-block elements occupy llIA(t3), N A(t4), VA(t5), VIA(t6), table is termed periodicity. The cause of periodicity is the
VIlA(17) and VIIIA(18) groups, i.e., right portion of the repetition of similar electronic configuration of the atom
periodic .table. in the valence shell after certain definite intervals. These
d-block . elements occupy IIIB(3}, NB(4), VB(5), VlB(6), definite intervals are 2, 8, 8, 18, 18 and 32.
VllB(7), VlIIB(8,9 and 10), IDOl) and llB(t2) groups, i.e., Periodicity is observed in a number of properties which are
central portion of the periodic table. There are four d-block directly or indirecUy linked with electronic configuration.
series, i.e., 3d series, 4d series, 5d series and 6d series, each (i) Effective nuclear charge increases across each period.
consisting of ten elements, i.e., in all, forty d-block elements (ii) Atomic radii generally decrease across the periods.
,are present in periodic table. (iii) Atomic radii generally increase on moving from top
f-block elements are accommodated in two horizontal rows to bottom in the groups.
(iv) Atomic radius is of three types:
below the main periodic table, each row consists of 14 ,
(a) Covalent radius: It is half of the distance between IEI < IEn < IEm .......
the centres of the nuclei of two similar atoms joined The largest jump in between first ionisation enthalpy
by a single covalent bond. This is generally used and second ionisation enthalpy is in the case of alkali
for non-metals. metals as ns 1 configurations change into inert gas confi-
(b) Crystal or metallic radius : It is. half of the gurations.
internuclear distance between two nearest atoms in The largest jump in between second ionisation enthalpy
the metallic lattice. It is generally used for metals. and third ionisation enthalpy is in the case of alkaline
(c) van der Waals' radius: It is half of the internuclear earth metals.
distance between two nearest atoms belonging to (xvi) The enthalpy change taking place when an electron is
two adjacent molecules in solid state. added. to an isolated gaseous atoUl of. the element is
van der Waals' radius> Metallic radius> Covalent called electron gain enthalpy. The first. electron gain
.radius enthalpy of most of the elements -is negative as energy
(for an atom) is released in the process but the values are positive or
(v) Cations are generally smaller than anions. near zero in case of the atoms having stable confi-
(vi) Cations are smaller and anions are larger than neutral guration such as Be, Mg, N, noble gases, etc.
atoms of the elements. (xvii) Electron gain enthalpy becomes more negative from left
Cation < Neutral atom < Anion to right in a period and less negative from. top to
size size size bottom in a group.
(vii) Elements of 2nd and 3rd transition series belonging to (xviii) Successive electron gain enthalpies are always positive.
same vertical columns are similar in size and properties (xix) The elements with higher ionisation enthalpy have
due to lanthanide contraction. higher negative electron gain enthalpy.
(viii) The first element is each group of the. representative (xx) Electronegativity is the tendency of an atom to attract
elements shows abnormal properties, i.e., differs from the shared pair of electrons towards itself in a bond.
other elements of the group because of much smaller (xxi) Electronegativity increases across the periods and
size of the atom. decreases down the groups.
(ix) The ions having same number of electrons but different (xxii) Metals have low electronegativities and non-metals
nuclear charge are called isoelectronic ions. have high electronegativities.
Examples, (xxiii) Metallic character decreases across the periods and
(a) N3-, 0 2-, 1', Na+, Mg2+, Al3+ increases down the group.
(b) F, , 0-, K+, ci+, Sc3+ (xxiv) Valency of an element belonging to s- and p-block
(except noble gases) is either equal to the number of
In isoelectronic ions, the size decreases if z/ e increases, valence electrons or eight minus number of valence
(e., greater the nuclear charge, smaller is the size of the electrons.
ion. (xxv) The reducing nature of the elements decreases across
. (x) The energy required to remove the most loosely held the period while oxidising nature increases.
electron from the gaseous isolated atom is termed (xxvi) The basic character of the oxides decreases while the
ionisation enthalpy. acidic character increases in moving from left to right
(xi) Ionisation enthalpy values generally increase across the in a period.
periods.
(xii) Ionisation enthalpy values generally decrease down the SOME IMPORTANT FACTS ABOUT ELEMENTS
group.
(i) Bromine is a non-metal which is liquid at room
(xiii) Removal of electron from filled and half filled shells
tempera ture.
requires higher energy. For example, the ionisation
(ii) Mercury is the only metal that is liquid at room
enthalpy of nitrogen is higher than oxygen. Be, Mg and
temperature.
noble gases have high values.
(iii) Gallium (m.pt. 29.8°C), caesium (m.pt. 28'soC) and
The following trend is observed in the first ionisation
francium (m.pt. 27"C) are metals having low melting
enthalpy of the elements of second and third periods.
points.
Second period U < Be > B < C < N > 0 < F < Ne
(iv) Tungsten (W) has the highest melting point (3380"C)
or U < B < Be < C < 0 < N < F < Ne
among metals.
Third period Na < Mg > AI < Si < P > S < Cl < Ar
(v) Carbon has the highest melting point (4100OC) among
or Na < AI < Mg < Si < S < P < CI < Ar
non-metals.
(xiv) Metals have low iorusation enthalpy values while non-
(vi) Oxygen is the most abundant element on the earth.
metals have high ionisation enthalpy values.
(vii) Aluminium is the most abundant metal.
(xv) Successive ionisation enthalpies of an atom have higher
(viii) Iron is the most abundant transition metal.
values.
(ix) Highest density is shown by osmium (22.59 g cm-3) or 1. Samarium (Sm) 2. Gadolinium (Gd) \
iridium (22.61 g em-3). 3. Curium (Cm) 4. Einsteinium (Es)
(x) Lithium is the lightest metal. Its density is 0.54 g cm-3. 5. Fermium (Fm) 6. Mendelevium (Md)
(xi) Silver is the best conductor of electricity. 7. Nobelium (No) 8. Lawrencium (Lr)
(xii) Diamond (carbon) is the hardest natural substance. 9. Rutherfordium (Rf) 10. Seaborgium (Sg)
(xiii) Francium has the highest atomic volume. 11. Bohrium (Bh) 12. Meitnerium (Mt)
(xiv) Boron has the lowest atomic volume. 13. Rontgenium (Rg)
(xv) The most abundant gas in atmosphere is nitrogen. The following elements have been named after planets
(xvi) Fluorine is the most electronegative element. and stars.
(xvii) Chlorine has the maximum negative electron gain
1. Mercury (Hg) 2. Uranium (U)
enthalpy.
3. Neptunium (Np) 4. Plutonium (Pu)
(xviii) Helium has the maximum ionisation enthalpy.
5. Titanium (Ti) 6. Zirconium (Zr)
(xix) Caesium or francium has the lowest ionisation
7.. Cerium (Ce)
enthalpy.
(xx) Helium and francium are smallest and largest atoms (xxxv) The members of the actinide series are radioactive and
respectively. majority of them are not found in nature.
(xxi) H- and r ions are the smallest and largest anions (xxxvi) The element rutherfordium 00, 104) is also called
respectively. Kurchatovium (Ku) and element dubnium (Db, 105) is
(xxii) H+ and Cs + ions are the smallest and largest cations also called hahnium.
respectively. (xxxvii) Promethium (Pm, 61) a member of lanthanide series is
(xxiii) Caesium is the most electropositive element. not found in nature. It is a synthetic element.
(xxiv) Element kept in water is phosphorus, P4 (white or (xxxviii) Special names are given to the members of these groups
yellow). in periodic table.
(xxv) Elements kept in kerosene oil are Na, K, Rb, Cs, etc. Group 1 or IA Alkali metals
(xxvi) Iodine is the element which sublimes. Group 2 or ITA Alkaline earth metals
(xxvii) Hydrogen is the most abundant element in the universe. Group 15 or VA Pnictogens
(xxviii) Only ozone is the coloured gas with garlic smell. Group 16 or VIA Chakogens
(xxix) Metalloids have electronegativity values closer to 2.0. Group 17 or VITA Halogens
(xxx) First synthetic (i.e., man-made) element is technetium Group 18 or VIllA Inert or noble gases
(At. no. 43). . . (zero)
(xxxi) Most poisonous metal-Plutonium. Group 11 or m Coinage metals
(xxxii) Rarest element in earth's crust-Astatine. (xxxix) Element having maximum number of isotopes-Sn
(xxxiii) The elements coming after uranium are called (10 isotopes)
transuranic elements.The elements-with Z 104 116, (xL) Least conductor among metals - Ph (Lead)
and 118 are called transactinides or superheavy (xLi) Heaviest naturally occurring element - 2~U
elements. All these elements are synthetic, i.e., man-
(xLii) Liquid radioactive element ~ Fr
made elements. These are radioactive elements and not
(xLiii) Element with highest tensile stress - B
found in nature.
(xliv) Number of gaseous elements in the periodic table = 12
(xxxiv) The elements ruthenium (Ru), germanium (Ge),
(H2, He, N2, ~, F2, au Ne, AT, Xe, Kr, Rn and Uno)
polonium (Po), francium (Fr) and americium (Am) were
(xLv) Most malleable metal - Au
named in honour of the countries named Ruthenia
(xLvi) Carbon has the maximum tendency for catenation.
(Russia), Germany, Poland, France and America,
(xLvii) Out of 117 known elements, 90 are found in nature.
respectively.
These are from atomic numbers 1 to 92 with the
The Swedish town of Ytterby has the distinction of
exception of technetium (43Tc-a transition element) and
having four elements named after it. These elements
promethium (61Pm-a member of lanthanide series).
are : erbium (Er), ytterbium (Vb), yttrium (Y) and
Traces of two posturanic elements neptunium (At. No.
terbium (Tb). An element has been named californium
93) and plutonium (At. No. 94) are found in nature in
(CO after an American state california. Few elements
pitchblende ore.
have been named after some famous scientists/people
but none of scientist/people discovered the element
named after them. These elements are :
44 G.R.B. InorganicChemistry for Competitions
-' I
-: ••• - PRACTICE PROBLEMS -:~" •• ~

• Subjective Type Questions (viii) 121 F2, Br2 and Cl2 (reactivity)
(ix) Lit Be and B (ionisation enthalpy)
1. Answer the following: (x) Li, Na, K, Rb· and Cs (hydra~d radii)
(a) Name the scientist who presented 'Law of octave'. (xi) Si02, P20 S, 503 and C12~ (acidic nature)
(b) Name the scientist who presented modified periodic (xii) F, CI, Br and 1. (electronegativity)
law. (xiii) Na, Cu and Zn (electropositive character)
(c) What is the basis for modern Mendeleey's periodic table (xiv) Na, AI, Fe and Pb (density)
and long form of periodic table? (xv) C,. N, 0 and F (2nd ionisation enthalpy)
(d) Name the anomalous pairs. 3. With reference to periodic table, indicate:
(e) Name the pairs showing a diagonal relationship. (a) an element that is in group InA and third period.
(f) What are inner-transition elements? (b) an element with an atomic number greater than 16 and
(g) .How many elements are present in each of the 3d, 4d • chemically similar to the element with atomic number
and 5d-series ? 10.
(h) Which is the longest period in the long form of periodic (c) first transition element .of fourth period.
table? (d) the inert gases placed in the 2nd and 5th period.
(i) Which is the shortest period in the long form of periodic (e) the group which accommodates lanthanides and
table? actinides,
(j) How many incomplete periods are there in the long (0 the group all members of which are metals.
form of periodic table? (g) position of most electropositive element.
(k) Write the general electronic configuration of d~block (h) position of most electronegative .element,
elements. (n the group to which most abundant element belongs,
(l) Write the general electronic configuration of f-block (i) the groups of 5~block elements.
elements. 4. (a) Group the following elements (atomic numbers given)
(m) Which element has the· highest ionisation enthalpy into various blocks noted below:
value? 12, 19, 17, 25, 31, 42, 54, 23, 38
(n) Which element has the highest negative electron gain (0 s-block (ij) p-block (iii) d-block
enthalpy value? (b) 'Which of the following are transition elements?
(0) Which .element has the highest electronegativity? K, Mn, Ca, Cs, Fe, Cu, Pb
(p) For what type of ions the ionic radius is less than the (c) In how many blocks have the elements of long form of
atomic radius? periodic table been divided? Name them.
(q) What are the units of Ionisation enthalpy or electron (d) The electronic configurations of some of the elements
gain enthalpy? are given below:
(r) Name the species (atoms or ions) having same number (A) 1/, 2s2 2p6, 3s2 (B) 182,2; 2p6. (C) 1/, 152 2p3
of electrons. (D) 152, 2i 2p6; 351 (E) 1/, 152 2pS
(s) Name three elements that exist in liquid state. (i) Name the elements.
(t) How many more elements are to be discovered to (ii) .Which of these has ,low ionisation enthalpy?
complete the last period of the periodic table? (iii) Whichis a halogen?
(u) How many metals and non-metals are known? (iv) Which .is an alkali metal?
(v) Name the extreme left and. extreme right groups of the (v) Which is an inert gas?
. extended form of the periodic table. 5. (a) From among the elements, chbose the following:
(w) What name is given: to the elements belonging to third CI, Br, F, 0, Al, C, Li, Cs and Xe
period of Mendeleev'speriodic table? (i) the element with highest electron gain enthalpy.
(x) How many inner-transition elements are. known? (ii). the. element with lowest ionisaticm. enthalpy,
z. Arrange the following in increasing order of the property (iii) the element whose oxide is amphoteric.
indicated: . (iv) the element which has smallest radius.
(i) F, CI, Br and I (electron gain enthalpy) [I.I.T. 1993) (v) the element' whose atom has 6 electrons in the
(ii) Mi+, 0 2-, Na+, F- and N3- (ionic size)· [LI.T. 1991)
outermost shell.
(iii) cr, S2-, Ca2+ and Ar (size)
(vi) the element which belongs to zero group,
(iv) Mg, Al, Si and Na (ionisation enthalpy) (vii;) the element which forms largest number of
(v) Br+, Br and Br- (size) compounds.
(vi) Pb, Pb2+ and Pb4+ (size) (viii) the element which shows diagonal relationship
(vii) HCI, HF, HI and HBr (acid strength) with Mg.
(ix) the element which is in liquid state under 9. The element 119 has not been discovered. What would be
ordinary atmospheric conditions. IUPAC name and symJ:>ol for this element? On the basis of
(b) The elements Na, Mg, Al, Si, P, S, CI and AI are arranged the periodic table, predict the electronic configuration of
in the periodic table in' the increasing order of their this element and also the formula of its most stable chloride
atomic numbers. and oxide.
(i) Which element is the most electronegative? 10. Predict the formulae of stable binary compounds that would
(li) Which element is the most electropositive? be formed. by the following pairs of. elements:
(iii) Which element is the least reactive? (a) element 114 and fluorine
(iv) Which elements are gases at room temperature? (b) element 120 and oxygen.
(v) Which element is the most abundant metal? 11. Write short notes on:
(vi) Which element is the strongest oxidising agent? (i) Dobereiner's triads
(vii) Which element has the electronic configuration? (ii) Law of octaves
ti, 2s2 2p6, 3i 3p; 3P13P! (iii) Lother Meyer's curve
(viii) Which element shows +6 oxidation state? (iv) The periodic law
(c) Pick up from the elements Na, Cl, Si and AI. (v) Groups and periods in modem Mendeleev's periodic
(i) the element with' highest ionisation enthalpy. table
(ii) the element with highest electron gain enthalpy. (vi) Groups and periods in extended form of periodic
(iii) the element with smallest size. table
(iv:) the element with largest radius; (vii) Representative elements
(v) the element with lowest ionisation enthalpy. (viii) Transition elements
(d) A, B and C are the elements of a short period of a (ix) Lanthanides
periodic table containing one, two and three electrons (x) Actinides
in their outermost shell, respectively. (xi) Defects of Mendeleev's periodic table
Arrange A, B and C in the increasing order of: (xii) Merits of extended form of periodic table
(i) their ionisation enthalpy (xiii) Isoelectronic speCies
(ii) basic character of their oxides (xiv) Screening effect
(iii) covalent character in their chlorides and (xv) . Effective nuclear charge
(iv) melting points of their chlorides. (xvi) Ionisation enthalpy
6. (a) Give the electronic configuration of third alkali metal. (xvii) Electron gain enthalpy
(b) Give the electronic configuration of fifth element of first (xviii) Electronegativity
.transition series. (xix) Covalent radii
(e) .Give the electronic. configuration of ninth element of (xx) Ionic radii
first transition series. 12. Explain the following:
(d) Give the names and atomic numbers· of the first and (0 There are only 14 lanthanides and only 14 actinides.
[Hint: In lanthanides and actinides, the differentiating
last members of the lanthanide series.
electron enters to (n 2)f-subshell. The maximum
(e) Give the ri.ames and atomic numbers of the first and
capacity of f-subshell is of 14 electrons. Thus, there
last members of the actinide series. are only 14 lanthanides (4t-14) and only 14
7. Answer the following: actinides (5f1-1-;.]
(a) Name of the groups of elements 'classified as 8-, p- and
{in Why argon (at. mass 39.94) has been placed before
d-blocks. potassium (at. mass 39.10) in the periodic table?
(b) In terms of electronic configuration, what the elements
[M.L.N.R. 1990]
of a given period and a group have in common? [Hint : In mooern periodic table, elements have been
(e) Name the groups whose elements are called represen- . placed in order of their increasing atomic numbers.
tative elements. The atomic number of argon is 18 and that of
(d) Write the general electronic configuration of S-, p-, potassium is 19. Thus, argon has been placed
before potassium.]
d- and I-block elements.
Explain: . (iii) 3d, 4d and 5d series consists of 10 elements each.
8.
2 [Hint: In 3d, 4d and 5d series, the differentiating electron
(a) Mg2+ ion is smaller than 0 - ion although both have enters to (n - 1)d-subshell. The maximum capacity of
same electronic configuration. d-subshell is of 10 electrons. Thus, there are 10
(b) Why nitrogen has slightly positive electron gain eJements each in 3d, 4d and 5d series [(n l)dl-lo].]
enthalpy? (iv) There are 2, 8 and 8 elements in first, second and third
(e) Sulphur has more negative electron gain enthalpy than periods of periodic table respectively.
oxygen. [Hint : In first period Is is completed. Its capacity is of
(d) In a period of normal elements, which element has two electrons. In second period 2s 2p and in third
period 35 3p are completed. The capacity of these
lowest ionisation enthalpy and which element has sheIls is of 8 electrons each. Thus, 2, 8 and 8
highe!4t. enthalpy?
elements .are present in first, second and third (xvii) Why is potassium a strongly electropositive element?
periods respectively.] [Hint : The ionisation potential of potassium is low. Hence,
(v) Why f-block elements are so called? it can lose an electron easily. Therefore, it is strongly
[Hint : The differentiating electron enters to (n 2)f-sub- electropositive in nature.)
shell.]
(xviii) Why alkali metals do not form dipositive ions?
(vi) Why zero group elements are inert?
[Hint : The alkali metals after loss of one electron achieve
[Hint ; Zero group elements are inert because they have
completely filled outermost shells. Neither they stable configuration of inert gases. The removal of
have a tendency to lose or gain or share electron/ second electron requires very high energy, hence,
electrons with other elements.] alkali metals do not form dipositive ions.]
(vii) The radius of a cation is lesser than atom while that 13. How do the following properties vary in a period and in a
of an anion is greater than the atom. group of periodic table?
[Hint : In a cation, the nuclear charge acts on lesser number (a) Covalent radii (b) Ionic radii
of electrons and thus, the electron cloud contracts. (c) Ionisation enthalpy (d) Electron gain enthalpy
Hence, the net result is decrease in size. In an anion, (e) Electronegativity (f) Metallic and non-metallic
the nuclear charge acts on larger number of nature
electrons and thus, the electron doud expands.
Hence, the net result is increase in size. This can
14. Write down the main characteristics of:
also be explained on the basis of z/ e ratio. In cation (a) s-block elements (b) p-block elements
z/e ratio increases, hence size decreases while in (c) d-block elements (d) f-block elements
.an anion zle ratio decreases and so the size 15. Calculate the electronegativity of· fluorine from the
increases.] following data:
(viii) Why the second ionisation enthalpy of an element is EH- H 104.2 kcal mol-I, EF- F == 36.6 kcal mort,
higher than the first? . EH--F 134.6 kcal morl, X H == 2.1. [M.L.N.R. 1996]
[Hint : The electrostatic attraction increases in unipositive
ion than in a neutral atom.] Solution: Let the electronegativity of fluorine be XF.
(ix) First ionisation enthalpy of nitrogen is higher than the Applying Pauling equation,
first ionisation enthalpy of oxygen. X F X H :: 0.208 [EH-F
[Hint : Nitrogen has stable configuration as p-orbitals are
22111 In this equation, dissociation energies are taken in kcal mori.
ill
half fed. 15, 2s 2p x 2p 11 2p z· Hence, more
,. 1
energy is required to remove an electron.]
XF - 2.1 0.208 [134.6 - '12 (104.2 + 36.6)]2- == 3.76
(x) Why are the electron gain enthalpies of halogens so
high? 16. Calculate the electronegativity of carbon from the following
[Hint : The electron is easily accommodated as halogens data:
acquire inert gas configuration after gaining the EH-H :: 104.2 kcal mort, Ec-c = 83.1 kcal mol-I,
electron.]
,EC-H 98.8 kcal mort, XH = 2.1.
(xi) Why noble gases have positive electron gain enthal-
pies? Solution:
[Hint : Noble gases have a stable electronic configuration. Let the electronegativity of carbon be Xc.
Hence, it is difficult to add the electron resulting Applying Pauling equation, 1
in positive electron gain enthalpy.]
(xii) Why most of the compounds of the transition XH = 0.208 [EC-H i (Ec-c + E )]'2
H- H
1
elements are coloured?
[Hint : The ions contain unpaired d-electrons.] Xc - 2.1 :: 0.208 [98.8 i (83.1 + 104.2)]2
(xiii) Why the atomic radii of 5d transition elements is same Xc == 2.5
as 4d transition elements? 17. Ionisation enthalpy and electron gain enthalpy of fluorine
[Hint : The increase in size that arises due to period are 17.42 and 3.45 eV respectively. Calculate the electro-
change is almost compensated by lanthanide
negativity of fluorine.
contraction.]
(xiv) .Chlorine can be converted into chloride ion easily as Solution:
compared to fluoride ion from fluorine. According to Mulliken equation,
[Hint :. Chlorine has higher value of electron gain enthalpy
as compared to fluorine.]
x IE when both IE and Eg are taken in eV.
(xv) s-block elements are very active.
[Hint : s-block elements have low ionisation enthalpies and
Xp 17.4~~ 3.45 = 3.726
thus, easily form cations.)
18. The electron gain enthalpy of chlorine is 3.7 eV. How much
(xvi) Why Be and Mg atoms do not impart colour in a energy in kcal is released when 2g of chlorine is completely
flame? converted to cr ion in a gaseous state?
[Hint : Be and Mg atoms are comparatively smaller and (1 eV == 23.06 kcal mol-I)
their ionisation energies are very high. Hence, their
electrons are not .excited by the energy' of the flame Solution:
to higher energy state. Therefore, these elements do
not give any colour in flame.]
CI + e ~ cr + 3.7 eV
35.5 3.7 x 23.06 kcal
:. Energy released for conversion of 2g gaseous chlorine 26: Give the name and atomic number of the inert gas atom in
into Crions which the total number of d-electrons is equal to the
= 3.7 x 23.06 x 2 = 4.8 kcal difference in numbers of total p and s-electrons.
35.5 [Hint: Inert gas atom is krypton. Its atomic number is 36. The
19. Calculate the electronegativity of silicon using AJlred- electronic configuration of Kr-atom is:
Rochow method. Covalent radius of silicon is 1.175 A. Ii, 2i 2p6, 3i 3p6 3d 10, 4i 4p6
Solution: Totals-electrons = 8
Allred-Rochow equation is,
Total p-electrons = 18
Zeff Difference = 18 - 8 = 10
X = 0.359 -2- + 0.744
r Total d-electrons = 10 ]
{Zeff is calculated on the basis of Slater's rules taking all the
electrons.)
Electronic configuration of Si is Is2, 2s2 2p6, 3s2 3p2. • Matching Type Questions
Zett = 14 - (0.35 x 4 + 0.85 x8 + 2 x 1) = 3.80 Match the following:
. 3.80
X = 0.359 (1.175)2 + 0.744 = 1.73 (A) (a) Normal element (i) Uranium
20. The first ionisation enthalpy of Li is 5.4 eV and th~ electron (b) Noble gas (ii) Copper
gain enthalpy of Cl is 3.6 eV. Calculate Mi in kcal morl (c) Transition element (iii) Cerium
for the reaction, (d) Lanthanide (iv) Radon
Li(g) + CI(g) -------7 Li+ + Cl- (e) Actinide (v) Potassium
Carried out at such low pressure that resulting ions do not (B) (a) Fluorine (i) Highest negative electron
combine with each other.
gain enthalpy
Solution: (b) Helium (ii) Most electropositive element
The overall reaction is written into two partial equations. (c) Chlorine (iii) Most electronegative element
Li(g) -------7 Li+ + e ,iEl = 5.4 eV
(d) Caesium (iv) Strongest reducing agent insoln.
Cl(g) + e -------7 Cl- ,iE2 = -3.6 eV
(e) Lithium (v) Highest ionisation enthalpy
,iH = ,iEl - ,iE2 = 5.4 - 3.6 = 1.8 eV
l l (C) (a) s-block element (i) Sulphur
= 1.8 x 23.06 kcal mor = 41.508 kcal mol-
(b) p-block element (ii) Argon
21. Calculate the electronegativity value of chlorine on
Mulliken's scale, given that IP = 13.0 eV and EA = 4.0 eV. (c) d-block element (iii) Neptunium
Ans. 3.03 (d). [-block element (iv) Iron
22. Find the electronegativity of lead with the help of the given (e) Inert gas (v) Radium
values. Screening constant (0) of Pb = 76.70, atomic number (D) (a) IA (i) Liquid metal (1) Halogen
of lead = 82 and covalent radius of Pb = 5.3 A.
Ans. 1.55
(b) d-block (ii) Liquid non-metal (2) 3s2 3p4
·23. The iOlusation enthalpies of atoms A and Bare 400 and 300 elements
kcal mol-l respectively. The electron gain enthalpies of (c) Mercury (iii) Diamond (3) ns 1
these atoms are 80.0 and 85.0 kcal morl respectively. Prove (d) Bromine (iv) VIA group (4) Variable
that which of the atoms has higher electronegativity?
valency
. 400+80 300+85
[Hmt: X A = 2x62.5 =3.84; X B = 2x62.5 =3.08] (e) Carbon (v) Alkali metals (5) Coinage metal
. Ans: A (f) Sulphur (vi) Noble metal (6) Amalgam
24. For the gaseous reaction, (g) Gold (vii) Transition (7) Hardest
K + F -------7 K+ + F-, Mi was calculated to be 19 kcal under metals substance
conditions where the cations and anions were prevented by (E) (a) A reactive non-metal; the atom (i) Sodium
electrostatic separation from combining with each other.
The ionisation enthalpy of K is 4.3 eV. What is the electron has a large negative electron affinity
gain enthalpy of F? (b) A soft metal; the atom has low (ii) Antimony
[Hint : K ~ K+ + e MOl = 4.3 eV ionisation energy
F + e ~ F- M02 = - EeV (c) A metalloid that forms an oxide (iii) Argon
2~g6 = LlEI - LlE2 = 4.3 - E of the formula R20 3
0.82 = 4.3 - E
(d) A chemically unreactive gas (iv) Chlorine
E = 3.48]
(F) (a) A reactive, pale yellow gas; the (i) Oxygen
25. How many Cl atoms can you ionise in the process atom has a large negative electron
Cl -------7 Cl+ + e by the energy liberated. for the process affinity
Cl + e -------7 cr for one Avogadro number of atoms? Given (b) A soft metal that reacts with (ii) Gallium
IE = 13.0 eV and Eg = 3.60 eV. water to produce hydrogen
[Hint ~ Let n atoms be ionised. (c) A metal that forms an oxide of (iii) Barium
6.02 x 1023 x Eg = n x IE formula R20 3
23 3 (d) A colourless gas; the atom has (iv) Fluorine
n = 6.02 Xl~3 x .60 = 1.667>.< 1023 ] moderately large negative
electron affinity
Answers .: Subjective Type Questions (c) (j) Ar, (li) Cl, (iii) CI, (iv) Ar, (v) Na.
l~.'(a) Newland; (b) Moseley; (d Atomic numbers of elements; (d) K, (d) 0) A < C < B, (ii) C < B < A, (iii) A < B < C, (iv) C < B < A.
Ar; Co, Ni; Te, I; Pa, Th; (e) Li, Mg; Be, AI; B, Si; (f) Lanthanides 6. (a) K-ll, 2s2zpo, 3s23p6, 451 ' .
and actinides; (g) Ten; (h) Sixth; (i) First; (j) one, i.e., 7th period; (b) Mn-ls2, 2s2zpo, 3s~p~;, 4;
(k) (n _l)dl-lO ns1 or 2; (I) (n _ 2)/ 1- 14 (n-l)d 0 or 1 ns 2; (m) Helium; (d Cu-l;, 2s22p6, 3s~po3d1O, 4s1
(n) Chlorine; (0) Fluorine; (p) Cations; (q) eV /atom or kcal/mol (d) Ce (Z = 58), Lu (Z = 71)
or kJlmol; (r) Isoelectronic; (s)Francium, mercury and bromine; (e) Th (Z = 90), Lr (Z 103)
(t) 4; (u) Out of 117 elements 94 metals and 23 non-metals; 7. (a) s-block = groups 1, 2
(v) I or IA (alkali group), zero group, 18 (inert or noble gases); p-block = groups 13 to 18
(w) Bridge elements; (x) 28. d-block = groups 3 to 12
2. (i) 1 < Br < F < Cl; (b) For elements in a period, the number of energy shells is equal
(li) Mg2T < Na+ < F- < d- < N:>- [Isoelectronic ions]; and for elements in the group, the number of electrons in the valence
(ili) ciT < Ar < Cl- < 5 -;
2 shell (outermost shell) is the same.
(iv) Na < AI < Mg < Si;
(v) Br+ < Br < Br-; (vi) Pb4+ < Pb2+ < Pb; (c) groups - 1, 2, 13-18
(d) s-block : ns 1-2; p-block : ni npl-6
(vii) HF < HCl < HBr < HI; (viii) 12 < Br2 < Cl2 < F~
d-block : (n _ l)d1-10nsO-2;
(ix) Li < B < Be; (x) Cs < Rb < K < Na < Li;
I-block : (n _ 2)l-14(n _ l)~-lns2
(xi) SiD,. < P20 S < 503 < C120 7; (xii) I < Br < Cl < F;
8. (a) Nuclear charge in Mg2+ is more than 0 2-.
(xiii) Cu < Zn < Na; (xiv) Na < Al < Fe < Pb;
(b) N has stable configuration since it has half filled 2p-orbitals.
(xv)C < N < F < 0.
3 •. (a) AI; (b) Ar; (c) SCi (d) Ne, Xe respectively; (e) IIIB; (f) lIA;
(c) ° has much smaller size than S. The electron density is high
in oxygen and thus, addition of electron is difficult.
(g) IA group, Vlth. period, (h) VilA group, 2nd period; (i) VIA (d) Alkali metal has the lowest and noble gas has the highest
group (oxygen); (j) IA and IlA groups. ionisation enthalpy in a period.
4. (a) (i) s-block-12, 19, 38, (ti) p-block-17, 31; 54, (iii) d-block- 9. Ununennium; 2, 8, 18, 32, 32, 18, 8, 1; MO; M20.
25, 42, 23; (b) Mn, Fe, CUi (c) Four blocks-{i) s-block, (ii) p-block, 10. (a) Element 114 belongs to carbon family. Hence, the formula with
(iii) d-block, (iv) I-block; (d) (i) (A) Mg (B) Ne (C) N (D) Na (E) F fluorine will be AF4, where A represents the element 114.
(ii) D, (iii) E, (iv) D, (v) B. (b) Element 120 belongs to alkaline earth metal's family. Hence,
5. (a) (i) 0, (ii) Cs, (iii) AI, (iv) F, (v) 0, (vi) Xe, (vii) C, (viii) Li, its formula of the oxide will be MO, where M represents
(ix) Br. , element 120.
(b) (i) 0, (ii) Na, (iii) Ar,(iv) CI; Ar, (v) AI, (vi) CI; (vii) P,
(yiii)' S.
'LtllST~T'ONS OF OBJECTIVE QUESTIONS

1. What is the atomic number of last member of the seventh 7. The formula of the binary compound formed by the
period of the extended form of periodic table? element with atomic number 120 and sulphur is:
Wlffi ~IW (a) XS (b) XzS (d XSz (d) X3 S
(c) 120 (d) 122 Ans. (a)
Ans. (b) [Hint : The electronic configuration of the element X with atomic
[Hint : The last member of the sixth period is radon. Its atomic number 120 is [Uuol 85 2. Thus, it belongs to second group
number is 86. In the seventh period energy shells 75, Sf, and its valency is 2.]
6d and 7p are completed, i.e., 2 + 14 + 10 + 6 = 32
electrons are to be accommodated. Thus, in the 7th
8. Elements A, B, C, D and E have the following er~ttronic
period, 32 elements will be present. So, the atomic number configurations:
of the last member will be 86 + 32 118.] (A) 152, 252 2pl (B) Is 2, 2s2 2p6, 382 3pl
2. An element 'X' with atomic number 114 has recently been (C) 152, 25 2 2p6, 38 2 3p3 (D) 182, 28 2 2p6, 352 3p5
discovered. Its IUPAC name is: (E) 15 2, 2s2 2p6, 3s2 3p6, 45 1
(a) Eka-Iead (b) Ununfortium The elements which belong to the "same group of the
(d Ununquadium (d) Bohrium periodic table are:
Ans. (c) (a) (A) and (0 (b) (A) and (B)
[Hint : Un - un - quad - iuml
(d (A) and (D) (d) (A) and (E)
1 1 4
Ans. (b)
3. The process requiring absorption of energy is:
9. In the long form of periodic table, the number 'of period
(a) F~ p- (b) H~ W ' 1
(d CI ~ Cl- (d) 0 ~ (jl-
indicates the value of:
Ans. (d) (a) atomic number
[Hint : Second electron gain enthalpy is an' endothe.rmic process (b) atomic mass
as the second electron is added to a negatively charged (d principal quantum number
particle. Energy is needed to overcome force of repulsion.l (d) azimuthal quantum number
4. Which transition involves maximum amount of energy? Ans. (c)
[Hint : The serial number of the period indicates the principal
(a) M-(g) ~. M(g) + e
quantum number (11) which is the value of the valence
(b) M-(g) ~ M+(g) + 2e shell of the atoms of the elements present in that period.]
(d M+(g) ~ MZ+(g) + e 10. Which one of the following statements is incorrect in
(d) M 2+(g) ~ M3+(g) +e relation to ionisation enthalpy?
Ans. (d) (a) Ionisation enthalpy increases for each successive
[Hint : 3rd I.P. > 2nd J.P. > 1st LP.] electron
5. Na+, Mgz+, Al3+and Si4+ are isoelectronic ions. Their ionic (b) The greater increase in ionisation enthalpy is
size follows the order: experienced on removal of electron from core noble gas
configuration
(a) Na+ < Mgz+ < A13+ < Si4+
(c) End of valence electrons is marked. by a big jump in
(b) Na+ < M~+ < Al3+ > Si4+ ionisation enthalpy
(d Na+ < Mgz+ > Al3+ > Si4+ (d) Removal of electron from orbitals bearing lower n value
(d) Na+ > M~+ > Al3+ > Si4+ is easier than from an orbital having higher n value
Ans. (d) Ans. (d)
[Hint : ~ Na+ = 1.1, Mg2+ 1.2, A13+ = 1.3 and Si4+ 1.4 [Hint: Removal of electron from orbitals bearing lower value of
11 is difficult than from the orbital having higher value of
As ~ increases, size decreases.] 11.1
6. (0 There are four d-block series. 11. The correct order regarding electronegativity of hybrid
(ii) Total d-block elements are 40. orbitals of carbon is: rCB.S.E. ZOGS]
(iii) Last d-block series starts with element actinium. (a) sp < sp2 < sp3 (b) sp < sp2 > Sp3
(iv) All members of d-block Sfiries are stable elements and (d sp > sp2 < sp3 (d) sp > sp'l > sp3
found in nature.
Ans. (d)
The correct statements are:
[Hint : Electronegativity increases as s-character in hybrid orbital
(a) (0, (ll) and (iii) (b) (i) and (iii) increases.] .
(d (0 and (iv) (d) All
Ans.· (a)
12. The electronic configurations of four elements are : 16. The radii of P, F-, 0 and 0 2- are in the order :
(0 [Xe] 6s1 01) [Xel 4f 145d 165 2 . .(a) 02- > F- > F> 0 (b) pc- >02- >F > 0
2
(iii) [Ar] 4s 4p5 (iv) tAr] 3d 7452 (c) o2~ > 0 > F-'- > F (d) 02- > F- > 0 > F
Which one of the following statements about these Ans. (d)
[Hint : Anions are larger than neutral atoms. Oxygen is larger
elements is not correct?
than fluorine as the nuclear charge is less.]
(a) (i) is a strong reducing agent
(b) (ii) is a d-block element 17. In the sixth period, the orbitals are filled as :
(a) 6s 5f 6d 6p (b) 65 4f 5d 6p
(c) (ill) has high negative electron gain enthalpy
(c) 55 5p 5d6p (d) 65 6p 6d 6f
(d) (iv)shows variable oxidation state Ans. (b)
Ans. (b)
18. In the periodic table, which of the following trends is correct
[Hint : (li) is a last member of lanthanide series, i.e., 4f-element.]
in a period?
13. Which of the following ions is most unlikely to exist? (a) Electron affinity decreases
(a) U- (b) Be2+
(b) Electronegative character decreases
(c) S- (d) P-
(c) Electropositive character increases
Ans. (a)
(d) Non-metallic nature increases
[Hint : Metals are electropositive, they do not form anion.]
Ans. (d)
14. The element having very high ionization enthalpy but zero
19. The atomic radius of elements of the following series should
electron gain .enthalpy is:
be nearly the same :
(a) H (b) F
(a) Na, K, Rb, Cs (b) Na, Mg, AI, Si
(c) He (d) Be
(d Fe, Co, Ni, Cu (d) F, Cl, Br, I
Ans. (d
Ans. (d
[Hint : Inert gases have zero electron affinity.]
!Hint : Transition metals of the same series have nearly the same
15. The second ionization energy is maximum for : atomic radius.]
(a) boron (b) beryllium
20. In the following, the element with the highest ionisation
(c) magnesium (d) aluminium energy is :
Ans. (a)
(a) [Ne] 352 3pl (b) [Ne] 382 3p3
[Hint : Bs _____ 152, 252, 2pl 2
(c) [Ne] 35 3p2 (d) [Ne] 3s2 3p4
Second electron is to be removed from completely filled Ans. (b)
s-subshell, which is difficult.] [Hint : lNe] 35 2 3p3 is a symmetrical configuration. Thus, this
atom has extra stability.]
... -
OBJECTIVE QUESTIONS -
Set I: This set contains questions with single correct answer.
1. The 'Law of triads' was enunciated by:
(a) Mendeleev 0 (b) Newland 0
I 12. The elements which occupy their positions in periodic table
just after the members of zero group are:
(c) Lother Meyer 0 (d) Dobereiner 0 (a) metals 0 (b) gases 0
2. The group number of an element in periodic table indicates:
(a) valency with respect to hydrogen 0 I! 13.
(c) radioactive
An element having
0 (d) alkali metals
electronic configuration [Ar]
0
3ci,4l
(b) the atomicity 0 belongs to:
(c) the number of electrons in the outermost shell 0 I (a) d-block D (b) {-block 0
(d) none of the above 0 (c) s-block 0 (d) p-block 0
3. Which of the following statements is not correct about 14. Elements belonging to same subgroup of periodic table
Lother Meyer's classification in the form of curve? have generally the same:
(a) The elements present at the peaks are chemically very (a) electronic configuration 0
active 0 (b) number of electrons in the outermost shell 0
(b) Alkaline earth metals are present at the descending (c) chemical properties 0
portions of the curve 0 I (d) physical properties 0
(c) Halogens occupy ascending portions of the curve 0 15. The number of elements in fifth period of periodic table is:
(d) The elements present in the troughs are chemically very (a) 8 0 (b) 32 0
reactive and are known as representative elements 0 (c) 18 0 (d) 19 0
4. Which element was named Eka-aluminium by Mendeleev? 16. An element which belongs to third period and fifth group
(a) Scandium 0 (b) Gallium 0 has electronic configuration: '
(c) Germanium 0 (d) Indium 0 (a) Ii, 2i2p6, 3i 3p3 0 (b). Ii, 152 2p3 o
5. Without looking at the periodic table, select the elements 2
(c) Ii, 15 2p6, 3i 3p4 0 (d) none of these o
of lIlA group of the periodic table (Atomic numbers are 17. Which of the following is a d-block element?
given): (a) Fr 0 (b) Al o
(a) 3, 11, 19, 37 o (b) 5, 13,21,39 o (c) Zn 0 (d) Ge o
(c) 7, 15, 31, 49 o (d) 5, 13, 31, 49 o 18. d-block elements in long form of periodic table are placed:
6. The transition elements have a characteristic electronic (a) on the extreme left 0 (b) on the extreme right 0
configuration which can be represented as: (c) at the bottom 0 (d) none of these 0
(a) (n - 2)s2p6i-1O (n - l)lp6 ns2 0 19. Ce (58) is a member of:
(b) (n - 2)ip6i-10(n _ l)s2p6d l or 2 ns1 0 (a) s-block 0 (b) p-block o
(C) (n 1)Slp6 at°
nslnp6ni-1O 0 (c) d-block 0 (d) {-block o
(d) (n l)lp6dl-l0nsl or 1 0 20. Which of the following is not an actinide ?
[D.P.M.T. 2005)
7. The attempt for classifying elements by plotting the atomic
masses of elements against the volumes was made by:
(a) Curium o (b ) Californium 0
(a) Dobereiner 0 (b) Newland o (c) Uranium o (d) Terbium 0
21. Europium is : .{D.P.M.T. 2005]
(c) Lother Meyer 0 (d) Mendeleev o (a) s-block o (b) p-block o
8. Who presented. the law of octave?
(a) Dobereiner 0 (b) Newland 0
(c) d-block o (d) {-block o
22. Variable valency is a general feature of:
(c) Lother Meyer 0 (d) Mendeleev IJ
9. How many elements. were known when Mendeleev
(a) s-block elements 0 (b) p-block elements o
presented the periodic table?
(c) d-block elements 0 (d) none of these o
23. Which one of the following ions is paramagnetic?
(a) 63 0 (b) 80 o (a) Ag+ D (b) Fe 2+ 0
(c) 92 D (d) 102 o (c) K+ 0 (d) Mg2+ 0
10. The basis of periodic law presented by Mendeleev was:
24. Mark the group which has maximum number of elements
(a) valency 0 (b) atomic mass 0
in Mendeleev's periodic fable:
(c) atomic number 0 (d) atomic volume 0
(a) I 0 (b) n D
11. The modern Mendeleev's periodic table consists of
groups:
(c) III D (d) IV o
25. Diagonal relationship in periodic table is shown by
. (a) seven D (b) eight D
elements of . . . . . . and . . . . . . periods :
(c) nine D (d) ten o
~:;~II~~~IIV ~ ;~d~,iat~dI~iE>~:"'~. 37; '. The halogens. are:

(a) normal elements- IJ
26. An element (X) which occurs j!F!1i"~"s~cQtt~L.1l~Q4,1):a~aI\
2 T- ... , '.'-- ,"-
(I,J) noble elements o
outer electronic configuration 8 p -what is the formula and (c) transition elements JJ
nature of its oxide? (d) inner-transition elements 0
(a) X03, basic o (b) X20 3, acidic 2-, F-, Na +, Mg2+ and AI3+ are isoelectronic. Their
~ I 38. The ions 0
(c) X203, basic o (d) X02, acidic ionic radii show: [CB.S.E. (P.M.T.) 2003]
27. An element of atomic mass 40 has 2, 8, 8, 2 as the electronic (a) an increase from 0 2- to F- and then decrease from Na+
configuration. Which one of the following statements ~~ 0
regarding this element is not correct? (b) a decrease from 0 2- to F- and then increase from Na+
(a) It forms an amphoteric oxide 0 ~~ 0
(b) It belongs to IIA group 0 (c) a: significant increase from 0 2- to A13+ 0
(c) It belongs to IV period 0 (d) a significant decrease from 0 2-:- to A13+ 0
(d) It has 20 neutrons 0 39. Modern extended periodic table was given by:
28. The most predominantly electrovalent compounds will be (a) Bohr 0 (b) Lother Meyer 0
obtained from the combination of elements belonging to: (c) Mosley D' (d) none alone 0
(a) I and VII groups 0 (b) II and VI groups 0 40. In the modern periodic table, one of the following does not
(c) III and V groups 0 (d) none of these 0 have appropriate position :
29. Which one of the following configurations represents a (a) inert gases 0
metallic character? (b) inner-transition elements D
(a) 2,8,2 o (b) 2,8,4 [J (c) transition elements o
(c) 2,8,7 o (d) 2,8,8 o (d) fluorine o
30. The first ionisation enthalpies of Na, Mg, Al and Si are in 41. Which one of the following grouping represent a collection
the' order of: of isoelectronic species? (At. numbers, Cs = 55 and Br = 35)
(a) Na < Mg > Al < Si 0 (b) Na > Mg > AI > Si [J [A.I.E.E.E. 2003]
(c) Na < Mg < Al > Si 0 (d) Na > Mg > AI < Si 0 (a) N;>-, F-, Na+ 0 (b) ci+, Cs+, Br . 0
31. Ionisation enthalpy of K would numerically the same as : (c) Be, Ae+, Cl- 2
0 (d) Na+, Ca +, Mg2+ 0
(a) Electronegativity of K+ 0 42. The formation of otg) starting from O(g) is endothermic
(b) Electron gain enthalpy of K+ 0 by 639 kJ morl. If electron gain enthalpy of O(g) is -141 kJ
l
(c) Electron gain enthalpy of Ar 0 mol- , the second electron gain enthalpy of oxygen would
(d) Ionisation enthalpy of Ca 0 be:
32. The electronegativity of the following elements increases (a) - 780 kJ morl o (b) + 780 kJ morl [l
l o l
in the order of: (c) + 498 kJ mol- (d) - 498 kJ mor o
(a) C, N, Si, P 0 (b) N, Si, C, P 0 [HInt: O(g)+2e- --->O(~) ;Ml~639kJmorl ... (i)
o(g)+e- --->o(g) ;Ml~-141kJmorl ... (ii)]
(c) Si, P, C, N 0 (d) P, Si, N, C 0
Subtracting equation (ti) from equation (i)
33. The order in which the following oxides are arranged
O(g) +e- ---> O(~) ; Ml ~ 639 + 141 ~ 780 kJ mor1 J
according to decreasing basic nature is: 43. Which of the following elements has the maximum electron
(a) CuO, Na20, MgO, Al20 3 o gain enthalpy?
(b) A120 3, MgO, CuO, Na20 o (a) oxygen· o (b) chlorine D
(c) MgO, A1 20 3, CuO, Na20 [J (c) fluorine o (d) nitrogen D
(d) Na20, MgO, Al 20 3,CuO o ! 44. The set representing the correct order of first ionisation
34. The difference between ions and atmns is of: enthalpy is: U.I.T. (S) 2001]
(a) relative size 0 (b) configuration o (a) K > Na > Li o (b) Be> Mg > Ca D
(c) presence of charge 0 (d) all of these o (c) B > C > N o (d) Ge > Si > C D
35. Na + is smaller than Na-atom because: (~ 45. If we go from Li to F in the second period, there would be
(a) nucleus in each case containsdifferen~'nucleons 0 a decrease in:
(b) sodium atom has an electron lesser t~an sodium ion (a) atomic mass 0 (b) atomic radii D
. 0
(c) ionisation enthalpy 0 (d) electronegativity D
(c) sodium atom has 11 electrons and sodium ion has 10 46. The element having electronic configuration [Kr] 4d lO
2 2
4l4
,
electrons 0 58 5p6 5i, 68 belongs to:
(d) the force of attraction is less in Na + than in Na-atom (a) 8-block 0 (b) p-block D
o (c) d-block 0 (d) f-block D
36. The highest valency of halogens with respect to oxygen is: 47. The correct order of atomic radii is: [U.T. (S) 2000]
(a) 1 0 (b) -1 0
(a) Na < Be < B 0 (b) F- < 0 2- < N;>- D
(c) 2 0 (d) 7 0
(c) Na < Li < K 0 (d) Fe3+ < Fe 2+ < Fe4 + D
Classification of Elements 'and Periodicity in Properties 53
48.· In gollig from left to right in a period: 59. Lowest ionisation enthalpy in periods is shown by:
(a) the basic nature of the oxides increaseS 0 (a) inert gases 0 (b) halogens 0
(b) acidic nature decreases 0 (c) alkali metals D· (d) alkaline earth metals 0
(c) the basic nature of the oxides decreases 0 60. Which of the following is basic?
(d) no gradation in the nature of oxides is observed 0 (a) 0 (b) Cl 2 0
49. The elements with atomic numbers 58 to 71 are called: (c) Br2 0 (d) 12 0
(a) normal elements 0 (b) transition elements 0 61. Strongest reducing agent among the following' is:
(c) lanthanides 0 (d)actinides 0 (a) P- 0 (b) CI- 0
50. An element R forms the highest oxide RzOs. R belongs to: ~B~ 0 ~I- 0
(a) rv group 0 (b) V group 0 62. The elements with atomic numbers 10, 18, 36, 54 and 86 are
(c) VI group 0 (d) VII group 0 all:
51. Transition metals are characterised by the properties except: (a) light metals 0 (b) inert gases 0
(a) variable valency 0 (c) halogens 0 (d) rare-earths 0
(b) coloured compounds 0 63. The elements on the right side of the periodic table are:
(c) high melting and boiling points· 0 (a) non-metals 0 (b)metals 0
(d) no tendency to form complexes 0 (c) transition elements 0 (d) metalloids 0
52. Ionisation enthalpy in the alkali group: 64. Which of the following atoms has the largest atomic radius?
(a) increases from Li to Cs 0 (a) Cs 0 (b) Ba 0
(b) decreases from Li to Cs 0 (c) Pb 0 (d) Cu 0
(c) remains the same 0 65. Which of the following is the weakest acid?
(d) bears no gradation 0 (a) HF 0 (b) HCI o
53: The ionisation enthalpy of isotopes of an element will be: (c) HBr 0 (d) HI o
(a) same 0 66. Electron affinity of :
(b) different 0 (a) carbon is higher than oxygen 0
(c) dependent on atomic masses 0 (b) sulphur is lesser than oxygen 0
(d) dependent on the number of neutrons present in the (c) iodine is higher than broroine 0
nucleus 0 (d) chlorine is higher than fluorine 0
54. The ionic radius of a cation is always: 67. The correct order of relative stability of half filled and
(a) less than atomic radius 0 completely filled shells is :
(b) more than atomic radius 0 (a) p3 < i < iO < p6 0 (b) dS > p3 > iO > p6 0
(c) equal to atomic radius 0 (c) p3 < iO < i < p6 0 (d) i < p3 < 410 < p6 0
(d) cannot be predicted 0 68. Z
The electronic configuration of an element A is 18 , 2l 2ps.
55. The screening effect of 'd' electrons is : The formula of substance containing only A will be:
(a) much more than s-electrons 0 (a) A 0 (b) A z D
(b) eqUal to s-electrons 0 (c) As 0 (d) A7 0
(c) equal to p-electrons 0 69. The electronic configuration 6f element A is 1l, 2i 2p6,
(d) much less than s-electrons 0 2
38 while of the element B is lsz, 28
2
2l The formula of
56. Which of the following statements is incorrect? the compound containing A and B will be:
(a) Among all the elements, fluorine has the highest (a) AB 0 (b) A2B 0
electron gain enthalpy 0 (c) AB2 0 (d) A2B6 0
(b) Among all the elements, helium has the highest 70. The valency shell of element A contains 3 electrons while
ionisation enthalpy 0 the valency shell of element B contains 6 electrons. If A
(c) Elements of groups 1,2, 13, 14, 15, 16 and 17 are called combines with B, the probable formula of the compound
representative elements 0 formed will be:
. (d) All the ·d-block elements are metallic in nature 0 (a) AB2 0 (b) A2B 0
57. Which of the fo~lowing elements has the lowest ionisation (c) AzB3 0 (d) A3B2 0
~'?nthalpy? . 71. Which one of the follOWing has the highest melting point?
(a) H o (b) CI o (a) Na 0 .{b)Mg 0
(c) He o (d) Pr o (c) K 0 (d) Al 0
58. The first ionisation erithalpies of four consecutive elements 72. Which one of the following is most acidic?
present in the second period· of the periodic table are 8.3, (a) Ah03 0 (b) Na20 o
11.3, 14.5 and 13.6 eVrespectively. Which one of the (c) MgO 0 (d) CaO o
following is the first ionisation enthalpy of nitrogen? 73. Which of the follOwing is an amphoteric oxide?
IE,,A,M,C,E.T, (M~d.) .2()04] (a) MgO 0 (b) Alz03 o
(a) 13.6 o (b) 14.5 0 (c) Si02 0 (d) PzOs o
(c) 11.3 o (d) 8.3 0
74. Which of the following is the correct statement? 88. In the series carbon, nitrogen, oxygen and fluorine, electron-
(a) SO:! is anhydride of sulphuric acid D egativity:
(b) N02 is anhydride of nitric acid D (a) decreases from carbon to fluorine D
(c) Cl20 7 is anhydride of perchloric acid D (b) remains constant []
(d) P20 5 is anhydride of orthophosphorus acid D (c) decreases from carbon to oxygen and then increases D
75. Which is the most acidic oxide? (d) increases from carbon to fluorine []
(a) Cl20 D (b) Cl 20 3 D 89. Ionisation energy of nitrogen is more than oxygen because:
(c) Cl20 5 . D (d) Cl 20 7 D
76: Which of the following halides is not oxidised by Mn02?
(a) F- D (b) CI- D
I! (a) nucleus has more attraction for electrons
(b) half filled p-orbitals are more stable
(c) nitrogen atom is small
D
0
0
77.
(c) Br-
strength of the acids?

D (d) 1-
Which of the following orders is correct for the relative
D
II
,
90.
\
(d) more penetration effect
Lanthanide contraction explains :
(a) density of the series
0
0
(a) HCI04 > HN03 > H 2SO4 > HCl D (b) atomic volume of the series 0
(b) HCl04 > HCI > HN03 > H 2SO4 D (c) chemical activity of the series 0
(c) HCl04 > H 2SO4 > HCI > HN03 D (d) size of the atoms of the series []
(d) HCl04 > HN03 > H 2SO4 > HCI [] 91. The outermost electronic configuration of the most electron-
78. The most non-metallic element among the follOWing is: egative element is:
(a) ni np3 0 (b) n52 np4 0
(a) 152, 2i 2p6 [] (b) 152, 2s2 2p5 []
2 [] (d) 152, 252 2p3
(c) nti np5 0 (d) nti np6 0
(c) 15 , 2i 2p4 []
92. Amongst the following elements (whose electronic config-
79. The highest bond strength amongst the following, is of:
urations are given below) the one having highest ionisation
(a) HF [] (b) HCI []
[] (d)HI
energy is: [I.LT. 1990; .C.B.s.E.(P..M.T.) 20091
(c) HBr D
(a) [Ne] 352 3pl [] (b) [Ne] 382 3p3 0
SO. An element M has an atomic number 9 and atomic mass 19. 2
(c) [Ne] 35 3p2 0 (d) [Ar] 3dlO, 45 2 4p3 0
Its ion will be represented by:
[] (b) M2+
93. The electronic configuration of the element which is just
(a) M D
(c) M- [] (d) M 2- []
above the element with atomic number 43 in the same
periodic group is:
81. The total number of elements known are:
(a) 1i, 2s2 2p6, 3l 3p6 3d5, 4s2 0
(a) 92 D (b) 117 []
(b) 152, 2i 2p6, 3i 3p6 3dlO, 482 4p5 0
(c) 100 [] (d) 118 []
(c) li, 2i 2p6, 3s2 3p6 3d 6, 451 0
82. Atomic and ionic radii are expressed in:
(d) 152, 2s2 2p6, 382 3p6 3d10, 451 4p6 []
(a) angstrom units [] (b) mm []
94. The statement that is not correct for the periodic classi-
(c) cm [] (d) nm []
fication of elements is:
83. The atomic masses of Li and K are 7 and 39, respectively.
(a) The properties of elements are periodic functions of their
According to law of triads the atomic mass of Na will be:
atomic numbers 0
(a) 23 D (b) 32 []
(b) Non-metallic elements are lesser in number than
(c) 46 [] (d) 64 []
metallic elements 0
84. Atoms of which of the following groups lose electrons most i
(c) The first ionisation energies of the elements along the
easily?
periods do not vary in a regular manner with the
(a) Li, Na, K D (b) Cl, Br, I []
increase .in atomic number 0
(c) 0, Sj Se D (d) N, P, As []
(d) For transition elements the d-subshells are filled with
85. The maximum ionisation enthalpy in a period is shown by:
electrons monotonically with increase in atomic
(a) alkali metals D
number 0
(b) inert gases []
95. If the atomic number of an element is 33, it will be placed
(c) representative elements []
[]
in the periodic table in the:
(d) halogens
(a) first group 0 (b) third group 0
86. The 14 elements have been placed in VIth period and third
(c) fifth group [J (d) seventh group 0
group of the periodic table. They are. called:
[]
96. Which one of the following ions has the smallest radius?
(a) alkaline earth metals [] (b) inert gases
(a) C 4- D (b) S2- 0
(c) alkali metals D (d) rare-earth metals []
(c) K+ 0 (d) Ca 2+ 0
87. Which of the following electronic configurations represents
97. The most electropositive element is:
most electropositive element?
(a) [He] 251 [] (b) [He] 2i D
(a) Cs [] (b) Ga o
(c) [Xe] 651 [] (d) [Xe] 65 2 []
(c) Li [] (d) Pb o
98. Among the following, the element which is not liquid at 112. Chloride of an element 'A' gives neutral solution in water.
room temperature (3O"C) is: In the periodic table, the element 'A' belongs to:
(a) Ga 0 (b) Ge 0 (a) first group 0 (b) third group 0
(c) Cs 0 (d) Br 0 (c) fifth group 0 (d) first transition series 0
99. Which of the block of elements does belong to inert gases? 113. Which one of the following belongs to representative group
of elements in the periodic table?
(a) 5-block 0 (b) p-block 0
(a) Lanthanum 0 (b) Argon 0
.(c)· d-block 0 (d) I-block 0
(c) Chromium 0 (d) Aluminium 0
100. Which of the following elements has the lowest ionisation 114. An element of atomic number 29 belongs to:
enthalpy? (a) 8-block 0 (b) p-block 0
(a) Na 0 (b) K 0 (c) d-block 0 (d) I-block 0
(c) Mg 0 (d) Al 0 115. A trend common to both groups 1 and 17 elements in the
101. Which one of the following is smallest in size? periodic table as atomic number increases is:
(a) Na+ [J (b) 0 2- 0 (a) increase in oxidising nature [J
(c) N - 3 0 (d) F- 0 (b) increase in atomic radius 0
102. Which of the following has the lowest ionisation enthalpy? (c) increase in maximum valency 0
(a) 45
1
0 (b) 3d 2 0 (d) increase in reactivity with water 0
(c) 3p6 0 (d) 2p6 0
116. Which of the following has largest radius?
(a) 0 2- 0 (b) Mg2+ 0
103. Of the following elements, which one has the highest
(c) Na+ 0 (d) F- 0
electronegativity?
117. Which one is the correct order of the size of the iodine
(a) I o (b) Br o species?
(c) CI o (d) F o (a) I > 1+ > r- 0 (b) I > r > r+ 0
104. Which of the following is the smallest cation?
(c) r+ > r > I 0 (d) 1- > I > 1+ 0
(a) Na+ 0 (b) Mg2+ 0
118. Which of the following configurations represents atoms of
(c) Ca 2+ 0 (d) A13+ 0
element having a large difference between first and the
105. Among the following outermost configurations of tran-
second ionisation energy?
sition metals which shows the highest oxidation state, is: (a) 1s2, 252 2p4 0 '(b) 152, 152 2p6 0
(a) 3d 3, 4; 0 (b) 3d S, 481 0 2
(c) 18 , 2sZzp6, 3s 1
0 (d) 152, 2s22p6, 352 0
2
5
(c) 3d , 45 0 (d) 3d 6, 4; 0 119. In which of the following arrangements, the order is not
106. Which of the following ions has the lowest magnetic according to the property indicated against it ?
moment? (A.I.E.E.E. 2005]
(a) Cu2+ o (b) Ni2+ o (a) A13+ <. Mg2+ <. Na+ <. F increasing ionic size 0
(c) C0 + 3 o (d) Fe2+ o (b) B <. C <. N <. 0 increasing first ionisation enthalpy 0
107. Modern periodic table is based on the atomic number of (c) I < Br < F < Cl increasing electron gain enthalpy
the elements. The experiment which proved the significance (with negative sign) 0
of the atomic number was:
(d) Li <. Na < K. <. Rb increasing metallic radius 0
(a) Millikan's oil drop experiment 0
120. A sudden large jump betweel!- the values of second and third
(b) Moseley's work on X-ray spectra 0 ionisation energies of an ele~ent would be associated with
(c) Bragg's work on X-ray diffraction 0 the electronic configuration:
(d) Discovery of X-rays by Rontgen. 0 (a) 152, 152 2p6, 3s1 0 (b) Ii, 2i 2p6, 352 3pI 0
108. Which of the follOwing pairs has bbth members from the (c) ls2, 2i 2p6,3s2 3p2 0 (d) Ii, 152 2p6, 3s 2 0
same group of the periodic table? 121. In the long form of the periodic table, all the non-metals
(a) Na, ea 0 (b) Na, CI 0 are placed with:
(c) Ca, CI 0 (d) CI, Br 0 (a) s-block 0 (b) p-block 0
109. Which of the following set of ions represents a collection (c) d-block 0 (d) I-block 0
of isoelectronic species? [A.I.E.E.E. 2006) 122. The lanthanide contraction is responsible for the fact that :
(a) Ba2+, 5r2+, K+, ci+ 0 (b) K+, Cr, ci+, 5c3+ 0 (A.I.B.E.E. 20051
(c) N3-, 0 2-, P-, 52- 0 (d) Li+, Na +, Mg2+, ea2+ 0 (a) Zr and Y have about the same radius o
110. Aluminium is diagonally related to: (b) Zr and Nb have similar oxidation state o
(a) Li 0 (b) Si 0 (c) Zr and Hf have about the same radius o
(c) Be 0 (d) B 0 (d) Zr and Zn have thL' ~,U1,e oxidation state o
111. I.n the sixth period of the extended form of periodic table, 123. Of cobalt and zinc salt!:-. which are attracted in magnetic
the orbitals are filled as : field?
(a) 68,5/, 6d, 6p 0 (b) 55, 5p, 5d, 6p 0 (a) Cobalt Snit... o
(c) 65, 6p, 6d, 61 0 (d) 6s, 4/, 5d, 6p 0 (c) Both o
124. The electronic configuration of an element is Ii, 2i 2p6, (b) The second ionisation potential of Mg is greater than
3i 3p3. What is the atomic number of the element which is the second ionisation potential of Na 0
just below the above element in the periodic table? (c) The first ionisation potential of Na is less than the first
(a) 34 0 (b) 49 0 ionisation potential of Mg 0
(c) 33 0 (d) 31 0 (d) The third ionisation potential of Mg is greater than third
125. Element X belongs to 4th period. It contains 18 and 1 ionisation potential of Al 0
electrons in the penultimate and ultimate orbit. The X 138, Element with atomic number 56 belongs to which block?
should be: [A.F.M.C. 2002]
(a) normal element 0 (b) transition element 0 (a) s 0 (b) p 0
(c) inert gas 0 (c) d ,0 (d) f 0
(d) inner-transition element 0 139. Which of the following orders is wrong? [C.B.S.E. 2002]
126. Electron gain enthalpy of X would be equal to: (a) NH3 < PH3 < AsH3 - Acidic 0
(a) electron affinity of X- 0 (b) Li < Be < B < C IE1 0
(b) ionisation potential of X- 0 (c) Alz03 < MgO < NazO < KzO Basic 0
(c) ionisation potential of X 0 (d) Li+ < Na+ < K+ < Cs+ Ionic radius 0
(d) none of the above 0 140, Which is true about electronegativity order of the following
127. Element with atomic number ~5 belongs to: elements? [B.V. (Pune) 2002]
(a) 3rd period 0 (b) 18th group 0 (a) P > Si 0 ' (b) C > N 0
(c) 5th period 0 (d) 17th group 0 (c) C > Br 0 (d) Sr > Ca 0
128. Most of the man-made synthetic elements occur: 141. Eka-aluminium and Eka-silicon are known as:
(a) in actinide series 0 (b) in lanthanide series 0 rM.E. E.!Kerala) 2002]
(c) in coinage metals 0 (a) gallium and germanium 0
(d) in alkaline earth metals 0 (b) aluminium and silicon 0
129. Which is the largest stable atom? (c) iron and sulphur 0
(a) V 0 (b) Na 0 (d) proton and silicon 0
(c) Al 0 (d) Pb 0 142. Two elements whose electronegativities are 1.2 and 3.0, the
130. Which of the following is strongest base? bond formed between them would be: [P,E.T.(M.P.) 2002]
(a) Be(OH}z 0 (b) Mg(OH)z 0 (a) ionic 0 (b) covalent 0
(c) Al(OHh o . (d) Si(OH)4 0 (c) coordinate 0 (d) metallic 0
131. Which has largest atomic size? 143. Chloride ion and potassium ion are isoelectronic. Then:
(a) AI 0 (b) AIz+ 0 [K.C.E.T. 2002]
(c) A13+ 0 (d) Al+ 0 (a) their sizes are same 0
132. Alkaline earth metals form ions of the formula: (b) 0- ion is bigger than K+ ion 0
(a) M+ d (b) M- 0 (c) K+ ion is relatively bigger 0
(c) MZ+ 0 (d) MZ- 0 (d) their sizes depend on other cation and anion 0
133. Which one of these is basic? 144. Identify the least stable ion amongst the following:
(a) COz 0 (b) SnOz 0 [I.I.T.(S) 2002]
(c) NO z 0 (d) S02 0 (a) Li- 0 (b) Be- 0
134. Of cobalt and zinc salts, which are attracted in a magnetic (c) B- 0 (d) C 0
field? 145. Increasing order of electron gain enthalpy is:
(a) Cobalt salts 0 (b) Zinc salts 0 [P.E.T.(Raj.) 20031
(c) Both (a) and (b) 0 (d) None 0 (a) N < 0 < a < Al 0 (b) 0 < N < AI < CI 0
135. Which of the following species has the highest electron g~in (c) AI < N < 0 < a o (d) CI < N < 0 < AI o
enthalpy?
146. Which of the follOwing sets is of coinage metals?
(a) F- 0 (b) 0 0
IO.P.M.T. 2003]
(c) 0- 0 (d) Na+ 0
136. Among the isoelectronic species, K+, S2-, cr and Ca2+ the
(a) Cu, Ag, Hg o (b) Zn, Cd, Hg 0
radii of the ions decrease as:
(c) Au, Ag, Zn o (d) Li, Na, K 0
147. According to modem periodic law, variations in the
WC?>r>cr>~ 0
properties of elements is related to their: IA.I.E.E.E. 2003]
(b) 0- > Sz- > K+ > Ca2+ 0
(a) atomic weights 0 (b) nuclear weights 0
(c) gZ-> cr > K+ > Ca + z 0
(c) atomic numbers 0 (d) neutron-proton ratios 0
(d) K+ > Ca2+ > S2- > cr 0
148. Which of the following has maximum ionisation enthalpy?
137. The incorrect statement among the following is:
[P.M.T. (PbJ 20031
(a) The first ionisation potential of Al is less than the first
ionisation potential of Mg 0
Classification of Elements and Periodicity in Properties
(a) K o (b) Na [J 158. Which of the following has lowest ionisation energy?
(c) Mg o (d) Be o [CP.M.T. 2007J
149. The electronic configuration of transition elements is (a) Oxygen o (b) Nitrogen o
exhibited Py: [P.M.T. (Pb.) 2003] (c) Fluorine o (d) Sulphur o
(a) ns 1 0 (b) n5 2 np5 0 159. The electronic configuration of the element With maximinn
(c) n5 2 (n . .:. l)d10 0 (d) (n - 1) i-10 nsO- 2 0 electron affinity is: [P.E.T. (Kerala) 2008]
150. General electronic configuration of outermost and penulti- 2
(a) 15 , 152 2p3 0 (b) Ii, 152 2p5 0
mate shell is (n - 1) 52 (n -1) p6(n - 1) d X ni. If n = 4 and 2 2 2 2
(d 15 , 15 2p6, 35 3p5 0 (d) Ii, 15 2p6, 3i 3p3 0
x = 5, then number of protons in the nucleus will be: (e) 152, 152 2p6, 3s 1 0 ..
[P.E.T. (M.P.) 2003J
160. The first ionisation energy of oxygen is less than that of
. (a) > 25 0 (b) < 24 0
nitrogen.. Which of the following is the correct reason for
(c) 25 0 (d) 30 0 this observation? [P.E.T. (Kerala) 2008]
151. Increasing order of density is: [P.E.T. (M.P.) 2003J (a) Lesser effective nuclear charge of oxygen than nitrogen
(a) Li < K < Na < Rb < Cs o o
(b) Li < Na < K < Rb < Cs o (b) Lesser atomic size of oxygen than nitrogen 0
(d Cs < Rb < K < Na < Li o (c) Greater inter-electron repulsion between two electrons
(d) K < Li < Na < Rb < Cs o . in the same p- orbital counter balances the increase in
152. Outer electronic configurations· of K, Cu and Cr are effective nuclear charge on moving from nitrogen to
respectively: [S.H.V. 2003] oxygen 0
(a) 451, 3d 10 3d
5 o (b) 4i, 3d 10 3d 4 0 (d) Greater effective nuclear charge of oxygen than nitrogen
(d 451, 3d 9 3d o (d) 45\ 3d 9 3d 4 o
4
0
153. Identify the correct order of the size of the following: (e) Higher electronegativity of oxygen than nitrogen 0
[CS.S.E. 2007, 10] 161. Column I Column II
. (a) Ca 2+ < K+ < Ax < Cl- < 52- o (A) He (n High electron gain enthalpy
(b) Ax < ea2+ < K+ < Cl- < o (B) CI (ii) Most electropositive element
(C) Ca (iii) Strongest reducing agent
(c) Ca2+ < Ax < K+ < Cl- < S2- o
(D) Li (iv) Highest ionisation energy
(d) Ca 2+ < K+ < Ax < S2- < cr o The correct match of contents in Column I with those in
154. With which of the following· electronic configuration an Column II is: [P.E.T. (Kerala) 2008]
atom has the lowest ionisation enthalpy? [C.B.S.E. 2007) (a) A-(ill), B--(i), C-(ii), D-(iv) 0
(a) Ii 2i 2p3 0 (b) Ii 152 2p6 351 0 (b) A-(iv), B--(ill), C-(li), D-(O 0
2 2 2
(d 15 25 2p6 0 (d) Ii 15 2p5 0 (d A-(li), B-(iv),C-(i), D-(ili) 0 .
155. In which one of the following pairs the radius of the second (d) A-(i), B--(ii), C-(ill),· D-(iv) 0
species is greater than that of the first? [P.E.T. {Kcl'ala) 2007J (e) A-(iv), B-(i), C-(li), D-(lii) 0
(a) Na, Mg 0 (b) 0 2-, N3- 0 162. An element X belongs to fourth period and fifteenth group
(c) Li+, Be2+ 0 (d) Bi+, s1+ 0 of the periodic table. Which one of the following is true
(e) Al, Be 0 regarding the outer electronic configuration of X? It has:
156. The electronic configurations of four elements are given [P.M.T. (Ke:rala) 2008]
below. Arrange these elements in the correct order of the (a) partially filled d-orbitals and completely filled s-orbital
magnitude (without sign) of their electron affinity. o
(i) 152 2p5 (ii) 3i 3p5 (b) completely filled s-orbital and completely filled
2 p-orbitals 0
(ill) 25 2p4 (iv) 3i3p4
(c) completely filled 5-<?rbital and half filled p-orbitals .0
Select the correct answer using the codes given below:
(d) half filled d-orbitals and completely filled 5-orbital 0
[P.M.T. (Kerala) 20071 (e) completely filled 5-, p- and d-orbitals 0
(a) (i) < (li) < (ill) < (iv) 0 (b) (li) < (D < (iv) < (ill) 0 163. The correct order of increasing electron affinity of halogens
(d (0 < (ill) < (iv) < (li) ·0 (d) (ill) < (iv) < (li) < (i) 0 is: U'.E.T. (MJ'.) 2oo8J
(e) (iii) < (iv) < (i) < (li) 0 (a) F < Cl < Br < I 0 (b) I < Br < F < CI 0
157. The electronic configuration of the atom having maximum (c) I < Sr < Cl < F 0 (d) Sr < I < F < Cl 0
difference in first and second ionisation energies is: 164. In which of the following auangements, the sequence is not
(P.M.T. (Kera}a) 2007J strictly according to the property written against it?
2
(a) 15 , 2i 2p6, 3s
1
0 (b) Ii, 152 2p6, 3i 0 rAJ.f.E-E, 200~]
2 2
(c) 15 , 15 2pl 2 2 2
0 (d) Is , 15 2p6, 35 3p3 0 (a) CO2 < Si02 < Sn02 < Pb02 : increasing oxidising power 0
(b) HF < HCl < HSr < HI : increasing acid strength 0
(e) 152, 152 2p3 0
(c) NH3 < PH3 < AsH3 < SbH3 : increasing basic strength 0 (a) Cl < F < 0 < S o (b) 0 < S < P < CI o
(d) B < C < 0 < N : increasing first ionisation energy 0 (c) F < S < 0 < 0 o (d) S < 0 < CI < F o
165. The set representing the correct order of ionic radius is: 171. In a periodic table, the basic character of oxides:
[A.I.E.E.E. 2009] lJ.KE. (W.B.) 2010]
(a) Li+ > Be2+ > Na+ > Mg2+ o (a) increases from left to right and decreases from top to
(b) Na+ > U+ > Mgz+ > Bez+ o bottom 0
(c) Li+ > Na + > Mgz+ > Bez+ o (b) decreases from right to left and increases from top to
(d) Mg2+ > Be2+ > Li+ > Na + o bottom 0
166. The correct order of ionisation energy of C, N, 0, F is : (c) decreases from left to right and increases from top to
[CKT. (Karnataka) 2009] bottom 0
(a) F < N < C < 0 0 (b) C < N < 0 < P 0 (d) decreases from right to left and decreases from top to
(c) C < 0 < N < F 0 (d):F < 0 < N < C 0 ~~m 0
167. Ionisation energy of He+ is 19.6 x 10-18 J atom-I. The energy 172. Which of the following orders regarding ionization energy
of the first stationary state (n = 1) of Li2+ is : is correct ? (J.E.E. (W.B.) 2010]
[AI.KKK 2010] (a) N > 0 > F 0 (b) N < 0 < F 0
(a) 8.82 X 10-17 J atom-1 0 (b) 4.41 x 10-16 J atom-l 0 (c) N > 0 < F 0 (d) N < 0 > F 0
(c) --4.41 X 10-17 J atom-lD (d) -2.2 x 10-15 J atom-1 0 173. The diagonal partner of element B is :[j.E.E. (Orissa) 2010]
[Hint: EH (for H) x Z2 = I.E. (a) Li 0 (b) Al 0
EH x 4 = I.E. of He+ -19.6 x 10":18 J (c) Si [j (d) Mg 0
19.6 x 10-18 174. The first (~#l)
and second (~#2) ionisation enthalpies
or. EH '" 4 (in kJ mol-I) and the electron gain enthalpy (~gH) in
kJ morl of elements I, It III, IV and V are given below :
18
-E x 9-
E·Li'+-H 19.6 x 10- 9
- 4 x
Element . ~#l ~#2 ~H
= -44.1 x 10-18 J -4.41)( 10-17 J] I 520 7300 60
168. The correct sequence which shows decreasing order of the II 419 3051 -48
ionic radii of the elements is : [AJ.B.B,E, 2010) III 1681 3374 -328
(a) Oz- > P- > Na+ > Mg2+ > Al3+ 0
IV 1008 1846 295
(b) Al3+ > Mg2+ > Na+ > P- > Oz- 0 V 2372 5251 +48
(c) Na+ > Mgz+ > Al3+ > 0 2- > F 0 The most. reactive metal and least reactive non-metal of
(d) Na+ > P- > Mgz+ > 02- > Al3+ 0 these are respectively: [P.E.T. (Kerala) 2010J
[Hint : The ionic radii decreases in isoelectronic species as atomic (a) I and V 0 (b) V and II . 0
number increases i.e., z/eincreases.
(c) II and V 0 (d) IV and V 0
Ions 0 2- P- Na+ Ml:l- -Ae+
[Hint : The values suggest that I is Li, II is K, ill is Br, IV is I
8 9 11 12 1.2 E.=1.3] and V is He.]
z/e 10=0.8 10 =0.9 10 1.1 10 10
169. Among the elements Ca, Mg, P, CI, the order of increasing 175. The electron affinity value~ <;if elements A, B, C and 0 are
atomic radii is : ,IC.B.s.E. (P.M.T,) 2010] respectively -135, ~, -200 and -348 kJ mOrl. The outer
(a) Mg < Ca < 0 < P 0 (b) CI < P < Mg < Ca 0 electronic configuration of B is : ll!.A.M,CE,T. (Engg-) 2010)
(c) P < 0 < Ca < Mg 0 (d) Ca < Mg < P < 0 0 (a) 3s z3p5 0 (b) 3i3p4 0
170. Which of the following represents the correct order of (c) 3s z3p3 0 (d) 3s 23p2 0
increasing electron gain enthalpy with negative sign ?
(CS.S.E. (P.M'.T.)2010j
Set II : This set contains questions with two or more correct· answers.
176. Covalency is favoured in the following cases: (c) Pb4+ salts are better oxidising agents 0
(a) a smaller cation 0 (d) As5+ salts are oxidising agents 0
(b) a larger anion 0 179. Which of the following oxides are amphoteric?
(c) large charges on cation and anion 0 (a) BeO 0 (b) SnO 0
(d) a cation without noble gas configuration 0 (c)Zno [j (d) Al20 3 0
176. Stability of ions of Ge, Sn and Pb will be in the order: 180. On moving down the group from F to I, which of the
(a) Ge 2+ < Sn2+ < Pb 2+ 0 (b) Ge4+ > Sn4+ > Pb4+ 0 properties decrease?
(c'i Sn4+ > Snz+ 0 (d) Pb2+ > Pb4+ 0 (a) Ionic radius 0 (b) Ionisation energy 0
178. Which of the following statements is/are correct? (d Oxidising agent 0 (d) Electronegativity 0
(a) Te+salts are oxidising agents 0 181. The elements which exist in liquid state at room tempera-
ture are:
(b) Ga+ salts are reducing agents 0
Classification of Elements and Periodicity in Properties 59,'
,::lt~:~~~i~Ji~:~iL~;!jf~1fo/~···
186.\lVhich ofthe following elements belongs to halpgen group?
, "'(a),' 152, is2 2p6~3523p5 0
$) ls2,2s2Zp6,3s2 3p6; 4i 0
(a) Lt < Na+ < K+ 0 (b) Na+ < Mg2+ < Al3+ 0 (c) [Ar] 3d lO, 4i 4p5 0 (d) [Kr] 4d10, 552 5p5 0
(c) Al3+ < Mg2+ < Na+ 0 (d) Li+ > Na+ > K+ 0 187. Which of the following represents the same element?
183. Stability order of +3 and +1 states of boron family element (a) 105 0 (b) Unnilpentium 0
is: (c) Ha 0 (d) Rf 0
(a) Ga3+ <; In3+ < n3+ o (b) Ga+ > In+ > n+ o 188. Ionic radius of : rl.l.T. 1999]
(c) Ga+ < In+ < n+ o (d) Ga3+ > Ga+ o (a) Ti4+ < Mn7+ o (b) 35Cl- < 37 cr 0
184. Which of the following pairs contain elements with similar (c) K+ > cr o (d) p3+ > p5+ 0
atomic radii? 189. Select the process/es which is/are endothermic in nature?
(a) Co, Ni 0 (b) Zn, Mo o (a) H + e- ~ H- 0 (b) 0- + e- ~ 0 2- 0
(c) Rh, Ir 0 (d) Hf, Ti o (c) Ar+e-~Ar- 0 (d) M~M++e- 0
185. Which of the following species has same number of 190. Choose the pair in which IE! of the first element is greater
unpaired electrons? than lEt of second element ,but in case of 1E2' The order is
(a) Cr 3+ o (b) Mn2+ o reversed :
3
(c) Fe + o (d) Cu2+ o (a) N,O o (b)F,O o
(c) Be, B o (d) P,S o
1. (d) 2. (c) 3. (d) 4. (b) 5. (d) 6. (d) 7. (e) 8. ,(b) 9. (a) 10. (b)
11. (c) 12. (d) 13. (a) 14. (b) 15. (e) 16. (a) 17. (c) 18. (d) 19. (d) 20. (d)
21. (d) 22. (e) 23. (b) 24. (e) 25. (b) 26. (b) 27. (a) 28. (a) 29. (a) 30. (a)
31. (b) 32. (c) 33. (d) 34. (d) 35., (e) 36. (d) 37. (a) 38. Cd) 39. (d) , 40. (b)
41. (a) 42. (b) 43. (b) 44. (b) 45. (b) 46. (d) 47. (b) 48. (e) 49. (c) 50. (b)
51. (d) 52. (b) 53. (a) 54. (a) 55. (d) 56. (a) 57. (d) 58. (b) 59. (c) 60. (d)
61. (d) 62. (b) 63. (a) 64. (a) 65. (a) 66. (d) 67. (d) 68. (b) 69. (c) 70. (e)
71. (d) 72. (a) 73. (b) 74. (c) 75. (d) 76. (a) 77. (b) 78. (b) 79. (a) 80. (c)
81. (b) 82. (a) 83. (a) 84. (a) 85. (b) 86. (d) 87. (c) 88. (d) 89. (b) 90. (d)
91. (d 92. (b) 93. (a) 94. (d) 95. (c) 96. (d) 97. (a) 98. (b) 99; (b) 100. (b)
101. (a) 102. (a) 103. (d) 104. (d) 105. (c) 106. (a) 107. (b) 108. (d) 109. (b) 110. (c)
111. (d) 112. (a) 113. (d) 114. (e) 115. (b) 116. (a) 117. (d) 118. (e) 119. (b) 120. (d)
121. (b) 122. (c) 123. (a) 124. (d 125. (p) 126. (b) 127. (d) 128. (a) 129. (d) 130. (b)
131. (a) 132. (e) 133. (b) 134. (a) 135. (b) 136. (c) 137. (b) 138. (a) 139. (b) 140. (a)
141. (a) 142. (a) 143. (b) 144. (b) 145. (c) 146. (a) 147. (c) 148. (d) 149. (d) 150. (e)
151. (a) 152. (a) 153. (a) 154. (b) 155. (b) 156. (e) 157. (a) 158. (d) 159. (c) , 160. (c)
161. (e) 162. (c) 163. (b) 164. (c) 165. (b) 166. (c) 167. (c) 168. (a) 169. (b) 170. (b)
171. (c) 172. (c) 173. (c) 174. (e) 175. (c) 176. (a,b,c,d) 177. (a,b,c,d) 178. (a,b,c) 179. (a,b,c,d) 180. (b,c,d)
181. (b,c,d) 182. (a, c) 183. (c, d) 184. (a, e) 185. (b,e) 186. (a,c,d) 187. (a,b,c) 188. (b,d) 189. (b,c,d) 190. (a,c,d)
60' G.R.B. Inorganic Chemistry for Competitions
,~, Objective Questions for liT ASPIRANTS ~

1. The paramagnetic species among the following is ; 5. If each orbital can take maximum of three electrons, the
. Na+ Zn2+ Cu + Fe3+ I "I I
number of elements in the third period of the periodic table
(a) Na+.· . (b) Zn2+ (c) Cu+ (d) Fe3+ will be.:
(a) 12 (b) 6 •
(Hint : Paramagnetic species have at least one unpaired electron.
Write the electronic configuration and observe the unpair- (c) 8 (d) 24
ed orbital. [Hint : In third period, 35- and 3p-orbitals ar.e filled. Total orbitals
Na+ ; 182, 2s2 2p6 All paired; to be filled = one s + three p 4. Thus, number of elements
=4x3 =I2J '.
(11)
2
bl+ : Ii, 2s 2l, 3i 3l3dlO
6. The number of elements which can be accommodated in
All paired;
(30)
the present set-up of the long form of the periodic table is:
Cu+ : Il, 2i 2p6, 3i 3p6 3io
(a) 120 (b) 118
All paired;
(c)' 122 (d) 124
(29)
[Hint: In the present set-up, on the basis of aufbau pnnciple
Fe3+ ; Ii, 2s2 2p6, 3l 3p6 3d 5 Unpaired orbitals]
and four blocks of elements, the last period, i.e., 7th period
(26)
is· to accommodate 32 elements (752, S/14, 6d 1O, 7p6).
2. The diamagnetic species among the following is : Thus, total elements can be accommodated 118 (86 up
Cu2+ , Cr3+, Co"+, Cd 2+ to 6th period plus 32 in the 7th period).]
(b) Cd2+ (c) Cr3 + (d) Co3+ 7. What would be the atomic number of the next halogen' if
[Hint ; Diamagnetic species have all paired electrons. discovered in future?
Cu2+ : 182, 2s2 2p6, 382 3p6 3d 9 - Unpaired orbital ; (a) 115 (b) 119
(29)
(c) 117 (d) 121
Cr3+ : 152, 2l 2p6, 3i 3p63d3 Unpaired orbitals; [Hint: The next halogen will have 7s 27p 5 outer configuration.
Since, the filling of 7p-orbitals will begin after S/- and 6d-
(24) 3d
orbitals, thus the atomic number of the new halogen will
Co3+ ; Ii, 252 2p6, 352 3p6 - Unpaired orbitals;
be 112 (up to the filling of 6d-orbitals) plus S, i.e., 117.)
(27)
Cd Z+: 15 2, 2s 2 2p6, 3s Z 3p6 3d 10, 45 2 4p6 4d 10 _ All paired) 8. The energies of the electron in a hydrogen like ion are given
by:
(48)
3. The correct decreasing (jrder of electropositive character En - (2.18 X; 10- 22
18) (~2)'
where n isp~cipal
quantum
among' the follOwing elements is ; number and 2 is the atomic number of the eleIIlent. The
Fe, Sc, Rb, Dr, Te, F, Ca ionisation energy (in kJ mor1) of the Li2+ ion is:
(a) Fe > Sc > Rb > Dr > Te > F > Ca '(a) 1.18 x 103 . (b) 118 x 10"
(b) Ca> Rb > Sc > Fe > Te > F > Dr (c) 0.118 x 10" (d) n.8 x 103
(c) Rb > Ca > Sc > Fe > Dr > Te > F
(d) Rb > Ca > Sc > Fe > Te > Dr > F [Hbit : Ionisation energy == (2.18 x 10- 18)Z2 (~Z) x N J moC' where
[Hint ; Remember the following points :
(i) Alkali and alkaline earth metals are most electro- N is the Avogadro number.
positive. Alkali metals' are more electropositive than For Liz+ (2.18 x 10-1S, x 32 (1) x 6.02 x l023J mol-I)
alkaline earth metals.
9. First and second ionisation energies of magnesium are
(in In d-block series, the. elements near alkaline earth
7.646 and 15.035eV respectively. The amount of energy in
metals are more electropositive than rest of the
members.
kJ needed to convert all the atoms of magnesium into Mg2+
(iii) Metalloids are less electropositive than metals. ions present in 12 mg of magnesium vapours is :
. (iv) Halogens (Non-metals) arE'! least electropositive. In [Given; leV = 96.5 kJ morl ]
halogen group, electropositive character increases as (a) 1.1 (b) 1.5
atOlnic number increases.] (c) 2.0 (d) 0.5
4. The correct decreasing order of atomic size among the [Hint: Total energy needed to convert one Mg atom into Mg2+
following species is : (gas) ion == lEI + lEn
AI, K+, CL, S2-, ci+ = 22.681 eV 2188.6 kJ mol-1
3
12 mg of Mg = O.S X 10- mole]
(a) Ci+>K+>AI>O->S2- (b) K+>Ca2+>CL>AI>S2-
. 10. Which of the following has highest electron gain enthalpy?
(c) S2-:>O->Ar> K+>ci+ (d) S2->Ar>CL>Ci+ >K+
(A) [Ne] 3i 3p3 ; (B) [Ne] 3i 3p4 ;
[Hint ! In isoelectronic ions, the atomic size decreases as ~ ratio
(C) [Ne] 3i 3p5; (D) [Ne] 3i 3p2
increases.
(a) (A) (b) (B)
S2- 3: == 16 . CI- 3 17 Ar 3: _ 18 . K+ Z _ 19 . C 2+Z _ 20]
e 18' e 18 e - 18' e -18' a e- 18 (c) (C) (d) (D)
Classification of Elements and Periodicity in Properties
.lHint.: .The element (Cl will have highest electron gain enthalpy .(d) The size of the cation is always less than the size of the
as it easily gains one more .electron to achieve stable • neutral atom
configuration of next inert . gas.l 17. (A), (B) and (e) are elements in the third short period. Oxide
11. The element with atomic number 35 belongs to : of (A) is ionic, that of (B) is amphoteric and of (e) a giant
(a) d-block (b) f~block molecule. (A), (B) and (e) have atomic number in the order:
(c) p-block (d) 5-block (a) (A) < (B) < (e) (b) (e) < (B) < (A)
[Hint : Write the electronic configuration on the basis of aufbau (c) (A) < (e) < (B) (d) (B) < (A) < (e)
principle. [Hint : A, B and C are magnesium, aluminium and silicon.
1;, 2l, 35
2
3l
1O 2
3d , 45 4p5
Magnesium forms ionic oxide,. MgO, aluminium forms
The last electron is accommodated on p-energy shell. ]
amphoteric oxide, AlzO" and silicon forms a giant
.12. The. electronic configurations for some neutral atoms are molecule, Si0:2.]
given below : 18.. Match the List I with List II and select the correct answer:
(A) Ii, 2s2 2p6, 35 2 (B) 15 2,2s2 2p6, 351
List I List II
(e) 15 , 2i 2p6, 35 3p2
2 2
(D) ls 2, 15 2 2p6, 3s 2 3p3
(A) Most electronegative element (1) Chlorine
Which of these is expected to have the· highest second (B) The element having highest (2) Hydrogen
ionisation enthalpy? electron gain enthalpy
(a) (A) (b) (B) (C) Most abundant element in (3) Nitrogen
(c) (e) (d) (D) the universe
[Hint : B atom after losing outermost electron acquires noble gas (D) Most abundant gas in atmosphere (4) Fluorine
configuration (stablec6nfigurationl. It is difficult to A B C D
remove the next electron from B+ (15 2, 15 2 2p6) ion.] (a) I 2 3 4
13. The amount of energy released when 106 atoms of iodine (b) 4 3 2 1
in vapour state are converted to r ions is 4.9 x 10-13 J. What (c) 4 1 2 3
is the electron affinity of iodine in eV per atom? (d) 2 3 4 1
. (a) 2.0 (b) 2.5 19. The five successive ionisation energies of the element are
. (c).2,75i ...·c ; -. '. (d)-:3;96 $00,2427, :?Q5~,25024 and 32824 kJ mor1 respectively.The
:tMin.t ;:A~oi.mt ~f en~gy rel~~edf~r. 1 m~leofiodine n~ber btv.alence el~ctrons is: .
.' . ". 4.~x 10;-13. " . .'23> -(a) '.$)·5 '.
106 x 6.02 x 10 (c) 4 (d) 2
29.5 X 104 J 295 kJ morl [Hint : Fourth ionisation energy abruptly increases. This shows
1 eV per atom = 96.3 kJ morl) that fourth electron isrernoved from inert gas core.]
14. Match the following lists and select the correct answer: 20. Which' of the following species has the negative electron
gain' enthalpy?
List I List II (a) F- (b) 0
(A) Is 2, 252 2p6, 3i 3p6, 4s1 (1) d-block element (c) 0- (d) Na+
(B) . Ii, 152 2p6, 3i 3p6 (2) Halogen [Hint : Energy is released when electron is added to 0 but energy
(C) Ii, 2s 2 2
2p 6, 35 3p6 3d 6
, 4i· (3) Alkali metal is absorbed in rest of the cases when electron is added.]
(D) Ii, 152 2p5 .. (4) Noble gas 21. The ionic radius of Cr is minimum in which of the
ABC D following compounds?
(a) 1. 2 3 4 (a) CrF 3 (b) CrCl3
[Hint: Cr has maXimum oxidation number (+6) in K2Cr04 and
(b) 3 4 1 2
thus, has minimum ionic radius.]
(c) 1 3 2 4
(d) 2 4 3 1 22. Arrange Ce3+, La3+, Pm3+ and Yb 3+ in increasing order of
15. Which of the following is the wrong statement? their size:
(a) Yb3+ < Pm 3+ < <
(a) All the actinide elements are radioactive
(b) Ce 3+ < Yb3+ < Pm 3+ < La 3+
(b) Alkali and alkaline earth metals are sMblock elements
(c) Yb 3+ < Pm3+ < La3+ < Ce3+
(c) Chalcogens and halogens are p-block elements
(d) The first member of the lanthanide series is lanthanum (d) Pm3+ < La3+ < < Yb3+
16. Which of the following is the correct statement? [Pint : Lanthanide contraction is observed in these ions, i.e., ionic
radius decreases as atomic number increases.]
(a) The second ionisation potential of an atom is always less
than the first ionisation potential. 23. Which of the following statements related to; the' modem
(b) The addition of an electron to a neutral atom is an periodic table is incorrect?
endothermic process (a) The p-block has 6 vertical columns, i.e., groups
(c) Fluorine has. the maximum electronegativity (b) The d-block has 8 vertical columns
(c) Each block contains a number of columns equal to the (d) In alkali group, the chemical reactivity increases but
number of electrons that can occupy that subshell decreases in the halogens with increase in atomic
(d) The block indicates value of azimuthal quantum number down the group
number (1) for the last subshell that received electrons 25. The values of electronegativity of atoms A and Bare 1.20
in building up the electronic configuration. and 4.0 respectively. The percentage ionic character of
[Hint : d-block has 10 columns.] A-Bbondis:
24. FollOwing statements regarding the periodic trends of (a) 50.0% (b) 72.2%
chemical reactivity of the alkali metals and the halogens (c) 55.3% (d) 43.0%
are given. Which of these statements gives the correct [Hint : % ionic character = 16(4 - 1.2) + 3.5(4 - 1.2)2 72.2]
picture? 26. The element with atomic number 118 (Duo) has been
(a) The reactivity decreases in tite alkali metals but discovered recently. Which of the follOWing is not expected
increases in halogens with increase in atomic number for this element?
down the group (a) It is radioactive and unstable element
(b) In both the groups, the chemical reactivity decreases (b) It is a solid at room temperature
with increase in atomic number down the group (c) Its ionisation enthalpy is minimum in the group
(c) In both the groups, the chemical reactivity increases
(d) It has 7i7p6 outer shell configuration
with increase in atomic number down the group
1. (d) 2. (b) 3. (d) 4. (c) 5. (a) 6. (b) 7. (c) 8. (d) 9. (a) 10. (c)
11. (c) 12. (b) 13. (d) 14. (b) 15. (d) 16. (c) 17. (a) 18. (c) 19. (a) 20. (b)
21. (d) 22. (a) 23. (b) 24. (d) 25. (b) 26. (b)
Matrix Matching Questions for liT Aspirants

1. Match List-I with List-II: (c),81 (r) s (w)DIA
List-I List-II (d) 64 (s) d (x) IA
(Group/Period)* (Element) 4. Match List-I with List-II:
(a) 7th period (p) Transition elements List-) List-II
(b) IIIB group (q) Inner transition elements (a) Halogen (p) Oxygen
(c) IA (r) Hydrogen (b) Chalcogen (q) Chlorine
(d) VIlA (s) Halogens (c) Noble gas (r) Sulphur
2. Match List-I with List-II: (d) Representative element (s) Neon
List-) List-II 5. Match List-I with List-II:
(a) (P + 1) > N (p) Al List-) List-II
(b) (P + 1) = 7 ('I) Pb (Element) (Information)
(c) (P + 1) <N (r) C (a) Rutherfordium (p) Z = 104
(d) (P + 1) N (s) Si (b) Kurchatovium (q) I-block
Here, P = Number of period. (c) Thorium (r) d-block
N = Number of valence electrons. (d) Neptunium (s) Transuranic element
[Hint :In p-block: 6. Match List-I with List-II:
(P + 1) > N; (P + 1) < N, (P + 1) = N 1
respectively represent metal, non-metal and metalloid. List-) List-II
(a) Dobereiner (p) Law of octave
3. Match the atomic number in List-I, with the block in List-II
(b) Alexander Newlands (q) Davy Medal
and groups in List-III:
List-II (c) A.E.B. de Chancourtois (r) Law of triads
List-I List-III
(Block) (Group)* (d) Dmitri Mendeleev (s) Based on atomic weights
(Atomic number>
'(a) 55 (p)p (u) VIII
(b) 45 (q) I (v) IIIB
*Modern Mendeleev's Periodic Table

7. Match. List;.I. with· LisHI:" 9. Match thecohirrm-lwithColumri-II and Column-III:
LisHI,· Column-I . ',C~lu.mn-II Column-III
(a) Lanth~de co~traction .' .(prd~block "," (AtQmichumper)' (Group)* (Period)
(b) Diagonal relationship (q) Elements of 3rd period (a) 13 (p) IlIA (u) 6
(c) Typical elements (r) I-block (b) 35 (q) VIlA (v) 5
(d) Inner transition elements (s) Be-AI (c) 56 (r) ITA (w)3
8. Match the electronic configuration (List-I) with the ioni- (d) 78 . (s) VIII (x) 4
sation energy (List-II): 10. Match the elements in List-I with their properties in List-II:
List-I List-II List-I List-II
(Electronic (Ionisation energy)
(a) Mercury (p) Metal
configuration) kJ/mol
(b) Bromine (q) Densest element
(a) ns 2 (p) 2100 (c) Osmium (r) Element with highest
(b) ns 2np l (q) 1400 melting point
(c) ns 2 np 3 (r) 800 (d) Wolfram (Tungsten) (s) Liquid at room temp
(d) ns 2np 6 (s) 900
1. (a-p, q) (b-p, q) (c-r) (d-r, s) 6. (a-r, s) (b-p, q, s) (c-s) (d~s)

2. (a-p, q) (b-q) (c-r) (d-s) 7. (a-p, r) (b-s) (c-q) (d-r)
3. (a-r-x) (b-q-r) (c-p-w) (d-q-v) 8. (a-s) (b-r) (c-q) (d-p)
4 •. (a-q) (b-p, r) (c-s) (d-p, q, r) 9. (a-p-w) (b-q-x) (c-r-u) (d-s-u)·
5. (a-p, r, s) (b-p, r, s) (c-q) (d-q, s) 10. (a-p, s) (b-s) (c-p, q) (d-p, r)
I Assertion-Reason Type Questions

The questions given below consist of an Assertion (A) and 5. (A) Cu2+ is diamagnetic.
Reason (R). Use the following key to choose the correct answer. (R)' All the orbitals present in Cu2+ ion are doubly occupied.
(a) If both (A) and (R) are' correct and (R) is the correct 6. (A) The size decreases as Pb > Pb 2+ > Pb4+.
explanation of the (A). (R) ~ increases, i.e., force of attraction towards nucleus
(b) If both (A) and (R) are correct and (R) is not the correct increases.
explanation of (A). 7. (A) There are fourteen elements in the lanthanide series and
(d If (A) is correct and(R) is incorrect. fourteen elements in the actinide series.
(d) If both (A) and (R) are incorrect. (R) All the elements of the actinide series are radioactive.
1. (A) Each d-block series contains ten elements. ~. (A) The ~oup 18 consists of elements which are in gaseous
. (R) The maximum capacity of d-orbitals is of ten electrons state under ordinary atmospheric conditions .
as in each series d-orbitals are ~adually filled up. (R) AIl the elements of group 18 have stable configuration.
2. (A) Helium and beryllium have similar outer electronic 9. (A) First ionisation energy of nitrogen is lower than oxygen.
configuration ns 2 • ' (R) Across a period effective nuclear charge decreases.
(R) Both are chemically inert. [A.I.I.MS. 1994] [A.I.I.M.S. 2005]
3. (A) Electron gain enthalpy of oxygen is less than that of 10. (A) F atom h,as a less negative electron affinity than chlorine.
fluorine but greater than that of nitrogen. (R) Additional electrons are repelled more effectively by 3p
(R) Ionisation enthalpy is as follows: ,N > 0. > F electrons in Cl atom than by 2p electrons in F atom.
[A.I.I.M.S. 19981 11. (A) The ionic size of Mg2+ is larger than AI3+.
4~ (A) The first ionisation energy of Be is greater thim that of B. (R) In isoelectronic species, greater the nuclear charge, less is
(R) 2p-orbital is lower in energy than 2s-orbital. [U.T. 2001] the size.
1. (a) 2. (c) 3. (c) 4. (a) . 5. (d) 7. (b) 8. (b) 9. (d) 10. (c) 11. (a)
"Modem Mendeleev's Periodic Table,

,64 G.R.B. Inorganic Chemistry for Competitions
111II1Ii THOUGHT TYPE QUESTIONS 11111111

THOUGHT 1 (c) 3rd period and 2nd group
(d) 4th period and 2nd group
Numerous forms of the periodic table have been devis- 5. Elel1\ents A, B, C, D and E have the follOwing electronic
ed from time to time. A modem version, which is most configurations :
convenient and widely used is the long or extended form of (A) ti, 2i 2pl (8) ti, 2i 2p6, 352 3pl
periodic table. The aufbau principle and the electronic.
(C) ti, 2i 2p6, 3i 3p3 (D) ti, 152 2p6, 3i 3p5
configuration of atoms provide a theoretical foundation for
(E) ti, 2i 2p6,3i 3p6
the periodic classification. The horizontal rows are called
Which among these will belong to same group in the
periods. There are altogether seven periods. The first period
periodic table ?
consists of 2 elements. The subsequent periods consist of 8,
(a) (A) and (C) (b) (A) and (D)
8, 18, 18 and 32 elements respectively. The seventh period is
(c) (A) and (8) (d) (A) and (E)
incomplete and like the sixth period would have maximum
6. The outer electronic configuration of an element is,
of 32 elements. (n 2) t (n -:-1) d1 ni,
Elements having similar outer electronic configurations To which block in the long form of the periodic table does
in their atoms are grouped in vertical columns. These are this belong ?
referred to as groups or families. According to the reco- (a) s-block (b) p-block
mmendation of IUPAC, the groups are numbered 1 to 18 (c) d-block (d) f-block
replacing the older notation of groups 0, IA, IIA, ......... VIlA, 7. The elements with atomic numbers 90 to 103 are known
VITI, IB, ......... VII B. as:
Each successive period in the periodic table is associated (a) d-block elements (b) lanthanides
with the filling up next. higher principal energy level (c) actinides (d) transition elements
following aufbau sequence. The number of elements in 8, In Me:l1deleev'spe,ri?dictaJ:>le,silverbelongstolB group.
each period is twice the number of atomic orbitals available The gi-oupto which silver :belongs inAongform Of periodic
in the energy level that is being filled. All the elements are table is:
classified into four blocks, i.e., s-block, p-block, d-block and (a) first (b) eleventh
I-block depending on the type of atomic orbitals that are (c) tenth (d) sixteenth
being filled with electrons. 9. The elements in which 4f-orbitals are progressively filled
are called as :
1. An element belongs to group t7. It is present in third period
(a) lanthanides (b) actinides
and its atomic number is t7. What is the atomic number of
(c) trarisition elements (d) chalcogens
the element belonging to same group and present in fifth
10. If aufbau rule is not followed, Ca-20 will be placed in
period?
(a) 25 (b) 33 ......block.
(a) s- (b) 'p-
(c) 35 (d) 53
(c) d- (d) f-
2. Elements in the same vertical group of the periodic table
[Hint ; U aufbau rule is not followed, the electroruc configuration
have generally the same :
of Ca-20 will be 1;, 2l 2p6, 352 3p6 3d l , i.e" last electron
(a) atomic number
will be accommodated on d- orbital.)
(b) electronic configuration
(c) atomic mass THOUGHT 2
(d) number of electrons in the outermost shell of their
atoms
The minimum amount of energy required to remove the
3. The element with atomic number Its is likely to have the most loosely bound electron from an isolated atom in the
same outer shell configuration as the element with atomic gaseous state is known as ionisation energy or first ioni- .
number: sation energy or ionisation enthalpy (IE 1) of the element.
(a) t8 (b) 28 The energy required to remove the second electron from
(c) 58 (d) 88 the monovalent cation is called second ionisation enthalpy
4. What is the position of the element in the periodic table (IE 2 ). Similarly, we have third, fourth ........... ionisation
satisfying the' electronic configuration (n - 1) d1 nJ- for enthalpies. The values of ionisation energy depends on a
n 4? number of factors such as (i) size of the atom (ii) screening
(a) 3rd period and 3rd group effect (iii) nuclear charge (iv) half filled and fully filled orbitals
(b) 4th, period and 3rd group (v) shape of orbital. .
Classification of Elements and Periodicity in Properties . 65
In a group, the ionisation energy decreases from top to electron affinity depends on a number of factors such as (i)
bottom. In a period, the value of ionisation energy increases atomic size (ii) effective nuclear charge (iii) screening effects (Iv)
from left to right with breaks where atoms have somewhat half and fully filled orbitals and (v) shape of orbital.
stable configurations. In general, electron affinity increases as the atomic radii
1. Compared to the second ionisation energy (IE 2 ) of an atom, decrease in a period. However, there are exceptions when
the third ionisation energy (IE 3 ) is: the atoms have stable configurations. In a group, electron
(a) the same (b) greater affinity decreases as the size increases. However, the members
(c) smaller (d) half of 3rd period have somewhat higher values than the members
2. In a· period, the ionisation energy is lowest for the: in the 2nd period of the same subgroups.
(a) noble gases (b) halogens 1. What is the MI of the follOWing reaction?
(c) alkaline earth metals (d) alkali metals Mg(g) + 2F(g) ----7 Mg2+(g) + 2F-(g) or MgF2 (g)
3. The electronic configurations of some neutral elements are
If electron affinity of F(g) ::: -328 kJ morl and
given below : .
(A) Ii, '1:il; (8) Ii, 2s2 2pI; (C) Is 2, 2s2 2p4 ; (0) Is2,2sZz p3 First ionisation energy of Mg = 737.7 kJ morl and
which of these electronic configurations would be expected Second ionisation energy of Mg = 1451 kJ mOrl.
to have highest second ionisation energy (IE 2)? (a) 1532.7 kJ mol-1 (b) 1860.7 kJ morl
l
(a) (A) (b) (8) (c) 2516.7 kJ mor (d) 2844.7 kJ morl
(c) (C) (d) (0)
[Hint: Mg(g) Mg2+(g) + 2e' lEI + lE2 = 2188.7 kJ morl
4. The first (IE I) and second (IE 2 ) ionisation energies
2F(g) + 2e -7 2F EA = -2 x 328 = -656 kJ mol-1
(kJmOrI) of a few elements are shown below:
llH 1532.7 kJ mol-I]
lEI IE2
2. Which one of the following arrangements represents the
(A) 2372 5251
(8) 520 7300 correct order of electron gain enthalpy (with negative sign)
(C) 900 1760 of the given atomic species? [C.B.S.E. (P.M.T.) 2005]
(0) 1680 3380 (a) F < CI < 0 < S (b) S < 0 < CI < F
Which of the above elements is likely to be a noble gas? (c) 0 < S < F < CI (d) Cl < F < S < 0
(a) (A) (b) (8) 3. Which of the following has least electron affinity?
(c) (C) (d) (0) (a) Oxygen (b) Argon
5. In question no. 4, which of the .element is likely to be a (c) Nitrogen (d) Boron
non-metal? 4. The electron affinities of halogens are:
(a) (A) (b) (8)
F ::: - 332, CI =- 349, Br - 324, I = - 295 kJ morl
(c) (C) (d) (0)
The higher value of CI as compared to that of F is due to:
6. Which of the order for ionisation energy is correct?
(a) higher atomic radius of F
(a) Be > B > C > N > 0 (b) B < Be < C < 0 < N
(b) smaller electronegativity of F
(c) B < Be < C < N < 0 (d) B < Be < N < C < 0
(c) weaker electron repulsion in CI
7. Which of the elements Na, Mg, Si and P would have the
(d) more vacant p-subshell in CI
greatest difference between the first and second ionisation
5. Which of the following species has the highest electron
enthalpies?
affinity?
(a) Na (b) Mg
(a) F- (b) 0-
(c) Si (d) P
(c) Na+ (d) 0
8. The first ionisation energy of Mg, AI, P and S follows the
6. Which of the following processes is endoergic in nature?
order:
(a) 0- + e ----702- (b) CI + e ----7 cr
(a) Mg < AI < P < S (b) Al < Mg < P < S
(c) S + e ----7 S- (d) F + e F-
(c) Al < Mg < S < P (d) Mg < AI < S < P
THOUGHT 3 THOUGHT 4
The first (6.#1) and the second (6.#2) ionisation enthal-
The amount of energy released when an electron is
pies in kJ mol-1 and the electron gain enthalpy in kJ moCl of
added to an isolated gaseous atom to produce a monovalent
a few elements are given below:
anion is called electron affinity or first electron 'affinity or
electron gain enthalpy. The first electron affinity is given a Elements !J.#l !J.#2 L\.egH
negative sign as the addition of an electron to a n~utral atom (A) 520 7300 -60
is an exoergic process. The addition of electron to A-requires (B) 419 3051 -48
energy to overcome the force of repulsion. Thus, the second (C) 1681 3374 -328
(0) 1008 1846 -295
electron affinity is an endoergic process. The magnitude of
(E) 2372 5251 +48 (5) The element (0) would be least reactive non-metaL
(F) 738 1451 -40 (6) The element (A) has low first ionisation enthalpy but
Answer the following questions. Only one alternative is very high second ionisation enthalpy. It would be
correct. least reactive alkali metal, i.e., lithium which forms
covalent MX.]
1. Which one of the above elements is least reactive?
(a) (C) (b) (D)
THOUGHT 5
(c) (E) (d) (F)
2. Which one of the above elements is most reactive metal? Atoms of metals have only a few electrons in their valence
(a) (A) (b) (B) shells while atoms of non-metals generally have more
(c) (F) (d) (D) electrons in their valence shells. Metallic character is closely
3. Which one of the above elements is most reactive non- related to atomic radius and ionisation enthalpy. Metallic
metal? character increases from top to bottom in a group and
(a) (C) (b) (D) decre<;lses from left to right in a period. Metallic character is
(c) (E) (d) (F) inversely related to electronegativity.
4. The metal which can form a stable binary halide. of the 1. Which of the following groups contains metals, non-metals
formula MX2 (X = halogen): and metalloids?
(a) (A) (b) (B) (a) Group 1 (b) Group 17
(c) (F) (d) (D) (c) Group 14 (d) Group 2
5. Which one of above elements is least reactive noh~metal? 2. Non-metals belong to:
(a) (C) (b) (D) (a) s-block elements (b) p-block elements
(c) (E) (d) (F) (c) d-block elements (d) f-block elements
6. The metal which can form predominantly stable covalent 3. Considering the elements B, C, N, F and Si, the correct order
halide of the formula MX (X halogen): of their non-metallic character is:
(a) (F) (b) (B) (a}~B > C > Si > N > F (b) Si> C > B > N > F
(c) (D) (d) (A) (c) F > N » C > B > Si (d) F > N > C > Si > B
[Hint : (1) The element (E) having very high ionisation enthalpy 4. The electronegativities of the following elements increase
and positive electron gain enthalpy would be a noble
in the order:
gas, i.e., least reactive.
(a) C, N, Si, P (b) N, Si, C, P
(2) The element (B) would be most reactive metal as it
(c) Si, P, C, N (d) P, Si, N, C
has low ionisation enthalpy and low negative
5. Considering the elements B, AI, Mg and K, the correct order
electron gain enthalpy. Probably it is an alkali metaL
of their metallic character is :
(3) The element (e) would be most reactive non-metal
(a) B> AI> Mg > K (b) AI> K> B > Mg
as it has high negative value of electron gain
enthalpy. Probably it is a halogen.
(c) Mg > Al > K > B (d) K > Mg > AI > B
6. The element with maximum electronegativity belongs to:
(4) TIle element (F) would form stable MX2 as it has
first two ionisation enthalpies low and low value of
(a) period 2, group 17 (b) period I, group 18
electron gain enthalpy, i.e., it belongs to second (c) period 3, group 17 (d) period 2, group 16
group.
Thought 1 1. (d) 2. (d) 3. (a) 4. (b) 5. (c) 6. (d) 7. (c) 8. (b) 9. (a) 10. (c)
Thought 2 1. (b) 2. (d) 3. (c) 4. (a) 5. (d) 6. (b) 7. (a) 8. (c)
Thought 3 1. (a) 2. (c) 3. (b) 4. (c) 5. (d) 6. (a)
Thought 4 1. (c) 2. (b) 3. (a) 4. (c) 5. (b) 6. (d)
Thought 5 1. (c) 2. (b) 3. (d) 4. (c) 5. (d) 6. (a)
,.
The answer to eacil of the follo'wing questiolts is a single 5. How many unpaired electrons are present in Co3+ ion?
digit il/teger, rangillgfrom 0 to 9. 6. The first ionisation energy of lithium is 5.41 eV and electron
1. Among the following, the number of elements showing gain enthalpy of" chlorine is 3.61 eV. The M:l in kJmorl
only. one non-zero oxidation state is : for the reaction :
0,0, F, N, P, Sn, TI, Na, Ti LI.I.T. 20101 Li(g) + O(g) ----7 Li+(g) + cr(g) is 1.737 x lit kJ mOrl
2. How many groups are occupied by p-block elements in long What is the value of x?
form of periodic table? 7. In a period, the element with largest atomic volume belongs
3. . How many diagonal' relatiOnships are . present in to which of the groups?
Mendeleev's periodic table? . 8. The ionistion energy of lithium is 500 kJ morl. The amount
4. If for an element (X), the values of successive ionisation of energy required to convert 70 mg of lithium atoms in
energies 11, 12, 13, 4 and 15 are 800, 2427, 3658, 25024, 32824 gaseous state into Li+ ions is:
kJ morl respectively, then the number of valence electrons
present are :
3
1. (2) Na exhibits +1 and F -exhibits only -1 oxidation state, 6. (2) ~ HLP. of Li + Eg of CI 5.41 - 3.61 1.8 eV
2. (6) 13, 14, 15, 16, 17 and 18th groups are occupied by p-block ~H morl 1.8 x 6.023 x 1023 eV
elements. = 1.8 x 6.023 x 1023 x 1.602 x 10-19 x 10-3 kJ
3. (3)
Li~ Be~ = 1.737 x 102 kJ
7. (1) In a period, alkali metal which belongs to group I shows largest
Mg Al 5i
(i) (ii)
atomic volume.
(iii)
70xlO-3 .
4. (3) As the difference between 13 and 4 is maximum, so the element 8. (5) 70 mg = 70 x 10-3 g = 7 1 x 10-2 mole
(X) has three valence electrons as after losing three electrons, Amount of energy required 1 x 10-2 x 500 kJ 5 kJ
it acquires stable inert gas configuration.
5. (4) Co3+-24 electrons are present. There are four unpaired
electrons.
3d
152, 2p6, 352 3p6 Irtlrlrlrlrl
2 8 8 ____ ~6 _______________________________________________________________
61 ~-
H
"
~
~ CHAPTER 2·.
Chemical Bonding
Contents:
21 INTRODUCTION
2.1 Introduction From the small number of elements there are derived millions of known
2.2 Cause of Chemical Combination compounds, and there are an infinite number possible. This is because
2.3 Lewis Symbols of Elements there are so many possible ways in which atoms combine to form
2.4 Electronic Theory of Valency molecules. This process seems similar to form words of a language from
2.5 Electrovalent or Ionic Bond a small number of letters of alphabet. In the formation of words, there
2.6 Determination of Lattice Energy are rules of the language which govern the types of possible
2.7 Types of Ions
2.8 Method of Writing Formula of an Ionic combination. In the case of atoms, the rules are based on the number
Compound and types of electrons which the atoms possess.
2.9 Difference between Atoms and Ions Most of the substances are found in nature in the form of clusters or
2.10 General Characteristics of Electrovalent aggregates of atoms. Any such aggregation, in which atoms are held
Compounds together and which is electrically neutral is called a molecule. The
2.11 Variable Electrovalency molecules are made of two or more atoms joined together by some force
2.12 Covalent Bond
acting between them. The force is termed as a chemical bond. Thus, a
2.13 Covalency
2.14 Covalent Compounds chemical bond is defined as a force that acts between two or more atoms
2.15 Covalent Molecules of Elements to hold them together as a stable molecule or as a force that holds
2.16 Characteristics of Covalent Compounds group of two or more atoms together and makes them function as a unit.
2.17 Comparison between Ionic and Covalent Bonds For example, in water the fundamental unit is the H-O-H molecule,
2.18 Comparison between Ionic and Covalent which is described as being held together by the two O~H bonds.
Compounds
2.19 Coordinate Bond
The beginning of our modern theory of
2.20 Failure of Octet Rule bonding can be treated to the concept of
2.21 Lewis Formulae for Molecules and Polyatomic valency introduced in 1850. The term
Ions valency has been derived from the Latin
2.22 Formal Charge word 'valentia' which means capacity. Each
2.23 Polarity of Covalent Bond element was said to have a valency equal
2.24 Dipole Moment
to its combining capacity. The number of
2.25 Polarisation (Change of Ionic Character to
Covalent Character) hydrogen or chlorine atoms with which
2.26 Hydrogen Bonding another atom combines is called its
2.27 Modern Concept of Covalent Bond combining capacity. The valency of these
2.28 Hybridization two elements was set as, one. Therefore,
2.29 Resonance oxygen which reacts with hydrogen to form
2.30 Prediction of Geometry (Shape) of Covalent
H 20, was said to have a valency of two. Mg
Molecules
2.31 Valence Shell Electron Pair Repulsion (VSEPR) combines with chlorine to form MgClz, Mg
Theory was said to have a valency of two. By using
2.32 Bond Characteristics Linus Pauling (1901-1994)
this definition, it is found that elements may
2.33 Odd Electron Bonds won the Nobel Prize in have multiple valencies and fractional
2.34 Molecular Orbital Thc>ory Chemistry in 1954 for his valencies in certain compounds. For
2.35 Metanic Bonding work in chemical bonding example, nitrogen forms a number of
Chemical Bonding 69
compounds with hydrogen such as NH3, N 2Rt, N3H in (b) Electrons repel each other, raising the energy and
which valencies of nitrogen come to 3, 2 and 1/3 respectively. reducing the stability.
Thus, the concept of valency asa mere number was very r(c) Nuclei repel each other, so reducing the stability also.
confusing. Later on, the definition of valency was changed. Electron
Valency was termed as the number of chemical bonds
formed by an atom in a molecule.
The modem concept of valency dealswith the interactions
between atoms in light of the structure of atoms, i.e., electronic
configurations of atoms. The modem concept believes that • +
electrons are responsible for chemical combination. It
provides tools to find· out the answers to the following
questions:
(i) Why do atoms combine?
(ii) How do atoms combine together?
Fig. 2.1 Electrostatic forces in hydrogen molecule
(iii) How can the properties of compounds be understood
in terms of chemical bonds? If the net result is attraction, the total potential energy of
the system decreases and a chemical bond results. No
Z.I·CAUSE OF CHEMICAL COMBINATION chemical bonding is possible if net result is repulsion.
The atoms interact with each other on account of the (ii) Lewis octet rule: The noble gases are known for
following reasons: their lack of chemical activity. There are no known com-
(i) Decrease in energy: It is a fundamental truth that pounds of helium, neon and argon. Why are these elements
all natural systems tend to lose potential energy and become so unreactive towards other elements? All these elements
more stable. Other things being equat a system that has have electronic structures that consist of filled 011termost
stored potential.energy is less stable than, a system that has shells. Except for helium, whose electronic configuration is
none. Jtis an observed fact that a bonded state is more stable Ii, the s-and p-subshells of the"'liighest energy level contain
than unbonded state. This is due to the fact that the bonded a total of eight electrons. It is, th~refore, concluded that il
state has lower potential energy than unbonded state. Hence, configuration in the outer energy level constitutes a structure
when two atoms approach each other, they combine only of maximum stability and therefore, of mini\num energy.
under the condition that there is a decrease in potential The atoms of all elements when enter into chemical
energy. combination try to attain noble gas configuration, i.e., they
When two atoms approach each other, new forces of try to attain either 2 electrons (when only one energy shell)
attraction and repulsion come into play. These forces are: or 8 electrons in their outermost energy level which is of
(a) .Electrons and nuclei attract one another. AttraCtiye maximum stability and hence of minimum energy. The
forces are energetically favourable, so an electron attracted tendency of atoms to achieve eight electrons in their outermost
to a nucleus is of lower energy and therefore more stable than shell is known as Lewis octet rule. Octet rule was the basis
a free electron. . of electronic theory of valency.
Noble Atomic Configuration of outer

Electronic configuration ,
number level
He 2 15 2 15
2
Ne 10 ll, 2s2 2p6 2s2 2p6

Ar 18 152, 2s2 2p6, 352 3p6 3s 2 3p6
Kr 36 152, 2s2 2p6, 3i 3p6 3d lO, 4l 4p6 45 2 4p6
Xe 54 Ii, 2s 2 2p6, 3s2 3p6 3dlO, 4i 4p6 4dlO, 5s2 5p6 55 2 5p6
Rn 86 li,2s 2 2p6, 352 3p6 3dlO, 4i 4p6 4a1° 4f 14, 5i 5p6 5d lO, 652 6p6 6i 6p6
2.3 1 LEWIS SYMBOLS OF ELEMENTS (iii) Atoms having less than 8 electrons in the outermost
Chemical bonding mainly depends on the number of orbit are chemically active. It is the tendency of these atoms
electrons present in the outermost energy level. These to achieve 8 electrons in the outermost orbit. [Hydrogen,
electrons are termed as valency electrons. The electronic lithium, beryllium try to achieve helium configuration.] The
configuration of sodium (Na) is 2, 8, 1 and that of sulphur number of electrons which take pirt determines the valency
has (S) 2, 8, 6. Thus, sodium has one valency electron while of the atom.
sulphur has six valency electrons. In the case of re- (iv) There are two ways by which the atoms can acquire
presentative elements, the group number (Modem noble gasconfigmation or 8 electrons in the outermost
energy level.'
Mendeleev's periodic table) is equal to the number of
valency electrons. (a) By losing or accepting electrons.
(b) By sharing electrons.
The valency electrons in atoms are shown in terms of
Lewis symbols. To write Lewis symbol for an element, we Sharing may be of two types:
1. Equal contribution of electrons is made by two atoms
write down its symbol surrounded by a number of dots or
crosses equal to the number of valency electrons. Paired and and these electrons are then shared equally to form covalent
bond,or
unpaired valency electrons are also indicated. The Lewis
symbols for hydrogen, sodium, nitrogen, oxygen and chlorine 2. Contribution of an electron pair is made by one atom
and both the electrons are shared equally by the two atoms
may be written as:
.. .. to form coordinate bond. The theory may be summarised in
H· Na· .
• N. .0.
Generalised, Lewis symbols for the representative
:Cl •
the following way. liThe union of two or more atoms
involving redistribution of electrons in their outer shells
elements are given in the following table: (either by transference or sharing) in such a way so that all
1 2 13 14 15 16 17 the atoms acquire the stable noble gas configuration of
Group lA IlA lIlA NA VA VIA VIlA
minimum energy is known as electronic theory of valency."
ns 1 ns 2 ns 2np l ns 2np2 ns 2np 3 ns 2np 4 ns 2np 5
x· ·x· · ·
·x·
.
·x·
.. ..
.x. :x.
Corresponding to the above three ways, there are three
Lewis symbol
Second period Li· ·Be· ·B·
·X.
· ·· ·N·.
·C·
.. :F·....
.0.
types of bonds or linkages which hold the atoms together in
a molecule.
· ·Si··· .p.... .. :ci. (0 Electrovalent or Ionic bond

Third period Na· ·Mg· ·AI· ·S· (ii) Covalent bond
0
(iii) Coordinate bond

2.4 ELECTRONIC THEORY OF VALENCY
2.~:q ELECTROVALENT OR IONIC BOND
The electronic theory of valency owes its rise to the
recognition of the existence of electrons in an atom. It was The chemical bond formed between two or more atoms as a
suggested that electrons themselves are responsible for result of the transfer of one or more electrons from electro-
chemical combination. Kossel and Lewis formulated a positive to electronegative atom is called electrovalent bond.
comprehensive statement which was completed by This bond is also called ionic or polar bond.
Langmuir and called electronic theory of valency. The main The electron transfer results in the formation of cations
points of the theory are: and anions. The cations are positively charged ions whereas
(i) Valency of an atom depends mainly on the number of anions are negatively charged ions. Oppositely charged ions
electrons present in the outermost orbit. These electrons are are attracted to each other and a bond between them is
termed as valency electrons. formed. The bond existing between the oppositely charged
(ii) Electronic configuration of noble gases is stable, i.e., ions is called an ionic or electrovalent or polar bond or the
eight electrons are present in the outermost orbit (except bond formed by the electrostatic attraction between positive
helium having 2 electrons). These gases are chemically inert and negative ions is called an ionic bond. Compounds
and do not form any compound. containing ionic bonds are called ionic, electrovalent or polar
compounds.
Chemical Bonding 71
[Note : Electrovalent bond is not possible between similar atoms. In all ionic compounds, the electrons lost by one or more
This type of bonding requires two atoms of different atoms in achieving the noble gas configuration of a cation
nature, one atom should have the tendency to lose are accepted by the requisite number of companion atoms to
electron or electrons, i.e., electropositive in nature and achieve noble gas configuration of the anions. Thus,
the other atom should have the tendency to accept
(number of cations formed) X (number of electrons lost in
electron or electrons, i.e., electronegative in nature.
fOrming one cation) = (number of anions formed) X (number
Actually ionic bond is not a true bond but just electro-
of electrons gained in forming one anion).
static attraction between closely packed ions. It is non-
directional in nature.]
III Conditions for Forming Electrovalent
III Examples of Eledrovalent Bond or Ionic Bond
(i) Potassium chloride:
The free potassium atom has one The following conditions favoUr the formation of an
valency electron (electronic configuration 2, 8, 8, I), i.e., 4s 1 electrovalent bond.
whereas, the chlorine atom has seven valency electrons (i) Number of valency electrons: One atom should
(electronic configuration 2, 8, 7), i.e., 3s2 3p5. In forming an possess I, 2 or 3 valency electrons while the other atom
ionic bond, the potassium atom loses its valency electron should have 5, 6 or 7 valency electrons. The atom which
which is accepted by chlorine atom. As a result potassium changes into cation should possess 1,2 or 3 valency electrons,
achieves noble gas configuration of argon (2, 8, 8) and i:e., it should belong to group IA, IIA or IlIA. It should be
becomes a positive ion· (K+). Chlorine achieves noble· gas metallic or electropositive in nature. The other atom which
configuration of argon (2, 8, 8) and acquires a negative changes into anion should possess 5, 6 or 7 electrons in the
charge (Cn. The attraction between potassium ion and valency shell, i.e., it should belong to group VA, VIA or VIlA.
chloride ion is an ionic bond. It should be non-metallic or electronegative in nature. The
A shorthand way of showing the formation of potassium atoms of transition metals can itlso lose electron or electrons
chloride from potassium and chlorine atoms involves and converted into cations. Thus,1:hey can also form electro-
electron dot symbols. valent bonds but do not acquire inert gas configuration
K
X ~.
• <;!: = K+
[ .. ]
':S}: or
always.
(ii) Difference in electronegativity: The formation of an
(2, 8, 8, 1) (2, 8, 7) (2, 8, 8) (2, 8, 8) electrovalent bond will be easier if the difference in the
electronegativities' of the two atoms is high. A difference of
(ii) Sodium sulphide: Sodium combines with sulphur
to form sodium sulphide, Na2S, Two sodium atoms, each about 2 is necessary for the formation of an electrovalent bond.
loses its valency electron, are converted into sodium ions The electronegativity of sodium is 0.9 and that of fluorine is
with neon like configuration (2, 8). Sulphur (2, 8, 6) which 4.0. Since the difference is 3.1 both will readily form an
has six electrons in the valency shell gains two electrons to electrovalent.bond.
achieve the argon like configuration (2, 8, 8). (iii) Overall decrease in energy: In the formation of an
2- electrovalent bond, there must be overall decrease in energy,
Na x~·
'5' Na+ x". . + 2- + 2- i.e., energy must be released. Energy changes are involved in
N a~.
•• Na+ [ X?: ] . o~ 2Na Sor Na2S
the following steps:
(2, 8 ,1) (2, 8, 6) (2, 8) (2, 8, 8)
(a) Energy equivalent to ionisation energy is required to
(iii) Magnesium fluoride: Magnesium combines with convert a neutral isolated gaseous atom into a cation.
fluorine to form MgF 2. Magnesium atom loses two electrons A + ionisation energy = A+ + e- ....0.)
and is converted into magnesium ion (Mg++) with neon like
configuration (2, 8). Lower the value of ionisation energy of an atom, greater
Each fluorine atom having seven electrons in valency shell will be the ease of formation of the cation from it, i.e., one
atom should have low value of ionisation energy.
r
requires one electron to acquire neon configuration (2, 8).
(b) Energy equivalent to electron affinity is released when
:f.M~":'~:=k Mg++ ['~l or MgH(Fl,

an electron is added to a neutral isolated gaseous atom to
make it univalent anion.
(2, 7)(2, 8, 2)(2, 7) (2, 8) (2, 8) (2, 8)
B + e- B- + electron affinity ... (ij)
Higher the value of electron affinity of the atom, greater The value of F increases if (i) ql and q2 are high and (ll)
the ease of formation of the anion from it, i.e., other atom (rA + + rB-) is small.
should have high value of el~ctron affinity. The stability of the ionic compound and the strength of
(c) Lattice energy: Cation and anion attract each other the ionic bond depends on the value of F. Higher the value
, by electrostatic force of attraction to give a molecule A +B-. of F, greater shall be the stability of the ionic compound and
hence greater shall be the strength of the ionic bond. For
example, NaCI is more stable than CsCI as (rNa+ + ro-) is
less than (rcs+ + rce). MgO is more stable than NaCI as the
product qlq2 is four times more in MgO than NaCl.
The lattice energy can also. be defined Cis the energy
required to separate one mole crystal of an ionic compound
into gaseous ions.
Fig. 2.2 Crystals of ionic compounds MX(s). +L.E. .) M+ X-

(g) + (g)
Since the electrostatic field of a charged particle extends in Theoretically, lattice energy is given· by Born-Lande
all directions, a positive ion is surrounded by a number of equation.
negatively charged' ions while each negative ion similarly
surrounded by a number of positive ions. These cations.and
L.E.= NOMz+z-e2 [1-';J
r
anions arrange systematically in an alternating cation-anion
where No = Avogadro'snumber
pattern as shown in Fig. 2.2. This is called a crystal lattice.
M = Madelung constant (depends on crystal
This process of clustering ions increases the force of attraction
structure)
and thus potential energy decreases. The energy released
Z+ and Z- = Charges on cation and anion
when the requisite number of positive and negative ions
e = charge on the electron,
are condensed into crystal to form one mole of the
r = r + (radius of cation) +. r - (radius of anion)
compound is called lattice energy (III step). Higher the
n = Born constant (depends on the electronic
lattice energy, greater will be the ease of forming an ionic
configuration of ions)
compound. If the energy released in steps (II) and (III) is
Note: In a number of cases, the results obtained from Bom-
greater than the energy used in step (I), the formation of an
Lande ~quation are different than experimental values.
ionic compound will be favoured.
Thus, the Born-Lande equation is not perfect and needs
The value of lattice energy depends on the charges present
modification.
on the two ions and the distance between them. According
to Coulomb's law, the force of attraction (F) between two Conclusions
oppositely charged ions in air with charges equal to q} and (i) An ionic bond is purely electrostatic in nature.
q2 and separated by a distance d is given by, (ii) Its formation is favoured by :
1 q}q2 (a) Low ionisation potential (I.P;) of the element
F= 41tEoKd2 that forms a cation on losing electron(s). The element should
where d is equal to sum of ionic radii of the two ions and be metal, i.e., electropositive in nature.
K is dielectrIc constant of medium. (b) High electron affinity (E.A.) of the element that
forms an anion on gaining electron(s). The element should
F=_1_ qlq2
be non-metal, i.e., electronegative in nature.
41teoi< (rA+ + rB-)2
Chemical Bonding 73
(c) High lattice energy (L.E.) :. The energy released when 2'.1 DETERMINATION OF LATTICE ENERGY
isolated ions form· a crystal. The value of lattice energy
The lattice energy of an ionic solid is determined experi-
depends on the charges present on the two ions and distance mentally by a process known as Born-Haber cycle. This cycle
between them. It shall be high if charges are high and ionic
is based on Hess's law, i.e., the formation of an ionic crystal
radii are small.
may occur either by direct combination of the elements or by
(d) The summation of three energies should be negative,
an alternate process in which' the following steps are
i.e., energy is released. '
involved. In both cases energy involved is the same.
I.P. + E.A. + L.E. = -ive (i) The reactants are converted into gaseous state.
'. (iii) Highly electropositive elements of groups I and II (ii) The gaseous atoms are converted into ions.
combine with highly electronegative elements of VI and VII (iii) The gaseous ions are combined to form ionic
(or 16th and 17th) groups to form electrovalent or ionic compound.
compounds. Halides, oxides, sulphides, nitrides and For example, the formation of KF can occur either directly
hydrides of alkali and alkaline' earth metals are generally ., or in steps. .
-".
ionic.
Direct Combination
(iv) Greilter the difference of electronegativity between
two atoms, higher will be the possibility of ionic bond K(s) + 21 F2Cg) ~ KF(s)
formation.
(v) Electrovalency : The capacity of an element to form AH or·heat of formation -562.6 kJ morl
electrovalent or ionic bond is termed as electrovalency. In Steps:
The capacity is measured in terms of the electrons lost or (i) Conversion of solid potassium into gaseous state.
accepted. Thus, electrovalency of an element is equal to the K(s)~K(g)
number of electrons lost by an atom of the element or gained H.A. or heat of atomisation =+89,6 L<J morl
by the atom of the element as to acquire inert gas (ii) Formation of a cation.
configuration. The elements which lose electron or electrons .
KCg) ~ rCg) + e-
show positive electrovalency and the elements which gain
electron or electrons show negative electrovalency. Generally J.P. or first ionisation potential = +419.0 kJ morl
positive and negative signs are not used in practice and only (iii) Conversion of molecular fluorine into gaseous atomic
the number is taken to represent electrovalency. fluorine.
No: of ele-
Element ctrons lost Eledr&- Change in electronic
or gained valency configuration
by an atom 1/2 H.D. or 1/2 (heat of dissociation)
... = + 1/2 (158.2) = 79.1 kJ morl
Na 1 (lost) 1 (Monovalent) 2,8, 1 to 2,8 (Na+)
(iv) Formation of anion.
K 1 (lost) 1 (Monovalent) 2, 8, 8, 1 to 2, 8, 8 (K+)
FCg) + e- ~ F-Cg)
Mg 2 (lost) 2 (Divalent) 2,8,2 to 2, 8 (Mg++)
E.A. or first electron affinity =-332.6 kJ morl
Ca 2 (lost) 2 (Divalent) 2,8,8,2 to 2,8,8 (ea++)
(v) Combination of K+Cg) and rCg) to form KF(s).
AI 3 (lost) 3 (Trivalent) 2, 8, 3 to 2, 8 (Al+++)
rCg) + F-Cg) ~ KF(s)
F 1 (gained) 1 (Monovalent) 2, 7 to 2, 8 (F-)
L.E.or lattice energy = -U kJ morl
CI 1 (gained) 1 (Monovalent) 2, 8, 7 to 2, 8, 8 (Cn
On the basis of Hess's law
0 2 (gained) 2 (Divalent) 2, 6 to 2, 8 (0--)
-562.6 = 89.6 + 419.0 + 79.1 - 332.6 -,- U
5 2 (gained) 2 (Divalent) 2, 8, 6 to 2, 8, 8 (5--)
U 817.7 kImorl ,
N • 3 (gained) 3 (Trivalent) 2, 5 to 2, 8 (N---)
i.e., lattice energy of KF =-817.7 kJ morl
2
Born-Haber cycle for formation of KF(s) may:be (ii) Ions with pseudo inert gas configuration:' The Zn +
represented as: ion is formed when zinc atom loses its outer 45 electrons. The
outer shell configuration ~f Zn2+ ion is 3i3p63io. The
+HA ninp6ndlO outer shell configuration is often' called
K(S) ------------------~) K(g)
{ ~F2(g) _---"=-HD-'--_----7 F~) 1 +l.P.

pseudonoble gas configuration which is considered as stable
one.
Examp-I'es: Zn,
e 2+ Cd2+, H g2+, Cu,
+ A g,
+ A u,+ Ga3+, etc.
'
tlli -E·A.l (iii) Exceptional configuration : . Many d- and f- block
KF (
-u
Lattice energies of some ionic compounds:
T elements produce ions with config!lfations different th-<'lll
the above two. Ions like Fe3+, Mnz+, etc., attain a stable
configuration half filled d-orbitals.
MnZ+
Name of the Lattice ene " .. ' .
of the Lattice energy Examples of other configurations are many.
compound in kJ mo.-I' ound in kJ moe l
Tiz+ (3i 3p6 3d z); VZ+ (3i 3p6 3i)
NaCl 769 NaBr 732
KCl 701 CaBrz 2132 . C?+ (35 Z 3p6 3d~ ; , Fez+ (35 Z 3p6 3d6)
MgClz 2326 Lil 730 However, such ions are comparatively less stable. '
BaClz 2033 NaI 682 (iv) Ions with ns 2 configuration: Heavier members of
NazO, 2481 Mglz 1944 groups III, IV and V lose p-electrons orily. to form ions with
MgO 3795 Balz 1831 niconfiguration. Tt, Snz+, Pbz+, Bi3+ are the examples of
CaO 3414 CaFz 2630 this type. These are stable ions.
BaO 3029 i AlC13 5492 (v) Polyatomic ions: The ions which are composed of
From the above table, it is clear that lattice energy is more than one atom are called polyatomic ions. These ions
affected by both the charge and size of the ions. Compounds move as such in chemical reactions. Some common,
with higher charges have large lattice energies and lattice polyatomic ions are:
. +
energy decreases as the size of one or both the ions, i.e., cation NH4 (Ammonium); N03 (Nitrate);
and anion, increases. In general, the compounds having high
values of lattice energy possess the following characteristics:
POt (Phosphate); . SO~- (Sulphate);
(i) High stability CO~- (Carbonate); SO~-(Sulphite), etc.
(ii) High melting points The atoms within the polyatomic ions are held to each
(iii) Low solubility in water (If lattice energy is higher other by covalent bonds.
than hydration energy). The electrovalem;ies of an ion (any type) is equal to the
20ft TYPES OF IONS number of charges present on it.
The following types of ions are encl;untered. METHOD OF WRITING FORMULA

(i) Ions with inert gas configuration: The atoms of the OF AN IONIC COMPOUND
representative elements of group I, II and III by complete loss In order to write the formula of an ionic compound which is
of their valency electrons and the elements of group V, VI made up of two ions (simple or polyatomic) having electro-
and VII by gaining 3, 2 and 1 electrons respectively form ions valencies x and y respectively, the following points are
either with ni configuration or ns2p6 configuration. followed:
(i) Write the symbol of the ions side by side in such a
(a) Ions with Is2 (He) configuration: H-, U+, Be2+, etc.
way that positive ion is at the left and negative ion
The formation of U+ and Be2+ is difficult due to their small at the right as AB.
size and high ionisation energy. (ii) Write their electrovalencies in figures on the top of
(b) Ions with nip6 configuration: More than three each symbol as AXBY.
electrons are hardly lost or gained in the ion formation. (iii) Divide their valencies by H.C.F.
~ X ~, i.e., formula
+ Ca
Cations : Na, 2+, Al3+, etc.
(iv) Now apply criss cross rule as
Anions: 0-, OZ-, N3--, etc. AyBx·
Chemical Bonding 75
Examples: Note : There is a difference, in their relative sizes. A positive
2 1 ion is always smaller and a negative ion is always larger
Calcium chloride Ca X CI ;:: CaCI2;
than the corresponding atom.
Na 1.54 A . N + < N Cl 0.99 A. i.e. 0- > CI
3 2 Na + 0.95 A' I.e., a a cr 1.81 A ' ,
Aluminium oxide' Al X ° = Al 0 2 3;
2~1;~ GENERAL CHARACTERISTICS OF
1 3 ELEC"rROVALEN.T COMPOUNDS
Potassium phosphate KX K P0 P04 = 3 4;
'i
The compounds having electrovalent bonds are called

23
electrovalent compounds. The following are some of the
Magnesium nitride Mg X N ;:: Mg N 3 2; general properties shown by these compounds:
1 1 (i) Crystalline nature: Electrovalent compounds are
2 2
Calcium oxide CaO or CaXO =CaOi usually crystalline in nature. The constituent units in an ionic
crystal are ions and not molecules. These ions are arranged
1 2
together in a regular way in an ionic lattice. Force of attraction
Ammonium sulphate NH4 X
504 = (NH4hS04 between the ions is non-directional and extends in all
The following table summarises general formulae of directions. Thus, electrovalent compounds consist of three
the binary ionic compounds formed by representative dimensional solid aggregates. Normally each ion is
elements: surrounded by a number of oppositely charged ions and this
number is called the coordination number. The coordination.
General
Metal Non-metal Ions present Example numbers of positive and negative ions are the same if there
formula
are equal number of both the ions as in NaCL The geometry
IA VIlA MX ArX- NaCl of the ionic crystal depends on radius ratio of the cation and
IIA VIlA MX2 M2 +2X- CaCl2 anion (rc+ /r(1-)' In the case of NaCl crystal, the coordination
IlIA VIlA MX3 M3+3X- AlF3 number is six that is each Na+ ion is surrounded by equally
2M+X 2-
IA VIA M2X K2S spaced six cr ions placed at the comers of regular
M2+X 2-
IIA VIA MX CaO octahedron and similarly each cr ion is surrounded by six
IlIA VIA M 2X3 2M 3+3X 2- Alz03 equally spaced Na+ ions placed at the comers of an
IA VA M3 X 3M+X3- Na3P octahedron (see Fig. 2.3 and 2.4). The-shape ofNaCI unit cell
IIA VA M3X2 3M 2+2X3- Mg3N2 is cubical.
IlIA VA MX M 3+X3- AlP
ill
2-:,~ . DIFFERENCE BETWEEN ATOMS AND IONS
The following are the points of difference between atoms and
ions:
Atoms Ions
1. Atoms are perfectly neutral in
Ions are charged particles, cations
nature, i.e., number of protons
are positively charged, i.e., number
equal to number of electrons.of protons more than the number
Na (protons 11, electrons 11)of electrons. Anions are negatively'
charged, i.e., number of protons less'
than the number of electrons.
Na+ (protons 11, electrons 10)'
cr (protons 17, electrons 18)
2. EXceptnoblegases,atomshave Ions have generally 8 electrons in Fig. 2.3 Actual compact structure of
less than 8 electrons in the the outermost orbit, i.e., ninp6 con- sodium chloride crystals
outermost orbit, figuration.
As electrovalent compounds have closed packed
Na 2, 8, 1; Ca 2, 8, 8, 2 Na+ 2, 8 ; cr 2, 8, 8 structures and ions have no freedom of movement, these are
Cl 2, 8, 7; S 2, 8, 6 Ca2+ 2, 8, 8
not found in liquid or gaseous states under ordinary
3. Chemical activity is due to loss The chemical activity is due to the conditions of temperature and pressure and exist as solids.
or gain or sharing of electrons charge on the ion. Oppositely
as to acquire noble gas configu- I charged ions are held together by
Electrovalent compounds have low volatility and high
ration. : electrostatic forces. stability because strong electrostatic forces of attraction bring
these ions very dose to one another, thereby decreasing the
volUme of thecrystal and hence, these compounds have high The positive end of the dipole interacts with the negative'ion
density. . of the electrovalent compound and the negative end of the
(ii) Melting and boiling points : Due to strong dipole interacts with the positive ion of the same electro-
electrostatic forces of attraction, the ions are held tightly in valent compound as shown in Fig. 2.5. Water molecules pull
their positions in the crystal lattice. To dislodge the ions from
their positions, a considerable amount of energy is negded
to overcome the forces of attraction. Thus, electrovalent
compounds possess high melting and boiling points. Melting
point of ionic solid is sharp and fixed. Cooling curve of ionic
solids is also not smooth (see cooling curve on Page 76).
Fig. 2.5 Solvation of NaCI in water
the ions from the crystal lattice. These ions are then
surrounded by water dipoles with the oppositely charged
ends directed towards them. These solvated ions lead an
independent existence and are thus dissolved in w~ter.
Fig. 2.4 . Cubical. structure of sodium. chloride crystal.
The solubility of an electrovalent compound in a polar
(iii) Hard and brittle: Electrovalent compounds are solvent can also be explained on the basis of lattice and
hardin nature. The hardness is due to strong forces of solvation (hydration in case if water is solvent) energies. The
attraction between oppositely charged ions which keep electrovalent compound dissolves in a solvent if the value
them in their alloted positions. The brittleness of the crystals of solvation energy is higher than the lattice energy of the
is due to movement ofa layer of a crystal on the other layer electrovalent compound. When the compound is dissolved
by application of external force when like ions come infront in a solvent, first the compound is broken down into ions.
of each other. The forces of repulsion come into play. The The energy required for this process is called lattice energy.
breaking of crystal occurs on ac~ount of these forces or AB + Lattice energy =A + + B-
repulsion.
(iv) Solubility: Electrovalent compounds are fairly These' ions are surrounded by solvent moiecules .•
soluble in polar solvents and insoluble in non-polar This process is called solvation. This process is ·exothermic.
solvents. The polar solvents have high values of dielectric A+ + x(solv.)---+ [A (solv')xt + energy
qmstan~s. *Water, the polar solvent, is one of the best solvents B- + y(solv.) ---+ [B (solv')yf + energy
as it has a high value of dielectric constant. Due to high value
The value of solvation energy depends on the relative size
of dielectric constant, the electrostatic force of attraction
of the ions. Smaller the ion more of solvation, hence solvation
between the ions decreases and these ions get separated
energy will be high. The non-polar solvents do not form
. and ultimately solvated by the molecules of the solvent. The
non-polar solvents have very low value of dielectric solvated ions and thus no energy is released. Hence,
constants * and are not capable of dissolving electrovalent solubility of electrovalent compounds in non-polar solvents
is not possible. It is notable point that if an electrovalent
compounds.
compouhd dissolves .in non-polar solvent then colloidal
The values of dielectric constants of. some of the
solution is formed, e.g., NaCl form colloidal solution in
compounds are given below:
kerosene. .
Compound. Water Methyl Ale. Ethyl Ale. Acetone Ether
(v) Electrical conductivity: Electrovalent solids do not
Dielectric constant 81 35 27 21 4.1
conduct electricity. The reason is that the ions, on account of
compounds decreases
electrostatic forces of attraction, remain intact occupying
fixed positions in the crystal lattice. The ions, thus, do not
The solubility in polar solvents like water can also be
move where electric current is applied.
explained by saying that the molecule of water is a dipole.
*rhe dielectric constant of a solvent is defined as its capacity to weaken the force of attraction between the electrical charges
immersed in that solvent.
Chemical Bonding 77
When electrovalent compounds are .melted or dissolved outermost energy level) is called a core or kernel. In the case
in a polar solvent, the ions become mobile. They are attracted of the atoms of transition elements, ions formed after the loss
towards the respective electrode~ and act as carrier of electric of valency electrons do not possess a stable core as the
current. Thus, electrovalent compounds in the molten state configuration of outermost shell is not ns2np6 but
orin solution conduct electricity. ninp6dltol0. The outershell generally loses one or more
(vi) Space isomerism : The electrovalent bond is non- electrons giving rise to metal ions of higher valencies. The
rigid and non-directional. Thus, the electrovalent compounds variable valencies of iron and copper can be explained on
do not show space isomerism or stereo-isomerism. this basis.
(vii) Isomorphism: Compounds having same electronic Fe 26 2, 8, 8 + 6, 2 3s2 3p6 3d 6, 4i
structures are isomorphous- to each other. For example, Fe2+ 24 2,8; 8 + 6 3s2 3p6 3d 6 (Not stable)
sodium fluoride and magnesium oxide are isomorphous to
Fe3+ 23 2, 8,8 + 5 3i 3p6 3d 5 (Stable)
each other.
Thus, iron shows +2 and +3 valencies. The compounds,
Na+F- Mg2+02- in which iron is in trivalent state, i.e., ferric compounds are
(2,8) (2,8) (2, 8) (2, 8) . more stable than the compounds in which iron is in divalent
Potassium sulphide, potassium chloride and calcium state (ferrous compounds). The atom of copper possesses .one
chloride are isomorphous to each other. electron in the outermost shell. It loses this electron to form
IC" S2- . IC" cr . Ca2+ cr Cu+ (cuprous) ion.
(2, 8, 8) (2, 8, 8) (2, 8, 8) (2, 8, 8) (2, 8, 8) (2,8,8) Cu 29 2, 8, 18, 1 3s 2 3p6 3d lO, 48 1
Cu+ 28 2,8, 18 3s2 3p6 3d 10
(viii) Ionic reactions: Electrovalent compounds furnish
ions in solution. The chemical reactions are due to the The s2p6io configuration is not as stable as s2 p6
presence of these ions. Such reactions are fast. For example, configuration and the nuclear charge is not sufficiently
SO~- ions present in Na2S04 solution, form white precipitate strong to hold all the electrons intact in their f'ositions. Thus,
of BaSQ4 as soon as BaCl2 solution is added to it. Cu+ ion loses one more electron to form Cu2+ (cupric) ion.
The Cu2+ ion is quite stable as the nuclear charge is sufficient
Na2S04 ~ 2Na+ + SO~ to hold 27 electrons intact.
BaCl2 ~ Ba2+ + 2Cr Cu2+ 2,8, 17 3i 3p6 3d 9
Bi+ + soi- ~ BaS04.,J.. Thus, cupric compounds are more stable than cuprous
White precipitate compounds.
(ix) Cooling curve: Cooling curve of an ionic compound The above two explanations fail to account why
is not smooth, it has two break points corresponding to time (a) C02+ ion cannot be easily converted into C03+ ion like
of solidification. 2
Fe + ion.
2
(b) Zn + ion does not lose one more electron as its
A Liquid configuration (3s 2 3p6 3io) is similar to Cu + ion. .
In general, we can say that whenever the core is unstable,
M.pt. it loses one or more electrons to show higher valency and if
8, C'I
Temp. I the core is comparatively stable it always resists the loss of
,,
I I
I
I ,,
I
D more electrons.
r I
,
I
I
, The cores of C02+ .ion and 2n2+ ion are comparatively
stable as the nuclear charges are sufficient to hold all the
-lime
'-.r----' electrons intact in their positions. C02+ ion changes into C03+
Solidification time ion in presence of an oxidising agent, but cobaltous
compounds are comparatively more stable than cobaltic
2~i1'l
.. VARIABLE ELECTROVALENCY
compounds.
[Note: Cu2+ is more stable in aqueous'solutionthan Cu+ due to
Certain elements (metals) show; morer than one electro- high hydration energy.]
valency in their electrovalent compounds. The atoms of (ii) Inert pair effect! Some of heavier representative
these elements lose different number of electrons under elements of third, fourth and fifth groups having confi-
different conditions, thereby showing variable electro-
valency. The following are two reasons for variable
ns
gurations of the outermost shell 2npl, ns2np2 arid ns2np3
show valencies with a difference of 2, i.e., 0; 3), (2; 4), (3; 5),
electrovalency : respectively. In the case of lower valencies, only the
(i) Instability of the core: The residue configuration left
electrons present on p~subshell are lost and nl electrons
after the loss of valency electrons (electrons present in the remain intact. The reluctance of s-electron pair to take part
in bond formation is known as the inert pair effect. A partial when atoms bonded together share two or three electron
explanation of the inert pair effect is due to the fact that outer pairs, respectively. These bonds are represented by double
ns 2 electrons penetrate to some extent to penultimate orbit dash (=) and triple dash (==) respectively. Some examples
consisting 18 electrons thereby attracted strongly towards of covalent bonding are given below:
nucleus. Inert pair effect increases in a group as the atomic (i) Formation of hydrogen molecule: In the formation
number increases. of hydrogen molecule, each hydrogen atom contributes one
Tl (III group) 2, 8, 18, 32, 18, 6i 6pl electron and then the pair is shared betWeen two atoms. Both
Tl+ 2, 8, 18, 32, 18, 6i Only 6p electron is lost the atoms acquire stable configuration of helium. Thus, the
00
Sn av
group) 2, 8, 18, 18, fjp2
molecule consists of one single covalent bond.
Sn2+ 2, 8, 18, 18, Only Sp electrons are lost
Pb (IV group) 2, 8, 18, 32, 18, 6i 6p2 HX+'H---> or H-H
Pb 2+ 2, 8, 18, 32, 18, 6i Only 6p electrons are lost
Bi (V group) 2, 8, 18, 32, 18, 6s2 6p3 (ii) Formation of chlorine molecule: Chlorine atom has
Bi3+ 2, 8, 18, 32, 18, 6i Only 6p electrons are lost seven electrons in the valency shell. In the formation of
chlorine molecule, each chlorine atom contributes one
When sufficient energy is available, the s-electrons also
electron and then the pair of electrons is shared between two
enter into bond formation and higher valencies are observed.
atoms. Both the atoms acquire stable configuration of argon.
This tendency to show higher valencies is less in: the case of
TI,'Pb and Bi but more in the case of comparatively lighter
•• xx
elements such as In, Sn, Sb, etc.
:CI.xCI~- or Cl-CI
•• , xx
Conclusions (2,8,7) (2,8,7)
1. In group 13, Ga, In and TI show variable valencies of (2,8,8) (2,8,8)
+3 and +1. The stability of +3 state decreases while that of
(iii) Formation of Hel molecule: Both hydrogen and
+1 state .increases. TI+ is thus more stable than Te+.
chlorine contribute one electron each and then the pair of
2. In group 14, Ge, Sn and Pb show variable valencies of electrons is equally shared. Hydrogen acquires the confi-
+4 and +2. The stability of +4 state decreases while that of guration of helium and chlorine acquires the configuration
+2 state increases. Thus, Ge4 is more stable than Ge2+ while of argon.
Pb 2+ is more stable than Pb4+.
3. In group 15, P, As, Sb and Bi show variable valencies X
••
H .CI: - or H-CI
of +5 and +3. The stability of +5 state decreases while that of ••
(1) (2,8,7)
+3 state increases.
(2) (2,8,8)
2.1~1. COVALENT BOND (iv) Formation of water molecule: Oxygen atom has 6
valency electrons. It can achieve configuration of neon by
The second· mode of combination was first proposed by
sharing two electrons, one with each hydrogen atom.
Lewis, in 1916, thatthere are atoms which attain noble gas
configuration by sharing one or more electron pairs when
each atom contributes equally. The pair or pairs of electrons or H-O-H
become a common property of both. Such a bond is possible
between similar and dissimilar atoms. In this bond the (2) (2,8) (2)
atoms do not acquire any charge as the electron or electrons (v) Formation of methane: Carbon has four electrons
are not lost completely. The electrons, which are shared, in the valency shell. It can achieve stable configuration of
occupy such a position in between the nuclei of the two atoms neon by sharing four electrons with four hydrogen atoms,
where there is maximum force of attraction from the two one with each hydrogen atom. Each hydrogen atom acquires
nuclei. The bond is, therefore, termed as non-polar bond. helium configuration.
A chemical bond formed by sharing one or more
/I
electron pairs between atoms when each atom cOl:ltributes H

equally is called a covalent bond." I
Covalent bond may be single, double or a triple bond. H-C-H
Double and triple covalent bonds are called multiple I
covalent bonds. Single covalent bond is formed by sharing H
of only one electron pair. This bond is represented by single
dash (-). Double and triple covalent bonds are formed
Chemical BQnding 79
(vi) Formation of O 2 molecule: Each oxygen atQm to. 8-grQUP number of Mendeleev's table to. which an
contributes two. electrQns and two pairs of electrQns are then element belongs. This is true fQr the elements ~longing to
shared equally. Both the atQms acquire configuration Qf neon. IV, V, VI and VII groups. '
x x •• Element Group (8-Group number) . Covalency
o ~ + : ••
xx
0 - Qr 0=0
C IV 8-4=4 4
(2,6) (2,6) Si IV 8-4 4 4
(2,8) (2,8) V- 8 5=3
N 3
(vii) Formation of N2 molecule: NitrQgen atQm has five P V 8 5=3 3
valency electrQns. BQth nitrogen atQms achieve configuration 0 VI 8 6=2 2
of neQn by sharing 3 pairs Qf electrons; i.e., each atom S VI 8-6=2 2
contributes 3 electrons. F VII 8-7=1 1
Cl VII 8-7 1 1
or N=N Generally, the cQvalency Qf an element is equal to. the tQtal

number Qf unpairedelectrQns in s- and p-Qrbitals of the
(2,5) (2,5)
(2,8) (2,8) valency shell. '
The shared pairs of electrons present between the atQms Covalency
are called bond pairs. On the Qther hand, the valency Hydrogen has one unpaired orbital One
electrQns which are nQt invQlved in sharing Qr in the 2s
fQrmatiQn of cQvalent bonds are termed lone pairs Qr non- Fluorine has only one unpaired orbital One
bonded electrons.
Oxygen has two unpaired p-orbitals Two
Lone pair
/
" Bond pair
Nitrogen has threeunpf\ired p-electrons IiJ, I II I I I I I ~
•• ~-1 These four elements do. nQt PQssess d-Qrbitals in their
j"
H;N~H
//H~
Bond pair
/ ..
: 0 ~H
valency shell.' However, the elements having vacant
d-orbitals in their valency shell like P, S, CI, Br, I, shQW
variable covalency by increasing the number of unpaired
Bond pair Lone pair
electrons under excited conditiQns, i.e., unpairing the paired
Ammonia molecule Water molecule Qrbitals and shifting the electrQns to. vacant d-orbitals. (Such
a shifting is not possible in the case of H, N, 0 and F
Iii Conditions for formation of covalent bonds because d-orbitals are not present in their valency shell.]
The fQllQwing cQnditions favQur the formation of cQvalent Phosphorus shows 3 and 5 cQvalencies.
bonds: 3s 3p 3d
(i) Electronegativity: An atQm will not transfer the Phosphorus atom in ground state [TI] I I II 1I II I I
electrQn Qr electrQns to. the Qther atQm if the electrQnegativity '--v-----
difference between the two. atQms is zero or very small (less Three unpaired electrons
covalency 3
than 1.6). Such atQms prefer to. share electrQns, i.e., fQrm
cQvalent bQnds. Phosphorus atom in excited state OJ II 1I II 11r-;-;I--'-I--'·I--'-'
v
(ii) When bQ,th the atQms' are shQrt in electrQns in the Five unpaired electrons
valency shell in cQmparison to. stable nQble cQnfiguratiQn, covalency = 5
then such atQms cQmplete the QutermQst shell by sharing
electrQns. Except hydrQgen which has Qne electrQn in valency Sulphur atom shQWS 2, 4 and 6 covalencies.
shell, such atQms have 5, 6 or 7 valency electrQns. The nQn- 3s 3p 3d
metals Qf grQup VA, VIA and VIlA satisfy this cQndition. Sulphur atom in ground state 11,1,1 I II!!
'--v---'
! 1
Two unpaired electrons
2.11 COVALENCY covalency := 2
It is defined as the number of electrons contributed by an Sulphur atom in excited state, 35 3p 3d
atom of the element for sharing with other atoms as to (a) When p-orbital is unpaired [ill!I!III!II! ! 1
achieve noble gas configuration. It can also. be defined as (first excited state.)
the number of covalent bonds formed by the atom of the Four unpaired electrons
element with other atoms. The usual cQvalency Qf an covalency = 4
element except hydrQgen (which has cQvalency 1) is equal
(b) When s- and p-orbitals areITJlililillil il

" , (b) Second excited state when
unpaired (second excited
state.) Six unpaired electrons two orbitals are unpaired
covalency = 6 Five unpa~ed electrons
Chlorine shows 1,3,5 and 7 covalencies. covalency == 5
~ 3p 3d
Chlorine atom in ground state lli.Jli.l.-li.l.-1 i IIL...-'-....I.I---,-I---,---, (c) Third excited state when [1J 1iii I i II iii 11' I
one s-and two p-orbitals
are unpaired Seven unpaired electrons
One unpaired electron
covalency = 1 covalency =7
Chlorine atom in excited state, Thus, variable covalency is shown by those elements
whose atoms have vacant d-orbitals in their valency shell.
(a) First excited state when !!II i.l.-I iii I L.. .!t.J-1
~
....1.---'----'---'
p-orbital is unpaired
Three unpaired electrons
covalency = 3
2. COVA~ENT COMPOUNDS
The compounds containing a covalent bond or a number of covalent bonds are termed as covalent compounds. Compounds
such as HO, Cl-4, COp SiOp H 20, NH3, P03, SOp etc., are some of. the examples of covalent compounds. All organic
compounds and the compounds formed by the combination of two different non-metals are covalent in nature.
COVALENT MOLECULES OF ELEMENTS

Some of elements are known to exist in molecular forms under ordinary conditions. These molecules also possess covalent
bond or bonds. For example, halogens, sulphtir, oxygen, nitrogen, hydrogen, phosphorus, etc., exist in molecular forms.
Carbon and silicon have complex structure. In these structures the atoms are also linked by covalent bonds.
Element Formula of the molecule Structure
Hydrogen H-H
•• ••
Halogens : X': X: x-x
(F, el, Br, 1)
•• ••
•• ••
Oxygen :0::0: 0=0
S-l
Nitrogen
•• ••
(
S : S
• e•• _ .,... •
Sulphur S8 • S •• •• S •
•• ••
(Every sulphur atom is linked to two other • •
S atoms by single covalent bonds.) •• S • __
• • .- •e. S ••
S-S/ S : S
•• ••
••
Phosphorus
(Every phosphorus atom is linked to other
three P atoms by single covalent bonds.)
2.1"~
"Y:i<i
CHARACTERISTICS OF COVALENT COMPOUNDS
(i) Physical state: Under the normal conditions of temperature and pressure, these exist as gases or liquids of low boiling
points. This is due to the fact that very weak forces of attraction (van der Waals' forces) exist between discrete molecules.
Chemical Bonding 81
Some exist as soft solids if their molecular masses are high. 2.1f:~
·CCC"1it
COMPARISON BETWEEN IONIC AND
Sulphur, phosphorus, iodine are soft solids. COVALENT BONDS
(ii) Melting and boiling points: With the exception of
few which have giant three dimensional strUctures such as Ionic bond Covalent bond
diamond, carborundum (SiC), silica (Si02), others have 1. Formed by the transference of Formed by sharing of electrons
relatively low melting and boiling points. This is due to the between two non-metal atoms
electron or electrons from electro
presence of weak attractive forces between the molecules. positive (metal) to electro- when the electrons are equally
On supplying heat energy, the molecules are readily pulled negative (non-metal) atoms. contributed by both the atoms.
SUcll a bond is possible betweenSuch a bond is possible between
out from these forces and move freely having high kinetic dissimilar atoms. similar and dissimilar atoms.
energy. 2. Consists of electrostatic force Consists of shared pair or pairs
(iii) Crystal structure: These are of three type«. between atoms. of electrons which are attracted
(a) First type : These are the crystals in which the unit is by both the nuclei.
molecules. The molecules are held by van der Waals' forces. 3. Non-rigid and non-directional, Rigid and directional, causes
These are readily fusible and volatile. Examples are sulphur, does not cause isomerism. space and structural isomerism.
iodine, phosphorus pentoxide, etc. 4. It is a weak bond, since the It is strong bond, since the paired
(b) Second type: This includes crystals which have electrostatic force between the electrons cannot be separated
ions can be broken easily. easily.
separate lattice layers. The best example of this type is
5. It is polar in nature. It is non-polar if the electronega-
graphite. Each atom has three neighbours. It is bonded to tivity difference is zero or ~mall.
two of them by single covalent bonds and to the third by
double bond. The bonds tie the atoms very tightly together 2.111 COMPARISON BETWEEN IONIC AND
into a layer. These layers can slide on one another. This
COVALENT COMPOUNDS
accounts for the softness of graphite.
(c) Third type : This includes crystals in which Ionic compounds Covalent compounds
every atom is bonded to four other atoms by single covalent
1. Crystalline solids at room Gases, liquids or soft solids
bonds resulting in the formation of giant structure. temperature. under ordinary conditions.
Examples are diamond, silicon carbide (SiC), aluminium 2. High melting and boiling points. Low melting and boiling points
nitride (AlN). These crystals are very hard and possess high with the exception of giant
melting points. . molecules.
(iv) Electrical conductivity : In general, covalent 3. Hard and brittle. Soft and waxy with the exception
of giant molecules.
substances are bad conductors of electricity. Substances 4. Freely soluble in water and in Usually insoluble in water and in
which have polar character like HCI in solution, can conduct polar solvents. Insoluble in non- polar solvents. Soluble in non-
electricity. Covalent solids having giant molecules, are bad polar solvents. polar solvents.
conductors since they do not contain charged particles or free 5. In solid state bad conductors of Badconductorsofelectricitywith
electrons. The graphite can conduct electricity since electrons electricity. Good conductors in few exceptions having layer lat-
can pass from one layer to the other. molten state and in.solutions. tice structure.
(v) Solubility : In general, covalent substances 6. Undergo ionic reactions. Rates of Undergo molecular reactions.
reactions are very high. Reactions Rates of reactions are low.
are insoluble in polar solvents like water but soluble in are fast and instantaneous. Reactions are slow.
non-polar solvents like benzene, carbon tetrachloride, "'~;.i!n'!
ether, etc. This is based on the principle, "Like dissolves like". 2.19/ COORDINATE BOND
Some of the covalent compounds like alcohols, amines
It is a special type of covalent bond in which both the shared
dissolve in water due to hydrogen bonding. Covalent solids
electrons are contributed by one atom only. It may be defined
having giant molecules are practically insoluble in all
as a covalent bond in which both electrons of the shared
U
solvents.
(vi) Molecular reactions: Covalent substances show pair are contributed by one of the two atoms". Such a bond
is also called as dative bond. A coordinate or a dative bond
molecular reactions. The reaction rates are usually low
is established between two such atoms, one of which has a
because it involves two steps (0 breaking of covalent bonds
complete octet and possesses a pair of valency electrons
of the reactants and (ii) establishing of new bonds while the
while the other is short of a pair of electrons.
ionic reactions involved only regrouping of ions.
(vii) Isomerism : The covalent bond is rigid and ••
directional. On account of this, there is a possibility of or A-B
different arrangements of atoms in space. Covalent com-
pounds can, thus, show isomerism (structural and space). This Bond is represented by an arrow (~).
The atom which contributes electron pair is called the

donor while the atom which accepts it is.called acceptor.
.ute : Coordinate bond after formation is indistinguishable
a
from covalent bond.
The formation of a coordinate bond can be looked upon
as a combination of electrovalent and covalent bonds. The
formation may be assumed to have taken place in two steps: .
(i) The donor atom loses one electron and transferred to (iii) Formation of H 20 2 : Oxygen in water has two lone
acceptor atom. As a result donor atom acquires a positive pairs of electrons, out of which one is donated to another
charge and the acceptor atom acquires a negative charge. oxygen atom forming hydrogen peroxide .
]+
[·fx~r
•• --...,.x x [ •• •• xx
: A : + 'B ~ - - . : A • H-O: + 0 ~ - - H-O-O
•• xx •• I xx I
These two charged particles now contribute one
(ii) H H·
Donor Acceptor
electron each and this pair is shared by both the atoms.
[:A... M XX]- --
. (iv) Formation of ozone: Oxygen molecule consists of
•• xx
: A+: lT~ two oxygen atoms linked by a double covalent bond. Each
+ .B~
•• xx •• x x oxygen atom has two lone pairs of electrons.When one lone
pair of electrons is donated to a third oxygen atoin which
As the coordinate bond is a combination of .one
has six electrons, a' coordinate bond is formed.
electrovalent bond and one covalent bond, it is also termed
as semi polar bond, •• •• xx
The compound consisting of the coordinate bond is : 0 = 0: + O~' - - 0=0-0

xx
termed coordilla~e compound. Some examples of coordinate Donor Acceptor
bond formation are given below:
(i) Combination of ammonia and boron trifluoride: (v) Formation of CO: Carbon has four valency electrons
Although the nitrogen atom has completed its octet in and oxygen has six. Two combine to form a double bond and
ammonia, it still has a lone pair of electrons in the valency a coordinate bond as to achieve their octet completed.
shell which it can donate. The boron atom in boron trifluoride •• xx
is short of two electrons which it accepts and completes its c:+ ~ 0 ~ - - : C~O ~
octet. Acceptor Donor
H F H F
.I I I I • Characteristics of Coordinate Compounds
H-N: + B-F H-N-B-F
I I I I The properties of coordinate compounds are intermediate
H F H F between the properties of electrovalent compounds and
Donor Acceptor Coordination compound covalent compounds. The main properties are described
Any atom or ion or molecule which has one unshared below:
electron pair which it can donate is termed as Lewis base (i) Physical state: These exist as gases, liqUids and solids
while those which are capable of accepting the lonepair are under ordinary conditions. .
termed as Lewis acids. In above example ammonia is a Lewis (ii) Melting and. boiling points: Their melting and
base while boron. trifluoride is a Lewis acid. boiling points are higher than purely covalent compounds
Note: H+ ion and cations of transition metals such as Cu2+,
and lower than purely ionic compounds.
(iii) Solubility: These are sparingly soluble in polar
Co2+, Fe2+, Mn2+, Cr3+, Ni+, ett., act as Lewis acids. The
solvents like water but readily soluble in non-polar (organic)
donors are also called as ligands.
solvents.
(ii) Formation of ammonium ion: Hydrogen ion (H+) (iv) Stability : . These are as stable as the covalent
has no electron and thus accepts a lone pair donated by compounds. The addition compounds are, however, not very
nitrogen. stable. It is also a strong bond because the paired electrons
cannot be separated easily.
Chemical Bonding 83
(v) Conductivity: Like covalent compounds, these are (v) IF7 molecule: Iodine forms seven single covalent
also bad conductors of electricity. The solutions or fused bonds with seven fluorine atoms utilising 7 valency
mass do not allow the passage of electricity. electrons. The iodine atom attains 14 electrons in outermost
(vi) Molecular reactions: These undergo molecular shell.
reactions. The reactions are slow.
(vii) Isomerism: The bond is rigid and directional. Thus,
FFF
coordinate compounds show isomerism. '
(viii) Dielectric constant: The compounds containing
coordinate bond possess high values of dielectric constants.
xx
~Ix+7·F:
x x
••
•• - 'W
F-I-F
F
A
F
2.2ff$1 FAILURE OF OC"rET RULE
::;0:;>;'
There are several stable molecules known, in which the octet To explain the above abnormalities, the following two
rule is violated, i.e., atoms in these molecules have number concepts were introduced:
of electrons in the valency shell either short of octet or:nore 1. Sugden's concept of singlet linkage :
than octet. Some important examples are:
(i) BeCl2 molecule: BeClz(beryllium chloride) is a stable Sugden introduced the idea of singlet linkage in favour of
molecule. Be atom forms two single covalent bonds with two octet rule. According to this concept the maximum number
chlorine atoms, i.e., it attains four electrons in the outer shell. of electrons in the outermost shell of any atom cannot exceed
eight. In the molecules of PCls, SF6, IF7, etc., the central atom
•• is linked with some of the combining atoms by single-
xBe x +2 . C I : - CI-Be-Cl electron bonds, called· singlet linkage while the remairting
•• atoms are linked by the: ,nornlal two electrons bonds. The
bond is represented by a half arrow ( ~) with the head
(ii) BF3 molecule: Boron atom forms three single covalent pointing from donor towards the acceptor.
bonds with three fluorine atoms, i.e., it attains six electrons In PC Is, three chlorine atoms are linked by normal
in the outer shell. covalent bonds and two chlorine atoms are linked by singlet
linkages, thus, phosphorus achieves 8 electrons in the
F outermost shell.
x •• ..I
x B x + 3 : F: - B-F CI
• ,I
. ,". 'F
\,
I CI
(iii) PCls molecule Phosphorus atom have five or CI-P(
electrons in valency shell. It forms five single covalent bonds J CI
with five chlorine atoms utilising all the valency electrons CI
and thereby attains 10 electrons in the outer shell.
,This structure indicates that the nature of two chlorine
'atoms is different than the other three as singlet linkage is
~Px
x
x
+5.CI:
••
•• - CI
Cl>r<CI
CI
CI weaker than normal covalent bond. The above observation
is confirmed by the fact that on heating, PCls dissociates into
PCl3 and Clz.
PCls ~ PCl3 + Clz
Similarly, in SF6, four singlet linkages are present while
(iv) SF6 molecule: Sulphur atom has six electrons in the
in IF7, six singlet linkages are present.
valency shell. It forms six single covalent bonds with six
fluorine atoms utilising all the valency electrons and thereby
attains 12 electrons in the outer shell.
x x
xSx+ 6 • F :
xx
••
•• -
2. Sidgwick's concept of maximum covalency (c) Hydrogen actually bonds to an oxygen atom and not
to the central atom in ternary acids (oxyacids).
This rule states that the covalency of an element may
exceed four and octet can be exceeded. The maximum For example: Nitrous acid HN02, has the skeleton
covalency of an element actually depends on the period of HONO. However, there are exceptions to this rule, such as
periodic table to which it belongs. The maximum covalency for H 3P02, the skeleton is H P Oll.
of the elements is tabulated below: o
H
Maximum No. of electrons in (d) For polycentred species such as C 214, the most
Period Elements
the outermost orbit
HH
1st H 2 4 symmetrical skeleton is used. C C is the skeleton for C2H 4·
2nd Li to F 4 8 HH
3rd Na to Cl 6 12
(ii) Calculate the number of electrons available in the
4th K to Br 6 12
valency shell of all the atoms.
5th} Rbonw.ro. }
and rest of 8 16
For negatively charged ions add to the total number of
electrons equal to the charge on the anion and for positively
6th the elements
charged ions, subtract the numb~r of electrons equal to the
This rule explains the formation of PCls and SF6. Thisalso
explains, why nitrogen does not form NFs or NCls because
charge on the cations.
The total number of electrons calculated in this way is
..
nitrogen belongs to second period and the maximum represented by symbol A.
covalency of nitrogen is four.
For example: A for H2S04
LEWIS' FORMULAE FOR MOLECULES A = 2 X 1 (for hydrogen atoms) + 1 x 6 (for 5 atom)
AND POLYATOMIC IONS + 4 x 6 (for 0 atoms)
:: 2 + 6 + 24
Lewis electron-dot formula of a molecule or a polyatomic ion
:: 32 electrons.
shows how atoms are bonded with each other. Bonding
electrons are indicated either by two dots or by a dash. For A for POrion
instance, a water molecule can be represented by either of A = 1 x 5 (for P atom) + 4 x 6 (for 0 atoms)
the follOWing two diagrams.. + 3 (for charge)
•• •• 5 + 24 + 3.
H-O:
= 32 electrons.
I A for NHl ion
H H
Lewis dot formula Dash formula A = 1 x 5 (for nitrogen atom) + 4 x 1 (for H atoms)
1 (for positive charge)
Lewis dot formulae show only the number of valency
electrons, the number and kinds of bonds, but do not depict 5+4-1
the three dimensional shapes of molecules and polyatomic 8 electrons.
ions. Lewis formulae are based on the fact that the (iii) Calculate the total number of electrons needed by
representative elements achieve a noble gaS configuration in all atoms to achieve noble gas configuration. This number
most of their compounds, i.e., 8 electrons in their outermost is represented by N.
shell (exceptfor H 2, U+ and Be2+ions which have 2 electrons). For example: N f01' H 2S04
The follOwing steps are followed in constructing dot
N =2x2+8xl+8x4
formulae for molecules and polyatomic ions:
(i) Write a symmetrical 'skeleton' for the molecules and =4+8+32
polyatomic ions. = 44 electrons.
(a) The least electronegative element is usually taken as (iv) Calculate the total number of electrons shared. This
the central element except ll. is represented by Sf which is equal to N - A.
For example: C02 has the skeleton OCO. For example: S for H 2SO 4
(b) Oxygen atoms do not bond to each other except in ~, .5 :::: N-A
0 3, the peroxides and superoxides. The phosphate i.on = 44 32
b
12 electrons.
(pot) has the skeleton 0 P O.
o
Chemical Bonding 85
(v) Place the shared pair of electrons into the skeleton, Step (ii)
using double and triple bonds only when necessary. A 1 X 6 (for S) + 4 x 6 (for 0) + 2 (for negative charge)
for example : 6 + 24 + 2
= 32 electrons
0..
o 0
I Step (till'
H 2SO4; HOSOH; H:O: S :O:H; H-O-S-O-H N = 1 x 8 (for S) + 4 x 8 (for 0)
0" I
o 0 8 + 32
40 electrons
Skeleton Dot formula Dash formula ,Step (iv) S N - A = 40 32 = 8 electrons shared
(vi) Place the additional unshared (lone) pairs of
electrons to fill the octet to every atom except hydrogen which
o
I
can have only 2 electrons as the total comes equal to A as Step (v) 0-S-02-
calculated in step (ii).
For H 2S04
o b
• O· Two coordi- •• 2-
:0: •• 2-
:0: :0:
• • ' , ' •• nate bonds to .. .. .. ,
Two coordinate
bonds to utilise all
.. .. ..
H:O: S:O:H or H-O-S-O-H
-l..
utilise all the
six valency .. .. ..
Step (vi) : 0: S: 0: or :O-S-O:
-l.. the six valency
..
:0: :..
0: electrons of S.
..
:0:
..
:0: electrons of S.
I SOME WORKED EX?\MPLE.8 '. Example 3. Write the Lewis dot formula or au::;" forll/ula
for the CO~- ion.
Example 1. Write the Lewis dot formula and dash formula
for CO2 , Solution: Step (i) Skeleton 0 C 0 2-
Solution: Step (i) The skeleton is acO. o
Step (ii) Step (ii)
A 1 x 4 (for C) + 2 x 6 (for 0) = 4 + 12 16 electrons A = 1 x 4 (for C) + 3 x 6 (for 0) + 2 (for negative charge)
= 4 + 18 + 2
Step (iii)
24 electrons
N 1 x 8 (for C) + 2 x 8 (for 0) == 8 + 16 24 electrons
Step (iii)
Step (iv) S N ~ A 24 16 = 8 electrons shared
N = 1 x 8 (for C) + 3 x 8 (for 0)
= 8 + 24
Step (v) 0: :c::O
::;; 32 el~ctrons
Step (iv)
Step (vi) : 0: :C: :0: or :O=C=Q:
S N-A
. Example 2. Write the Lewis dot formula and dash formula ::;; 32 - 24
for the SO~- ion. ::;; 8 electrons shared (4 pairs shared)
Solution: Step (i) The skeleton [ 0 !r

0
Step (v)
Step (vi)
O:C: :02-
••
o
:O:C::O:
•• 2-
or :O-C=02-
•• I ••
:0: :0:
Electron dot formulae and Bond formulae or H-C==C-H

Dash formulae of some compounds
Molecular Electron dot Dash Formula or H H H H
Formula Formula Bond Formula eX eX
I I
H~C~C~H H-C-C-H
(a) Compounds baving electrovalent bonds only I I
H H H H
••
NaCI Na+ :CI:- Na+Cr H H
•• .x I
•• •• H-P
MgC12 : Cl ~- Mi+ ~ Cl :- .x I
•• •• H H
•• •• • ••
CaC12 : Cl ~- Ca2+ ~ Cl : - : Cl:
•• •• Cl
•• •x I
:Cl~P~ CI-P
MgO •• • x
I
: Cl: CI
••
••
Na+: S :2:- Na+
•• •• ••
H~O:O~H H-O-O-H
CaR2
•• ••
•• •• (c) Compounds baving electrovalent and covalent bonds

: F:- A13+ : F :-
•• ••
x.
: F :-
NaOH Na+[~ ~ ~ Hr
••
(b) Compounds baving covalent bonds only KCN K+[.x C ~:
x. N .]-
•
••
HCI H ~Cl: H-Cl
••
H20
••
H~O~H H-O-H [ .. .. .. ]2-
Ca2+ : 0 : C : 0 :
•• : ~..
[
Ca++ O-~-O
]2-
••
•• ••
H~S~H H-S-H (d) Compounds baving covalent and coordinate bonds
••
H H
co C:!ii:O
x. I ••
H-N
• x
I N20 •• N:~
ex N xx 0 ••
H H ••
xx xx ••
HCN H-C N
~O~~N~N~~O: O=N-N=O
•• ~
H H o
xx
.x I xX ••
H~C~H H-C-H
~O~:N~N~:O: O=N-N=O
.x I •• xx
~ ~
H H : 0:: 0 : o 0
•• ••
xx xx xx
H H H H ~O~:N:O~N:~O~ O=N-O-N=O
x. eX I I •• xx ••
~ ~
C~~C C=C
x. ex I I ~O~ ~O~ o 0
H H H H xx xx
Chemical Bonding 87
xx XK xx
H ~ 0 ~ N : ~ 0 .~ . H-O-N=O ~ 0 ~ o
xx •• ~
~ 0 ~ o
xx •• xX
t
H~O~P~O~H H-O-P-O-H
xx xx ex xx I
xx xx o
[NO) .~ 0 ~ N :~0 ~ I
xx •• H
H
~ 0 ~
xx Note: For sol- remove protons from H3P04 molecule.
xx xx
Note: Remove proton from HN03 molecule.
~O~ ~O~ o
xx •• xx xx •• xx •• xx
H~O~N:~O~ H-O-N=O
xx
xx.. xx
[N02: ~O~N:~O~ -O-N=O]
xx
Note: Remove proton from HNOi molecule.
xx.. xx Note: For P20t remove protons from ~P207 molecule.
~O:S:~O~ O-S=O H
xx 0
Note: On the basis of overlapping and hybridization concept, the.
xx .x xx I
H •x O~P~O~ H H-O-P-O-H
o xx •• xx ~
structure ofS0 2 is, s( ,i.e., octet rule is not followed. ~ 0 ~ 0
o xx
xx xx
~O: S :~O~ O-S=O •• •• ••
xx ••
~ : Cl CI: : C1:
~O ~ o •• +. .+ .~
• •+
xx Al Al
A12C16
Note: On the basis of overlapping and hybridization concept, the (Anhydrous)
••
+. •• ••
structure OfS03 is, O=S= 0, i.e., octet rule is not followed. : Cl : Cl: CI:
II . •• ••
o
xx
Cl):Al<Cl)Al<Cl
~ 0 ~ o
xx •• xx t CI CI Cl
H ~ 0 ~ S ~ O·~ H H-O-S-O-H
Note: Anhydrous aluminium chloride is a dimer.
xx •• xx ~
~ 0 ~ o xx
xx o
xx • ++ .,.:f.
~ 0 ~ :0·
••
:0:
••
xx •• xx
SO~- ~O~S x• O~ xx
xx xx •• ~ Cl ~ Cl
~ 0 ~ xx eX xx
I
xx ~O:S:O~ O-S-O
Note: Remove protons from H2S04 molecule. xx eX xx
I
~ CI ~ Cl
xx •• xx xx
H2S03 H •x o ~ S~O~ H H-O-S-O-H xx •• xx
xx •• xx ~ SOC12 ~ 0: S ~Cg O-S-Cl
xx eX xx
~ 0 ~ 0 I
xx ~CI~ Cl
xx
xx •• xx
SO~- ~O~S~O~ -O-S-O- xx •• xx
xx •• xx ~ RI03 H~O;I:O~ H-O-I-O
xx •• xx
~ 0 ~ 0 ~O~
!
xx xx o
Note: Remove protons from H2S03 molecule. Note: For I03' remove proton from HI03 molecule.
xx molecule is assigned a formal charge. It is defined as the

; 0 ; o difference between the number of valence electrons in an
xx ••
H ~ 0 ~ CI: 0 ;
xx
H-O-CI~O
t isolated (i.e., free) atom and the number of electrons
assigned to that atom in a Lewis structure. The counting of
xx •• xx -J, electrons is based on the assumption that the atom in the
xx -
o _molecule owns-one electron of each shared pair and both the
Note: For 004 remove proton from HCI04 molecule.
xx •• xx
a
electrons of lone pair.
HCI03 H~O~CI:O; H-O-CI~O Formal charge on an atom::::: total number of valence
xx •• xx
~O;
-J, in a Lewis structure electrons in the free atom
xx o - total number of non
Note: For 003 remove proton from molecule. bonding (lone pair) electrons
(e) Compounds having electrovalent, covalent and - ~ total number of bonding
coordinate bonds (shared) electrons
The concept of formal charge can be explained by nitrous
oxide molecule, N 20. The electron dot structure for NP can
be written as:
eX ••
°NoxNXO'
• eX ••••
Using the given relationship, the formal charges on the

three atoms can be calculated as follows:
N
(a) Terminal nitrogen atom:
Valence electrons = 5
Lone pair = one (two electrons)
Total number of bonding electrons = 6
1
Formal charge = 5 - 2 - :2 x 6 ::::: 0
(b) Central nitrogen atom:
N Valence electrons = 5
N
Isosters: Molecules or ions (polyatomic) containing Lone pair = nil
same number of atoms and the same total number of electrons Total number of bonding electrons::::: 8
1
are called isosters. Usually, isosters have same identical Formal charge = 5 - :2 x 8 ::::: + 1
Lewis structures. (c) Terminal oxygen atom:
No. of No. of Valency Valence electrons = 6
Isosteric species Lone pair : : : three (six electrons)
atoms electrons electrons
Total number of '-'
CH 41 NH! 5 10 (8)
bonding electrons = 2
C0 21 N20, CNO-, NOZ: 3 22 (16)
NOi, CO~-I BOr 4 32 (24) Formal charge = 6- 6- :21 '
x2=- 1
NH31 H30 + 4 10 (8)
Thus, the structure can be written as follows:
Cl031 SO~- 4 42 (26) + •• -
00'4, pot 5 50 (32) :N N-O:
••
Mn04! 5 58 (32) The advantage of calculation of formal charges is that it
helps to select the most stable structure of the molecule or
N2! CO and CN- are isosters. Their Lewis structures are
ion. The most stable structure is the one which has the
identical.
smallest formal ch.3.rges on the atoms or zero formal charges
~C:;:O: XXXNX]-
[ •• C ••• x on the atoms. Negative formal charges should appear on the
N=N most electronegative atoms. Adjacent atoms in the structure
should not carry the formal charges of same sign. The total
2. FORMAL CHARGE formal charges on the atoms in a Lewis structure must be
zero for a neutral molecule and must equal to net charge for
In case of the polyatomic ions, the net charge is possessed a polyatomic ion.
by an lOn as a whole and not by a particular atom. However,
for some purposes each atom in a polyatomic ion or
Example 4. Calculate the formal charges on atoms in
(a) CS2 and (b) CO~- ion
Chemical Bonding 89
Solution: (a) Lewis structure of CSz is When the heteronuclear diatomic molecule is considered
the situation is not simple. Electronegativity is defined as
the tendency of an atom to attract electrons towards itself
Formal charge on each sulphur atom = valence electrons . in a chemical bond. Thus, in heteronuclear diatomic
- lone pair electrons - (1/2) bonding electrons
molecule, both the atoms jomed by the covalent bond possess
= 6 4 - (1/2) x 4 = 0
different electronegativity. As a result, the atom having higher
Formal charge on carbon atom ::= valence electrons lone
value of electronegativity attracts the shared electron pair
pair electrons - 1/2 bonding electrons
=4 - 0 - (1/2)x 8 0 much more strongly than the other atom. For example, in HF
(b) Lewis structure of CO~- ion is
the electron pair is more attracted towards F as it is more
2- electronegative than hydrogen. Due to this, the fluorine end
:0: of the molecule appears negative and the hydrogen end
II positive. Such molecules having two oppositely charged
poles are called polar molecules and the bond is said to be a
.. /C\ ..
..
:0 ..
0: polar covalent bond.
F _ _ _e _ _ _
F
H _____e_
F
Formal charge on carbon atom ::= 4 - (1/2) x 8 ::= 0 • •
Equally shared Unequally shared
Formal charge on double bonded 0 atom
= 6 - 4 - (1/2) x 4 ::= 0 A covalent bond, in which electrons are shared
Formal charge on single bonded 0 atom unequally and the bonded atoms acquire a partial positive
6 - 6 - (1/2) x 2 =-1 and negative charge, is called a polar covalent bond or a
Example 5. Select the most stable correct structure of covalent bond between two dissimilar atoms is a polar
COC12 covalent bond.
Two kinds of notation are used to indicate a polar covalent
(a) :O-C=Cl: (b) :C = o-ci: bond.
I I
0+ 0_ ~
:Cl: :C1:
(c) :O=C-CI:
.. H-F or H-F
Polar covalent bonds may be thought of as being inter·
I mediate between the non·polar bonds and pure ionic bonds.
:C1: Bond polarity is described in terms of ionic character
which usually increases with increasing difference in the
Solution: (a) FC on 0 atom 6 - 6 - (1/2) x 2::=-1 electronegativity (EN) between bonded atoms. .
FC on C atom = 4 - 0 - (1/2) x 8 0
H-F H-Cl H-Br H-I
FC on C1 atom = 7 - 6 - (1/2) x 2 0 EN 2.1 4.0 2.1 3.0 . 2.1 2.8 2.1 2.5
FConClatom=7-4-(1/2)x4 +1 Difference in EN 1.9 0.9 0.7 0.4
)
(b) FC on C atom = 4 - 4 - (1/2) x 4 = -2 Ionic character decreases as the difference
FC on 0 atom = 6 0 - (1/2) x 8 = +2 in electronegativity decreases
FC on CI atom == 7 - 6 - (l/2) x 2::= 0 Pauling has estimated the approximate percentage of ionic
character in various A-B covalent bonds from the (XA - X B)
(c) FC on 0 atom = 6 4 (1/2) x 4::= 0
values, i.e., electronegativity difference of the two atoms
FC on C atom = 4 - 0 (1/2) x 8 ::= 0 forming the covalent bond.
FC on 0 atom = 7 - 6 - (1/2) x 2::= 0
Percentage of
Structure (c) with formal charges of zero is the most stable XA-XB
ionic character
Nature of A-B bond
correct structure.
0 0 Purely covalent
2.~1 POLARITY OF COVALENT BOND 0.1 to 0.8

0.9 to 1.8
0.5 - 15
19 47
Covalent
Polar covalent
In all homonuclear diatomic molecules like hydrogen 1.9 50 50% ionic and 50% covalent
molecu].e{H2), chlorine molecule (02), fluorine molecule (F2), 2 to 3.2 55-93 Ionic
oxygen molecule (02), the electron pair or pairs is shared
Hanny and Smyth gave the following equation for calcula·
equally between the two atoms. This means that shared
ting the percentage of ionic character in A-B bond on the
electrons are equally attracted to both the nuclei and therefore
basis of the values of electronegativity of the atoms A and B.
spend equal amounts of time near each nucleus. As a result,
the molecule is neutral or non-polar. Percentage of ionic character::::: [16(XA - XB) + 3.5(XA -XB)2]
This equation gives approximate calculation of percentage Molecule ' H-I. H-Br H-CI H-F
of ionic character, e.g., 50% ionic character corresponds to % ionic character 7 12.9 17.2 43
(XA - XB) equal to 2.,1. (XA - Xg) 0.4 0.7 ' 0.9 1.9
Dipole moment 0.38 D 0.78 D 1.03 D 1.92 D
Example 6. Calculate the percentage of ionic character in
Cs-CI bond in CsCI molecule. The electronegativity values of Cs Dipole moment is a vector quantity,' i.e., it has both
and CI are 0.7 and 3.0 respectively. magnitude as wen as direction. The overall value, of the
dipole moment ofa polar molecule depends on its geometry
Solution: XA - XB Xa-Xcs = (3.0 - 0.7) = 2.3 and shape, i.e.,vectorial addition of dipole moment of the
Percentage of ionic character in Cs--CI bond constituent bonds. A s~metrical molecule is non-polar
= [16 x 2.3 + 3.5 x (2.3)2] even though it contains polar bonds. For example, CCh, BF3,
, [36.8 + 18.51] CH4, CC4 being symmetrical molecules have zero resultant
= 55.31 dipole moments and hence are non-polar since dipole
Example 7. Arrange molecules HF, HCI, HBr andHI in moments summation of all the bonds present in the molecule
the decreasing order of the percentage of ionic character. Electro-, cancel each other. Dipole momentis usually indicated by an
negativity values are as follows: arrow having + on the tail (~), above the polar bond and
pointing towards the negative end.
H = 2.1, F :::; 4.0, CI 3.0, Br 2.8, I = 2.5
Solution: Percentage of ionic character inH-F F H
:::; [16 x 1.9 + 3.5 x (1.9)2]
tlB It
, C;:::-..,.
43
.
F~~F Hx7~H
,
% ionic character in H-Cl :::; [16xO.9 +3.5 x (0.9)2]

H
17.2
% ionic character in HBr = [16xO.7 +3.5 x (0.7)2] Unsymmetrical non-linear polyatomic molecules
always have net value of dipole moment, thus such
12.9 molecules are polar in nature. H 20, CH3Ct NH3, etc., are
% ionic character in HI = [16 x 0.4 + 3.5 x (0.4)2] polar molecules as they have some positive values of
= 7.0 dipole moments.
Order HF > HCl > HBr> HI •I
I
I
2. DIPOLE MOMENT H~O~H o#f~o

Water j.l = I.S4D
, I
Sulphur dioxide
Difference in polarities of bonds is expressed on a numerical
scale. The polarity of a molecule is indicated in terms of
•I
I
I
j.l 1.60D
dipole moment (11). To measure dipole moment, a sample of Cl

the substance is placed between two electrically charged
II •, .
I
plates. Polar molecules orienUhemselves in the electric field I
causing the measured voltage between the plates to change. H~\\~H H~\\~H
The dipole moment is defined as the product of the
distance separating charges of equal magnitude and opposite H H
Methyl chloride Ammonia
sign, with the magnitude of the charge. The distance between j.l= I.S6D Il = 1.46D
the positive and negative centres is called the bond length:
Thus, • 'Calculation of Resultant 'Bond' Moments
11 :::; electric charge x bond ,length
Let AB and AC are two polar bonds inclined at an,angle
=qxd a, their dipole moments are 111 and 112' .
As q is in the order of lO-10 esu and d is in the order of 0_ B
10~ em, 11 is in the order of lO-~8 esu cm. Dipole moment is
measured in 'Debye' unit (D).
1 D = 10-18 esu cm 3.33 X" lO-30 ~oulomb metre,
Generally, as electronegativity difference increases in
diatomic molecules, the value of dipole moment increases.
Greater the value of dipole moment of a molecule, greater the
polarity of the bond between the atoms.
Chemical Bonding 91,
Resultant dipole moment may be calculated u~ing MOLECULAR GEOMETRY AND DIPOLE MOMENT
vectorial method.
General
Molecular geometry Dipole moment Example
=~Ilr + Il~ +2111112 cosO
lIR fonnula
when, a = 0, the resultant is maximum. AX Linear ~ay be non-zero HP, HCl
AX 2 Linear Zero CO 2,CS2
lIR = 1I1 + 1I2 _-l)~-,Q""".L..18_0-<E°(:---_ Bent or V-shape Non-zero H 20, N02
when, a= 180°, the resultant is minimU~. Q1800 ) AX 3 TriangUlar planar Zero BF3
Pyramidal Non-zero NH3, PCl3
lIR = 1I1 - 1I2
T-shape Non-zero CIF3
DIPOLE MOMENT OF SOME COMMON SUBSTANCES
AX 4 Tetrahedral Zero CH4, CC4
Square planar Zero XeF4
1
.' Dipole Dipole See-saw Non-zero SF4, TeC4
Dipole
Compound moment Compound moment Compound moment AXs Trigonal bipyramidal Zero PCls
(D) (0) (0)
Square pyramidal Non-zero BrCls
HF 1.92 NH3 1.46 CH3Cl 1.86 AX 6 Octahedral Zero SF6
HO 1.03 H2O 1.84 C2HsOH 1.68 Distorted octahedral Non-zero XeF 6
HBr 0.78 H 2S 0.92 CH3COCH3 1.30 AX 7 Pentagonal bipyramidal Zero 1F7
HI 0.38 502 1.60 C6HsCI 1.57
(i v) To distinguish cis and trans forms of geometrical
• Applications of Dipole Moment isomers: Experimental values of dipole moment of the
isomers (cis and trans) are determined. The trans isomer
(i) To decide polarity of the molecule: Molecules
usually possesses either zero dipole moment or very low
having zero dipole moment" are said to be non-polar
value in comparison to cis form.
molecules and those having lIR "# 0 are polar in nature.
(ii) To determine percentage of ionic character : H-C-Cl H-C-Cl
The value of dipole moment can be used for determining the I II
amount of ionic character in a bond. Consider a diatomic H:""-C-Cl CI-C-H
molecules say HCl. Suppose this. molecule is completely Cis- 1,2-dichloroethene Trans-l,2-dichloroethene
ionic. Under this condition H+ and cr ions would bear a Jl = 1.9 D Jl '" 0
unit charge equal to 4.8 x 10-10 esu and the bond distance It should be noted that if two groups have opposite
between H and CI atoms = 1.27 A. inductive character then trans isomer will have greater dipole
Thus, theoretical value of )l (considering molecule ,moment of,
completely ionic)
= 4.8 x 10-10 x 1.27 X 10-8 = 6.09 D
Dipole moment of HCl is also determined experimentally.
Let the experimental value be 1.03 D.
Percentage of ionic character in H-CI bond in HCl
molecule
Experimental value of 11 x 100 = 1.03 x _ Trans Cis
= Theoretical value of 11 6.09 100 - 16.9
11 Trans' > 11 Cis
Thus, percentage of ionic character
Experimental value of dipole moment (v) To determine orientation in benzene ring: Dipole
= Theoretical value of dipole moment x 100 moment is useful to ascertain the orientation of substituents.
(iii) To determine geometry of molecules: The values The greater the dipole moment, the greater is the asymmetry.
of dipole moments provide valuable information about the In general, dipole moment follows the order:
structure of molecules. Ortho > meta> para
(a) C02, CSz molecules are linear as values of their dipole
Cl CI CI
moments are zero.
(b) H 20 is not a linear molecule as it has dipole moment.
Actually, it has V-shaped structure and the bond angle is
©Cl ©Cl ©
105°. Similarly, 502 has a bent structure. CI
(c) In ammonia, three hydrogen atoms do not lie Ortho Meta Para
11= 2.54 D 11 = 1.48 D 11=0
symmetrically with respect to nitrogen as it has dipole
moment. It has pyramidal structure.
*In the symmetrical molecules having polar bonds, centre of positive and negative poles coincides leading to zero dipole moment.
In ortho isomers, experimental value of dipole moment is POLARISATION (CHANGE OF IONIC

found different from theoretical value of dipole moment. This CHARAC"rER TO COVALENT
difference is due to dipole-dipole interaction of two groups.
CHARACTER)
c0 When two oppositely charged ions of unequal size approach
~exp ~theo
(No interaction
a~I
d
~exp < ~theo
(Repulsion)
~exp > ~theo
(Attraction due to H-bond)
between two groups) (9 increases, Il decreases) (9 decreases, Il increases)
each other closely (during formation of an electrovalent
bond), the ion smaller in size attracts outermost electrons of
the other ion and repel its nuclear charge. The net result is
distortion or polarisation of the bigger ion. This distortion is
usually done by the cation as its size is smaller than the
anion. The electron cloud of anion no longer remains
(vi) Bond moment: The contribution of individual bond symmetrical but is elongated towards. the cation. The ability
in the dipole moment of a polyatomic molecule is termed of a cation to polarise the nearby anion is called its polarising
bond moment. The measured dipole moment of water power and the tendency of an anion to get distorted or
molecule is 1.85 D. This dipole moment is the vectorial sum
of the individual bond moments of two O-H bonds having
bond angle 104.5°.
Thus,
or
llobs = 21l0-H cos 52.25
1.85 =21lO-H x 0.6129
8
(a) No polarisation (b) Polarised anion
llO-H = 1.51 0 Fig. 2.6 Representation of Polarisation
Conclusions deformed or polarised by the cation is called its polarisability.

(i) Dipole moment 0<: Electronegativity difference Due to polarisation, sharing of electrons occur between two
ions to some extent and the bond shows some covalent
For example, HF > HCl > HBr > HI
character. This is shown in Fig.2.6.
(li) Dipole moment 0<: Number of lone pairs of electrons
The magnitude of polarisation depends upon a number
For example, HF > H20> NH3 of factors or the increased covalent character is favoured by
Fluorine has 3 lone pairs, oxygen has 2 lone pairs a number of factors. These factors were suggested by Fajan
and nitrogen has one lone pair. and are known as Fajan's rules.
(iii) Dipole moment 0<: 1/ e (i) Charge on cation: As the charge on the cation
For example, ortho > meta> para increases, its tendency to polarise the anion increases. This
X X X brings more and more covalent nature in the electrovalent
I X I I compound.
~ P"n fIl For example, in the case of NaCl, MgCl2 and AICl3 the
V ~X T polarisation increases, thereby covalent character becomes
X more and more as the charge on the cation increases.
180"
Cation Formula of Melting point of the
(iv) Homoatomic molecules and molecules having normal the chloride chloride, °C
shapes such as linear, trigonal, tetrahedral possess
Na+ +1 NaCl 800 Covalent
zero dipole moment.
Mg++ +2 MgCl2 712 character
For example, Clz, N 2, Oz, COz, BCI3- CCl4, SiC4 Al+++ +3 A1Cl3 Sublimes increases
(v) Molecules having distorted shapes like angular,
pyramidal, sea-saw, etc, show dipole moments. Similarly, lead forms two chlorides PbCl2 and PbCl4
having charges +2 and +4 respectively. PbC4 shows covalent
For example, H 20,SOz, H 2S, NH3- SF4
nature.
(vi) Dipole moment of a cis-alkene is more than trans-
In general, if a metal forms more than one halide, the
alkene. In trans-alkenes, it is zero due to similar
halide haVing higher charge on the cation (i.e., higher
groups (symmetry).
oxidation state) is usually more covalent in nature in
It should be noted that if two groups have opposite comparison to halide having a cation with lower charge, i.e.,
inductive character, then trans isomer will have lower oxidation state or in other words, the melting point of
greater dipole moment. the halide having higher oxidation state is less than the
melting point of halide having lower oxidation state.
Chemical Bonding 93
(ii) Size of the cation: Polarisation of the anion in- I'oints to Remember
creases as the size of the cation decreases, i.e., theelectrovalent
compounds having smaller cations show more of the (i) On moving down a group, the polarising power of the
covalent nature. For example, in the case of halides of cations goes on decreasing.
alkaline earth metals, the covalent character decreases. (ii) Polarising power of the cations increase in moving left
to right in a period.
Cation Radius of Formula of Melting point of the (iii) The polarisability of the anions by a given cation
the cation A the chloride chloride, °C decreases in moving left to right in a period.
Be2+ 0.31 BeCl2 405
(iv) The polarisability of the anions by a given cation
r
Mg2+ 0.65 MgC12 712 § s i .[
~ increases moving down a group .
Ca2+ ...... <:.)
'" e bile
'"
:§~
0.99 CaCl z 772
(v) Increase of polarisation brings more of covalent
S~+ u15]8
Ba2+
1.13
1.35
SrClz
BaClz
872
960 1 <:.).~ <U "0
~
character in an ionic compound. The increased covalent
character is indicated by the decrease in melting point of the
Low melting point indicates more covalent nature. ionic compound. Examples:
(iii) Size of anion: The larger the size of the anion, more Polarisation increases ~
easily it will be polarised by the cation, i.e., as the size of the Covalent character increases ~
anion increases for a given cation, the covalent character Melting point decreases ~
increases. For example, in the case of halides of calcium, the
(a) NaF < NaCl < NaBr < NaI
covalent character increases from F- anion to 1- anion. (Size of anion increases)
801 755 651
Cation Anion Anion size Formula of Melting point of the
A the halide halide,oC
(b) CaF2 < CaCl2 < CaBr2 < CaI2
2
Ca + F- (Size of anion increases)
CaF2
1931~~~
"· \"~~·
1.36
cr 1.81 CaClz m.pt. (OC) 1392 772 730 575
772
Br- 1.95 CaBrz 730 8.g.~ ~ j (c) BaCl2 < SrCI2 < CaCl2 < MgCh < BeCl2
(Size of cation decreases)
1- 2.16 CaI2 575 ::E
m.pt. (OC) 960 872 772 712 405
Similarly, in the case of trihalides of aluminium, the
(d) NaCl < MgC12 < AlCl3
covalent character increases with increase in size of halide
(Charge on the cation increases)
anion. m.pt. (0C) 801 712 sublimes
(e) LiCl < < BCl3 < CC4
Covalent character increases as the size of the (Size of the cation decreases)
halide ion increases
(iv) Configuration of cation: The cations with 18 (f) GeCl2 < GeCl4; SnCl2 < SnC4; PbCh < PbC4
electrons in outermost shell bring greater polarisation of the (g) HF < H 2O < NH3 < CH4
anion than those with inert gas configuration even if both
(h) HF < HCI < HBr < HI
the cations have same size and same charge. For example,
CuCI is more covalent than NaCL (i) NaCl < CuCl; NaI < AgI
Cu+ Ion 2,8, 18 Na+ 2, 8
Size 0.96 A 0.95 A HYDROGEN BONDING
Melting point CuCI, 442°C NaCl, 800°C
In 1920, Latimer and Rodebush introduced the idea of
Cations having more of core electrons are more
"hydrogen bond" to explain the nature of association in
polarising and thus, favour covalency.
liquid state of substances like water, hydrogen fluoride,
In general, all those electrovalent compounds having high
ammonia, formic acid, etc. In a hydrogen compound, when
values of polarisation (more covalent character) are found to
hydrogen is bonded to highly electronegative atom (such as
be less soluble in water but more soluble in organic solvents.
F, 0, N) by a covalent bond, the electron pair is attracted
The following examples support this view:
towards electronegative atom so strongly that a dipole
. (0 Sulphides are less soluble in water than oxides of the
results, i.e., one end carries a positive charge (H-end) and
same metal.
other end carries a negative charge (X-end).
(ii) Lithium salts are soluble in organic solvents.
(iii) Beryllium compounds are less soluble than corres- ~Lo+ 0_ 0+
ponding other alkaline earth metal compounds. X:H or X-H
(iv) The solubility of aluminium halides decreases from ~
Electronegative atom
I
AlF3 to A1I3 ·
If a number of such molecules are brought nearer to each Intermolecular hydrogen bond is also responsible for
other, the positive end of one molecule and negative end of increase in the viscosity. Greater is the extent of hydrogen
the other molecule will attract each other and weak bonding more is the viscosity.
electrostatic force will develop. Thus, these molecules will CHzOH
associate together to form a duster of molecules. CHzOH I
~L 0+ 0_ 0+ 0_ 0+ 0_ 0+ 0_ 0+ I CHOH
X-H---X-H- X-H - X-H-~-X-H CHzOH I
11 = 1.2 CP. 11 = 17 CP. CHzOH
The attractive force that binds hydrogen atom of one
molecule with electronegative atom of the other molecule of 11 = 1070 CP.
the same or different substance is known as hydrogen c.P. stands for centipoise.
bond. This bond is represented by 3 dotted line. (b) Intramolecular hydrogen bonding: This type of
Hydrogen bonding is of two types. bonding results between hydrogen and an electronegative
(a) Intermolecular hydrogen bonding: This type of element both present in the same molecule. This type of
bonding results between the positive and negative ends of oonding is generally present in organic compounds.
different molecules of the same or different substances. Examples are o-chlorophenol, o-nitrophenol, o-hydroxy
Examples B. benzoic acid, etc.
(i) Hydrofluoric acid:
(X0,
~
I. CI/
~
(X0,~
~ I w. . .6
(X0,
~
I 7
c,p,o
~o
OH
I
a-Chlorophenol a-Nitrophenol a-Hydroxy benzoic acid
This type of bonding decreases the boiling point of the

compound. The solubility of the compound also decreases.
(m Ammonia:
• Nature and Importance of Hydrogen Bond
(i) Hydrogen bond is merely an electrostatic force rather
than a chemical bond.
(li) Hydrogen bond never involves more than two atoms.
(iii) Bond energy of hydrogen bond is in the range of 3 to
10 kcal/ mole (10 to 40 kJ per mole), i.e., aboutl /10 the energy
(ill) Water: of a covalent bond (strength 50-100 kcal morl ).
0+ 0+ (iv) With the increase of electronegativity and decrease in
H H size of the atom to which hydrogen is covalently linked, the
I I 0+ strength of the hydrogen bond increases. It·is evident from
O-H ---O-H --- the energies of hydrogen bonds in the three elements.
(iv) Formic acid: H-F - - - H > H-O - - - H >
. O_H __~160pm H-N - • - H
10 kcal morl 7 kcal mol-l . 2 kcal mol-l
H-C( )C-H Energy of some hydrogen bonds in neutral molecules are
tabulated below:
. O----H~lOOpm
(v) p-chlorophenol: Bond Average bond energy kJ mor
F-H--O 40-45
---Cl 00-
~ ;) O-H --- CI 0-
~ ;) O-H ---CI F-H---F 23-25
. a.. O-H---O 20-30
0- ~ ;) O-H--- O-H---S
O-H---F
15-20
12-15
This type of hydrogen bonding increases the boiling point
of the compound and also its solubility in water. The increase N-H---N 12-25
in boiling point is due to association of several molecules of N-H---O 20-25
the compoUnd:
Chemical Bonding 95
(v) All the three atoms in X-H- - - X lie in the straight To explain the above limitations~ the following two theories
line. based on quantum mechanics have been proposed.
Without hydrogen bonding water would have existed as (a) The valence bond theory and
a gas like hydrogen sulphide. In that case, nollfe would have (b) Molecular orbital theory.
been possible on this earth. Hydrogen bonding exists in The valence bond theory: This theory was presented
molecules of living organisms. It exists in various tissues, by Heitler and London, in 1927, to explain how a covalent
blood, skin, bones, etc. The cotton, siIkor synthetic fibres bond is formed. This theory was extended by Pauling and
possess rigidity and tensile strength due to hydrogen Slater, in 1931. The main points of the theory are:
bonding. The stickiness of glue or honey is also due to (i) A covalent bond is formed by overlapping of atomic
hydrogen bonding. Thus, hydrogen bonding has great orbitals of valency shell of the two atoms*.
importance in everyday life. (Ii) Only half filled atomic orbitals, i.e., orbitals singly
, occupied can enter into overlapping process. The resulting
• Properties Explained by Hydrogen Bonding bond acquires a pair of electrons with opposite spins.
(a) High boiling and melting points of NH 3, H20 and HF (iii) The atoms with half filled orbitals must come closer
in comparison to hydrides of other elements of V, VI and VII to one another with their axes in proper directions for
groups to which N,O and F belong, respectively, are du~ to overlapping.
hydrogen bonding. H 20 exists in liquid state under ordinary (iv) As a result ofoverlappin~ there is maximum electron
condition while H2S in gaseous state as hydrogen bonding density somewhere between the two atoms. A large part of
exists in water and no hydrogen bonding exists in H 2S. bonding force comes into existence from the electrostatic
(b) Unique properties of water and ice are due to hydrogen attraction between the nuclei and the accumulated electron
bonding. Density of ice is less than water and water cloud between them.
contracts when heated between O°C to 4°C. These two unique (v) Greater the overlapping, higher is the strength of the
properties are on account of open cage structure of ice due chemical bond. The amount of energy released per mole
to hydrogen bonqing. . during overlapping is termed bond energy. This energy
(c) Strength of certain acids and bases can be explained stabilises the system. Hence; the molecule formed has less
on the basis of hydrogen bonding. energy and consequently more stability than the isolated
(d) Solubility: A substance is said to be insoluble in atoms.
water if it does not form hydrogen bonding with water. The (vi) Electrons which are already paired in valency shell
organic compound .like alkanes, aIkenes,ethers, etc., are can enter into bond formation if they can be unpaired first
insoluble in water as they do not form hydrogen bonding and shifted to vacant orbitals of slightly higher energy of the
with water, while alcohols and acids are soluble because they same main energy shell (valency shell), This point explains
readily form hydrogen bonds with water. the trivalency of boron, tetravalency of carbon, pentavalency
Note : Chlorine has the saine electronegatiVity as nitrogen but of phosphorus, hexavalency of sulphur and heptavalency of
does not form strong hydrogen bonds. This is because halogens (CI, Br, I) inspite of the fact that these atoms have
of the larger size than that of nitrogen with the result paired orbital or orbitals in the valency shell. .
that its electrostatic attractions are' weak.
25 2p 25 2p
2.' MODERN CONCEPT OF B [li] Iii I C [li] Ii It I I

'.
COVALENT BOND
Excited state [I] I t Ii I Excited state [1J Iiii I i I
The LeWis or octet concept does not explain thefollowing
points: One electron' is shifted III One electron is shifted I
(i) The cause of covalent bond formation. .
(ii) Nature of the forces operating between the atoms
. I to p:-orbital
'------'--_I ~-------'
to p-orbital
forming a covalent bond. ' 35 3p 3d

(iii) Why different amounts of energies released during the P lliJ I iii I i I ,------,----r---.---,--~
formation of different molecules. "
(iv) Shape and geometry of molecules. rn '----'-'--'----' '----L._'---'---'---'----J
(v) Why the molecules are stable in which central atoms One electron is shifted to
have either less than 8 electrbnsOr more than 8 electrons in d-orbital
the outermost shell., '
*Only symmetrical overlap bring out the covalent bond fonnation, e.g.,
C><illY<3 ~ c:><ill?>G
Synunetrical <;vmmetrical Asymmetrical
(vii) Between two orbitals of the same stability (i.e., having (b) Formation of water molecule: Oxygen atom has the
same energy) one more directionally concentrated would configuration of valency shell Is2 2p;' pyl Pxl, i.e., it has two
form a stronger bond. Dumb-bell shaped p-orbitals will orbitals singly occupied. These two orbitals overlap with Is-
form stronger bond as compared to spherically symmetrical orbital of two hydrogen atoms forming sigma bonds.
s-orbitaI. It is formed by head on or axial overlap.
(viii) Two types of bonds are formed on account of
overlapping. These are (a) Sigma (cr) and (b) Pi (n) bonds.
20
Hydrogen atoms
II (a) Sigma (0) Bond
(15 )
A bond formed between two atoms by the overlap of singly py
occupied orbitals along their axes (end to end overlap) is Oxygen atom ~. .~erlap
called sigma (cr) bond. In such a bond formation, maximum
overlap is possible between electron clouds and hence, it is
a strong bond. Electron cloud of this bond is symmetrical
H '045~ - 0
about the line joining the two nuclei of the two atoms. Sigma GM.O.
H
bond can, thus, be defined as:
"Bond orbital which is symmetrical about the line Fig. 2.9 Formation of water molecule by Sop overlapping
joining the two nuclei is known as sigma bond." It is formed Since the two orbitals of oxygen are at right angle to each
by head on or axial overlap. other an angle of 90° is expected between two sigma bonds
Sigma bonds are formed by three types of overlapping: but actual bond angle observed is 104.5°.
(j) s-s overlapping (Formation of hydrogen molecule) : (c) Formation of ammonia molecule: Nitrogen atom has
Each hydrogen atom has OIle electron in Is-orbital which is the configuration of valency shell2s2 2Pxl 2py1 2pz l, i.e., three
spherical. Is-orbital of both the hydrogen atoms approach singly occupied orbitals are present. These orbitals overlap
each other closely and when they reach a point of maximum with Is-orbitals of three hydrogen atoms forming three sigma
attraction by the two nuclei, they overlap and form a sigma bonds.
bond.
~
pypz~ N
30 -H .
px"
-~H~.o
uo
r ... \ H
8-- 8-- . . . ffi . . . EM:)

Hydrogen Nitrogen (J M.D. H
atoms atom
Molecularaxis
Flg.2.10 Formation of NHs molecule by sop overlapping
Fig.2.7 Formation of H2 molecule by s-s overlapping Since the three orbitals of nitrogen are at right angle to
each other, the expected angle between two sigma bonds
The bond has two electrons which have opposite spins. should be 90 but actual bond angle observed is 107°. '
The probability of finding these electrons is maximum in the (iii) p-p overlapping (Formation of fluorine molecule) :
region between the two nuclei on the molecular axis. The This is illustrated by the formation of fluorine molecule. The
electron density of the bond is distributed symmetrically electronic configuration of fluofit:\e atom is 1;
2s22pi 2pl
about the molecular axis. 2pz l, i.e., one orbital is singly occupied. When p-orbitals of
(ij) s-p overlapping (Formation of HF, H 20, NH3 two fluorine atoms approach each other with their heads
molecules) : directly towards one another, they overlap and form a sigma
(a) Formation of HF molecule: In the formation of HF bond.
molecule the 1s-orbital of hydrogen overlaps with the p-
25. 2p;irover~ '- 2p 2s
orbital of fluorine containing unpaired electron.
,..,..----- [III Ittl.tl {I • ItlI
m
1s ./
Hydrogen atom
'- - - - - -
',.... 2p
,;,; z y x
25 15
IJlulu I [tl] [tl]
Fluorine atom Pz
Fluorine atom . . , ____ ~,/
Pz overlap p-p overlap

onne atom
-c::x::::rHead o~ C><::][>C)- -c:x:::=:><=r

(J M.O.
Fig. 2.11 Formation of F2 molecule by pop overlapping
Note : Strongness of overlapping follows the following order :
Fig. 2.8 Formation of HF molecule by s-p overlapping p-p > s-p > s-s
Chemical Bonding 97
fc1 (b) Pi (n) Bond 6. The shape of the molecule is These bonds do not affect the
determined by these bonds. shape of the molecule.
n-bonds are formed by the sidewise or lateral overlapping 7. a-electrons are referred as 1t-electrons are referred as mobile
of p-orbitals. The overlapping takes place at the side of two localized. electrons.
lobes and hence, the extent of overlapping is relatively 8. a-bond can have independent n;-bond always exists along with a
smaller. Thus, 1t-bond is a weaker bond in comparison to existence. a-bond.
sigma bond. The molecular orbital is oriented above and
All single bonds are sigma bonds. A double bond consists
below the plane containing nuclear axis.
of one sigma and one 1t-bond while a triple bond consists of
one sigma and two 1t-bonds.
C) (i) Bond energy increases from a single bond to a triple
- - o bond.
Bond energy: Single bond < Double bond < Triple bond
(ii) Bond strength increases from a single bond to a triple
bond.
p p p-p overlapping 1tM.O.
Bond strength: Single bond < Double bond < Triple bond
Fig. 2.12 Formation of 1t-bond (iii) Bond length of a multiple bond (double or triple) is
Formation of oxygen molecule: Oxygen atom has two always shorter than the corresponding single bond.
p-orbitals singly occupied in the valency shell. When two . Bond length: Single bond> Double bond> Triple bond
oxygen atoms approach each other, one set of p-orbitals (iv) Reactivity of a multiple bond it; always more than the
experiences head on overlap forming a sigma bond while single bond. This is due to the fact that 1t-electrons are mobile
other set of p-orbitals overlaps sidewise to form a 1t-bond. in nature.
Thus, oxygen molecule has one 0- and one 1t-bond. Reactivity: Single bond < Double bond < Triple bond.
.... ----
1t-bond
..... 2.2!~ HYBRIDIZATION
25 2p />poverra;>,2p 25 The valence bond theory (overlapping concept) explains
[ll] IWtrtl ~Head on) L+I +INI [ll] satisfactorily the formation of various molecules but it fails
~'s!. .-~n~d/ PL'Py Px to account the geometry and shapes of various molecules. l'
Oxygen atom ',;p overl;p Oxygen atom
does not give explanation why BeCl2 is linear, BF3 is plana)
(sidewise)
Sidewise CH4 is tetrahedral, NH3 is pyramidal and water is V-shape~
++
~ _o={)~e:p~ molecule. In order to explain these cases, the valence bone.
theory has been supplemented by the concept of hybridi-
pz pz ~~ zation. This is a hypothetical concept and has been
crM.O~
Py P Head on . I introduoed by Pauling and Slater. According to this concept
. y overlap 1t M.O. any number of atomic.orbitals of an atom which differ in
Fig. 2.13 Formation of 02 molecule
energy slightly may mix with each other to form new orbitals
called hybrid orbitals. The process of mixing or
Similarly, the formation of nitrogen molecule can be amalgamation of atomic orbitals of nearly same energy to
explained. It has one sigma bond and two 1t-bonds. produce a set of entirely new orbitals of equivalent energy is
known as hybridization. The following are the rules of
COMPARISON OF SIGMA (0) AND PI (n) BOND
hybridization:
Sigma bond Pi bond (i) Only orbitals (atomic) of nearly same energy belonging
1. The bond is fonned by the The bond is fonned by sidewise to same atom or ion can take part in hybridization.
overlap of orbitals along their overlapping of orbitals Oateral (ii) Number of the hybrid orbitals formed is always equal
axes (end to end overlap). It overlapping). . It includes pop to. number of atomic orbitals which have taken part in the
includes s-s, sop and pop overlapping. . process of hybridization.
overlapping.
(ill) Most of the hybrid orbitals are similar but they are
2. It is a strong bond. It is a weak bond.
not necessarily identical in shape. They may differ from one
3. Electron cloud is symmetrical Electron cloud is unsymmetrical.
about the line joining the two
another in orientation in space.
nuclei. (iv) Actually the orbitals which undergo hybridization and
. 4. There can be free rotation of Free rotation is not possible around not the electrons. For example, for orbitals of nitrogen atom
2
atoms around this bond. this bond. (28 2px12py12pzl) belonging to valency shell when hybridize,
5. These are less reactive. These are more reactive. form four hybrid orbitals,one of which has two electrons (as
before) and other three have one electron each.
No. of atomic
Type of No. of hybrid
orbitals ~volved Shape of molecules Bond angles Examples
hybridization orbitals
in hybridization
2 sp 2 Linear
(s + p)
3 Sp2 3 Plane triangular

(s + p + p)
4 sp3 4 Tetrahedral 109° 28' CH4, CCl4

(s + p + p + p)
4
dsp2
one'd' (d}-i) + one
's' + two 'p'
4 Square planar IX:
I
"I·
t
I
I
I
I
j_________ I1
I
90" [Ni(CN)4f-, [PtC4]2-
dsp3 or sp3d
5 one's' + three 'p' 5 Trigonal bipyramid 1200 and 900 PCls
+ one d (di)
is p3 or sp3i
6 one '8' + three 'p" + 6 Octahedral
two 'd' (di-i,di)
~Sp3 or sp3~
7 one's' + three 'p' + 7 Pentagonal bipyramid
three 'd ' (dxy,dyzA,:.)
(v) The electron waves in hybrid orbitals repel each other (pairs). This type of observation has been made, for example,
and this tend to the farthest apart. in the molecules of ammonia and water. The following table
(vi) Hybrid orbitals form only sigma bonds. A hybrid bond shows the type of hybridization and the geometry of the
is always stronger than a non-hybrid bond. Hybridization molecules containing only bond pairs of electrons.
increases stability and decreases reactivity and energy of the
molecule. e Some Typical Cases of Hybridization
(vii) Depending on the number and nature of orbitals (i) BeF molecule: Beryllil111'\ atom has the config-
undergoing hybridization, various types of hybrid orbitals uration 18t ,2i. Since there are no unpaired eleCtrons in the
directing towards the corners of specified geometrical valency shell, it cannot form any covalent, bond. Thus,
figures come into existence. The molecule has a regular 2s-orbital is first unpaired and an electron is shifted to
geometry if all the hybrid orbitals after overlapping contain 2p-orbital.
shared pair of electrons, i.e., there are no orbitals containing 2s 2p
lone pairs in the valency shell. If, however, the central atom
is surrounded by one or more orbitals containing lone pairs Ground state of Be atom [ill I I
of electrons in the valency shell, the geometry of the molecule
is distorted to some extent. Thus, the presence of one or more Excited state of Be atom W
orbitals with lone pairs affect the bond angle to some extent sp hybridization
due to repulsion between lone pair (pairs) with bonded pair
. f ....
Chemical Bonding 99
Now, there is hybridization between one s- and one
p-orbital. Two orbitals (hybrid) of same shape and energy H
come into eXistence. These overlap with p-orbital (singly
occupied) each of the two fluorine atoms forming two
sigma bonds. The molecule formed is linear with a bond
angle 180°,
F._-x-__
F _6W\I-1_8
--'-- F H H
Be
Hybrid orbitals
H
Fig.2.14 Formation of BeF2 molecule
(ii) BF3 molecule: Boron atom has configuration'ls2, 282
2pl. In ground state, it has one unpaired orbital which can Fig.2.16 Formation of CH4 molecule
(iv) PCl s molecule: P-atom has configuration 182,2822p6,

2
F
3s 3pi 3pi 3pz l. In ground state, it can form three covalent
bonds as three unpaired orbitals are present in the valency
CI
F F Cl ~:':"----!...f:'
Fig.2.15 Formation of BF3 molecule

CI
only form only one covalent bond. To get trivalency, the
18-orbital is unpaired and the electron is shifted to 2p-orbital.
Now in excited state the three unpaired orbitals undergo Fig. 2.17 Trigonal bipyramid
hybridization giving rise to three hybrid orbitals which are shell. To get pentavalency, 38-orbital is unpaired and the
120° apart. The three hybrid orbitals overlap with three electron is shifted to 3d-orbital. Now, in the excited state the
p-orbitals from three fluorine atoms forming three sigma five orbitals involving one 8-, one d- and three p-orbitals
bonds. The molecule formed is triangular and planar. undergo hybridization giving birth to five hybrid orbitals
bls, ~i2 which overlap with five chlorine atoms forming five sigma
Boron atom in ground state Ii, 282 2Pxl L!.±J ~ bonds. Out of five a-bonds, three bonds which are located at
1200 angle are equitorial and. the remaining two are axial.
Boron atom in excited state Il, 2s1 2Px12p/[!] 1 Iii 1 1 Axial bond length is greater.
35 3p 3d
srl hybridization
2
(iii) C'H4 molecule: Carbon atom has configuration ls2, Ground state of P-atom 1 ·1 1 1
18 2Px12pl In ground state, it has two unpaired orbitals
which can form only two covalent bonds. To get tetra- Excited state of P-atom
v
II 1 1 1 1
valency, 2s-orbital is unpaired and the electron is shifted to
sp3d hybridization
2p-orbital. Now in excited state the four unpaired orbitals
undergo hybridization giving rise to four hybrid orbitals (V) SF6 Molecule:
which are 109°28' apart. The four hybrid orbitals overlap 35 3p 3d
with s-orbital of each of the four hydrogen atoms forming four Ground state of S-atom @]
sigma bonds. The molecule formed is tetrahedral.
2s 2p Excited state of 5-atom 1IIIIillilii ,
Carbon atom in ground state sp3d2 hybridization
3s- and paired 3p-orbital are uripaired and electrons are

Carbon atom in excited state shifted to d-orbitals. After hybridization six hybrid orbitals
Sp3 hybridization directed towards the corners of a regular octahedron come
100 C.R.B. Inorganic Chemistry for Competitions
into existence which overlap with six fluorine atoms. The 25 2p

SF6 molecule has octahedral structure.
F
Ground state of O-atom [IT] litl I I I I
sp3 hybridization
F. _____ _______ :0._____ F
1
1
1
1
1
-r - -
1 1
/ I /
1
1
1 I
I
I 1
1
1
of
~H
F '-------------
F
.•
F H
Fig. 2.18
Hybrid orbitals of 0 Overlapping with Water molecule
hydrogen atoms (V-shaped)
II Geometry of Some Molecules Fig. 2.20
Containing Lone Pairs of Electrons 1
The expected bond angle is 109°28 but the actual bond
(i) NH3 molecu : Nitrogen atom undergoes sp3 angle is 104°35 /. This is dVe to the presence of two lone pairs
hybridization forming four hybrid orbitals. Three of the which repel each other and the bonded pairs more strongly
hybrid orbitals contain one electron each while the fourth and cause them to come closer and thereby reducing the bond
25 2p angle from 109°281 to 104°35 /. Similarly, the geometry ofPH31
Ground state of N-atom [!IJ II II I I I PCl31 NF31 H 2S, etc., can be explained. It is dear from the
above two structures that higher the number of lone pairs
Sp3 hybridization present on a central atom, the greater is the contraction
caused in the bond angle. The bond angle is also decreased'
as the size of the central atom increases.' The bond angle in
1
PH3 is 93°20 •
• Geometry of Molecules Involving

Sigm~.. (O') and Pi (7t) Bonds
It is observed that it is not necessary to involve all the
Hybrid orbitals of N Overlapping with . Ammonia orbitals present in the valency shell of the atom in the process
hydrogen atoms
of hybridization. The following two examples illustrate this
Fig. 2.19 fu~ , .
(i) Ethylene molecule '(C2~) : -Ethylene molecule is
one has apair of electrons. Three hybrid orbitals havin~ one formed as a result of sp2 hybridization of carbon. Each
electron each overlap with three hydrogen atoms forming carbon atom in excited state undergo sp2 hybridization giving
three sigma bonds while the lone pair of fourth hybrid orbital rise to three hybrid orbitals each.These hybrid orbitals lie in
remains unused.
1
the xy plane wlUle the fourth unhybridized orbital lies at
Tne expected bond angle should be 109°28 but the actual
1
right angle to the hybridized ?rbitals. In the formation of
bond angle is 106°45 because of the repulsion petween lone ethylene two hybrid orbitals, i.e., one from each carbon atom
pair and bonded pairs due to which contracpon oc~urs. Thus 1
form a sigma bond by h~ad on overlap while the remaining
ammonia molecule is pyramidal in shape. overlap with hydrogen atoms. ,The unhybridized p~orbitals
. . 3
(ii) Water molecule : Oxygen atQm undergoes sp
undergo sidewise overlap to form a 1t~bond.
hybridization forming four hybrid orbitals. Two of the
hybrid orbitals contain one electron each while other two a 25 2p
pair of electrons each. The hybrid orbitals having one
electron each overlap with hydrogen atoms forming two
Gmund state bf carbon atom IIJ, I Ii II I .I
sigma bonds while the lone pairs of the other hybrid orbitals
remain unused.
Excited state of carbon atom IT] III I I_I I
~
sp2 hybridization
Chemical Bonding 101
and oxygen in carbon dioxide is 1.15 A. Thus, none of the
above structures correctly explains the obserVed bond length.
It is, thus, said that a hybrid form of these structures can
provide the exact' explanation. The various structures' of
which the molecule is a resonance hybrid are known as
canonical forms or mesomeric forms. Actually resonance
Unhybridized orbital hybrid does not oscillate between the cam;miqd forms of a
mixture of tI!ese forms but it is a definite form and has a
Fig. 2.21 Formation of Ethylene molecule
definite structure which cannot be written on paper.
The molecule of ethylene is planar one:
(ii) Acetylene molecule (C 2H:z): Acetylene molecule is • Rules for Selecting Canonical Forms or
formed as a result of sp hybridization of carbon. Each carbon Mesomeric Forms:
atom in excited state undergoes sp hybridization giving rise (i) The relative position of all the atoms in' each of the '
to two hybrid orbitals each. Each carbon atom is left with canonical forms must be the same. They should differ only
two unhybridized p-orbitals. in the position of electro,ns.
,
28, '
2p Oi) The number of unpaired and paired electrons in each
of the canonical forms must be same.
Grourid state of carbon atom 'I i.j, 1
(iii) The contributing structures should not differ much in
energy.
Excited state of carbon atom '
~
OJ I'i 1iii I (iv) The contributing structures should be such that
negative charge resides on, more electronegative and positive
sp hybridization
charge on the electropositive. Like charges should not reside
The two hybrid orbitals of each carbon atom are used up on atoms dose together in the canonical forms.
in forming C-C and C-H sigma bonds. The unhybridized Formal charges on the atoms in the molecule help us in
orbitals overlap sidewise to form two 1t-bonds. choosing the most appropriate' resonance structure. For
example, nitrous oxide molecule is represented by ,two
resonance electron dot structures, one of which has a
negative formal charge on the oxygen atom and the other of
H-C==C-H, which has a negative charge on the terminal nitrogen atom.
+.. -.. + ••
:N=N-O: ~
..
N=N 0
Since oxygen is a' more electronegative element than
Fig. 2.22 Formation of acetylene molecule nitrogen, the structure that places a negative formal charge
on oxygen is probably lower in energy than the structure that
Acetylene has linear structure.
has a negative formal charge on nitrogen.
. + •• '-
2.2~B RESONANCE Thus, the actual structure of N 20 is :N=N - 0 : ..
It is generally observed that a single valence bond structure (v) As a result of resonance, the bond order changes in
of a molecule cannot correctly account for the properties of many molecules or ions.
the molecule. In such cases, the concept of resonance is Total number of bonds between two
introduced. According to this concept if two or more atoms in all the structures
Bond order =
alternate valence bond structures can be written for a Total number of resonating structures
molecule, the actual structure is said to be a resonance or
mesomeric hybrid of all these alternate structures. For
example, carbon dioxide molecule can be represented by the
e.g., (a)O ~ 0 B.0.=2;1=1.5
following three structures:
- +
O=C=O +---t '-..I==--..--""'J +---t O--c==O
I II ill
The calculated values of bond distances between carbon
and oxygen in C=O and C==O are 1;22 A and 1.10 A,
respectively but the observed bond distance between carbon i
B.0.=,2+ + 1 = 1.33
II Resonance Energy (vi) NO'3 ion:

It has been observed that the molecule which shows
resonance has greater heat of formation than the calculated
heat of formation of anyone of canonical forms. The difference
is represented by AE and its called resonance energy.
E .. t I al ) (calculated value of heat)

AI = xperunen a v .ue _ of formation of most
( of heat of formation
2.3Q~! PREDICTION OF GEOMETRY (SHAPE)
stable canonical form OF COVALENT MOLECULES
On account of AE, the hybrid form is more stable than any Geometry of a molecule or ion can be predicted if the state
of the canonical forms. of hybridization at central atom is known. The type of
Energy difference between most stable resonating structure hybridization can be known by the following methods:
and resonance-'nybrid structure is called resonance energy. First Method: The state of hybridization at central atom
in a molecule can be known by counting the number of
II Some Examples Showing Resonance orbitals involved in co-axial overlappings and the number
(i) Nitric oxide molecule: It is a resonance hybrid of
of orbitals with lone pair of electrons, i.e., by counting the
following two stnlctures: number of a-bonds and the number of lone pair of electrons
at central atom. Adding the two, if the total is 4, the
x •• xx • hybridization is Sp3. If this total is 3, the hybridization is sp2
~ N=O : - . , - ~ N-=O :+ and if this total is 2, the hybridization is sp.
A few examples are being given below:
(ii) Nitrogen dioxide molecule: It is a resonance hybrid (ct) Beryllium chloride (BeCI2)
of the following structUres: No. of a-bonds at Be atom == 2
x x No. of lone pair of electrons at Be atom = 0
Total = 2 + 0 = 2
Hybridization is sp, i.e., BeCl2 is linear and bond angle is
•• •• •• •• 180°.
xx xx (b) Boron trichloride (BCla)
No. of a-bonds at B atom = 3
No. of lone pair of electrons at B atom = 0
Total 3
Hybridization is sp2, i.e., BCl3 is trigonal planar and bond
(iii) Carbonate ion: It is the resonance hybrid of the angles are 120° each.
following forms:
(c) Carbon tetrachloride (CCl4)
o 0- O- No. of a-bonds at C atom =4
Il I I No. of lon~ pair of electrons at C atom = 0
C ~ C ~ C
Total =4
-dAo- ~o- -o~ Hybridization is sp3, i.e., CC4 is tetrahedral and bond
angles are1()9°28' each.
(iv) Ozone:
(d) Ammonia (NHa)
No. of a;bonds at N atom = 3
No. of lone pair of electrons at N atom 1
(v) 502 molecule: Total 3 + 1
:::;4
/S~ . Hybridization is sp3.

:0: .R: Shape is trigonal pyramidal (not tetrahedral) and bond
angles are not 109°28' but 106°45',
(e) Water (H2 0) Third Method: The number of orbitals involved in

No. of a-bonds at 0 atom = 2 hybridization can be determined by the application of the
No. of lone pair of electrons at 0 atom = 2 following formula:
Total = 2 + 2 = 4 H =+ ~ [V + M - C + A]
Hybridization is sp3.
where H = number of orbitals involved in hybridization
Shape is angular or V-shape (not tetrahedral) and bond V valence electrons of central atom
angle is not 109°28' but 104°35'. M =
number of monovalent atoms linked with
Second Method: Number of electron pairs in the valency central atom
shell of the central atom can be determined by applying the C = charge on the cation
following formula: A = charge on the anion
For neutral molecules : From the value of H, the type of hybridization can be
predicted.
No. of electron pairs
= No. of atoms bonded to it + ~ [Group number Value of H 2 34567
Hybridization sp sp2 sp3 sp3 d sp3 d2 sp3 d1
of central atom - Valency of the central atom]
No. of electron pairs at the central atom in CH4 Type 1. Neutral molecules:
= 4+ ~ [4 - 4] = 4 (sp3 hybridization) (i) CO2 : V = 4, M = 0, C = 0, A = 0
No. of electron pairs- at the central atom in PCls

H =~ [4 + 0 - 0 + 0] = 2, sp hybridization
(ii) S02 or V = 6, M = 0, C = 0, A = 0 •
= 5 + ~ [5 - 5] =5 (sp 3d hybrid~ation)
503 : H = ~ [6 + 0 - 0 + 0] = 3, sp2 hybridization
No. of electron pairs at the central atom in SF6
(iii) BCl3 : V = 3, M = 3, C = 0, A = 0
= 6 + ~ [6 - 6] =6 3
(s p a2 hybridization) 1 o.
H = -2 [3 + 3 - 0 ..+ 0] = 3, sp2 hybridization
.
0
No. of electron pairs at the central atom in BF3

(iv) SiC4 : V = 4, M = 4, C = 0, A = 0
=3 + ~ [3 - 3] =3 (sp2 hybridization) H = ~ [4 + 4 - 0 + 0] = 4, sp3 hybridization
No. of electron pairs at the central atom in H 20 (v) CIF3 : V = 7, M = 3, C = 0, A = 0
= 2 + ~ [6 - 2] =4 (~p3 hybridization) H 0 + 0] = 5, sp 3d hybridization
= .l. [7 + 3 -
2
For ions: (vi) XeF4: V = 8, M = 4, C = 0, A = 0
No. of electron pairs = No. of atoms bonded to it
1 H =~ [8 + 4 - 0 + 0] = 6, sp3d2 hybridization
+T[GrouP number of central atom - Valency of the
central atom ± No. of electrons] Type 2. When the species is a cation:
No. ~f electron pairs in NH4 (i) NH.t: V = 5, M = 4, C = 1, A = 0
= 4 +.l.[5
2
- 4 - 1] =4 (sp3 hybridization) H =~ [5 + 4 - 1 + 0]
No. of electron pairs in SO~- = 4, sp3 hybridization
=4 + ~ [6 - 8 + 2] =4 (sp3 hybridization) (ii) CHj: V = 4, M = 3, C = 1, A = 0
No. of electron pairs in BF4 '0

H =~ [4 + 3 - 1 + 0]
= 3, sp2 hybridization
= 4 + ~ [3 - 4 + 1] = 4 (sp3 hybridization)
(iii) NO~ : V = 5, M = 0, C = 1, A = 0
No. of Geometrical
Examples H = ~ [5 + 0 - 1 + 0]
electron pairs figure
= 2, sp hybridization
2 Linear BeC12, C021 ZnCl2
3 Triangular Planar BCI3: 503, CO~ Type 3. When the species is an anion:
4 Tetrahedral CH4, H 20, NH3 (i) CO~-: V = 4, M = 0, C = 0, A = 2
5 Trigonal bipyrarnid PFs, CIF3, SF4
H = ~ [4 + 0 - 0 + 2]
6 Octahedral SF 6, IFs, SiF~-
= 3, sp2 hybridization
(li) SO~- : ,V = 6, M = 0, C = 0, A 2 No. of 2 3 4 5 6

electron pairs .
H ~ [6 + a - a + 2J ~ 4, sp3 hybridization Geometrical Unear Triangular Tetra- Trigonal Octa-
(iii)ICLi:: V 7, M = 4, C 0, A = 1 figure planar hedral bipyramidal hedral
H = ~ [7 + 4 - 0 + 1] = 6, sp3d2 hybridization Examples BeCIl< BClg, 503 CF:I4, H20 PFs, CIF3, SF6< IFs
COl< ZnCl2 CO~- NHg SF4 , SiFg-
2.31'}~ VALENCE SHELL ELECTRON PAIR (vi) If the central atom is linked to similar atoms and is
~urrounded by bond pairs of electrons, the repulsions
." REPULSION (VSEPR) THEORY
between them are similar. As a result the shape of the
Lewis-Langmuir concept of covalent bonding is unable to molecule is symmetrical and the molecule is said to have a
explain the shapes of the covalent molecules. In case of regular geometry. On the other hand, the molecules in which
covalent molecules having three or more atoms, one of the the repulsive interactions between the electron pairs
atoms a~ts as a central atom and rest of the atoms are linked around the central atom are unequal have irregular or
to it in definite directions in space. This definite arrangement distorted geometry. In fact, the presence of lone pairs in
of the bonded atoms with the central atom in a molecule is addition to bond pairs in the molecule causes distortion in
known as shape or geometry of the molecule. the geometry of the molecule. For example, in the NH3 and
The first simple theory that was put forward to predict H 20 molecules, the bond angles are not 109"28' but 106.so
the geometry or shape of a covalent molecule is known as and 104.so respectively due to presence of one lone pair in
Valence Shell Electron Pair Repulsion Theory (or VSEPR NH3 and two lone pairs in H 20.
theory). This theory was first proposed by Sidgwick and [In the VSEPR notation used to. describe molecular
Powell in 1940 and was further developed by Nyholm and geometries, the central atom is denoted as A, terminal atoms
Gillespie in 1957. as X and lone pairs as E.AX2E2 describes a structure with
The theory, known as VSEPR theory, is primarily based two terminal atoms and two lone pairs around a central atom,
on the fact that in a polyatomic molecule, the direction of for example water molecule. Similarly, AX3E2 describes a
bond around the central atom depends upon the total structure with three terminal atoms and two lone pairs
number of electron pairs (bonding as well as non-bonding) around a central atom. For example CIF3 molecule.J
in its valence shell. These electron pairs place themselves as (vii) A multiple bond is treated as if it is a single electron
far apart as possible in space in order to have minimum pair and two or three electron pairs of a multiple bond are
forces of repulsion between them. The minimum repulsions treated as a single super pair.
correspond to the state of minimum energy and maximum (viii) Where two or more resonance structures can
stability of the molecule. represent a molecule, the VSEPR model is applicable to any
The main postulates of VSEPR theory are as follows: such structure.
(i) The shape of a molecule depends upon the number of
valence shell electron pairs (bonded or non-bonded) around • A Strategy for Applying .VSEPR Method
the central atom. To predict the shape of a molecule or polyatomic ion, the
(li) Pairs of electrons in the valence shell repel one another following four steps can be followed: '
since their electron clouds are negatively charged. Step 1 : Draw a Lewis structure of the molecule or poly-
(iii) The positions of the electron pairs in space around atomic ion. The structure must be plausible but it does not
central atom are such that minimise repulsion and thus need. to be the best one.
maximise distance between them. Step 2: Determine the number of electron groups around
(iv) The magnitudes of the different types of electronic the central atom (bonding and non-bonding both). A double
repulsions follows the order given below: and a triple bond each is counted as one electron group.
Lone pair - Lone pair> Lone pair - Bonding pair > Step 3: Identify the electron group geometry. This may
Bonding pair - Bonding pair be linear, trigonal planar, tetrahedral, trigonalbipyramidal
These repulsive forces alter the bond angles of the molecule or octahedral corresponding to two, three, four, five and six
or ion. electron groups respectively.
(v) The electronic repulsion between two pairs of electrons Step 4: Identify the molecular geometry. This is based
will be minimum if they are as far apart as possible. On this on the positions around the central atom occupied by other
basis, the following geometrical arrangements are most atoms (not by lone pairs).
suited.
Molecular Geometry Around Atoms with 2, 3, 4, 5 II illustration of the Theory by
and 6 charge clouds (Total number electron ,Considering a Few Examples
pairs-bonding and non-bonding)
(A) Molecules containing bond pairs only
Total
Number (i) Shape of BeF2 molecule: Be-atom is surrounded by
Number of Lo Number VSEPR Molecular
ne • Example
of Bonds (a) Pairs (b) of Charge notaHonGeometry two bond pairs of electrons. These should be localised in such
Clouds (a + b) a way that there is minimum repulsion between them, i.e.,
bond angle should be 180°, hence BeF2 molecule is Linear.
2 o 2 <>+-0
Lmear
CI-Be-CI
Molecules such as BeCI21 ZnCl2, HgCl2' etc., have a linear
shape.
[ ~]
(ii) Shape of BF3 molecule: The Lewis structure of BF3
3 planar
is:
?-:
Bent
F
oX
F~B~F
V B-atom is surrounded by three bond pairs. According to

4 o AX4 o}-o H·~p-H VSEPR theory they must be situated at an angle of 120° as
they will experience minimum repulsion, i.e., shape of BF3 is
o-r
Tetrahedral H
3 4 AX3E
"I triangular planar.
H'-'~-H
Trigonal H
Molecules such as BCI3, AICl3, etc., have a triangular
pyramidal
planar shape.
2 2 AX2E2 of: w»-:
Bent
O(
H is:
(iii) Shape of CH4 molecule: The Lewis structure of CH4
H
oX
CI H~CxH
CI"'~_CI
o
*
oX
5 CI.... I H
Trigonal CI
hipynunidal C-atom is surrounded by four bond pairs. These four bond.
pairs adopt tetrahedral structure as to remain as far apart as
4
5
*:
Sec-saw
F
F····SI •
F.... I-·
F
F
possible in order to have minimum repulsion. The bond angle
is 109°28' (or approximately 109.5°). Species such as Sif4,
CC4, SiH4, NHt, etc., have tetrahedral structure.
(iv) Shape of PCls molecule: The Lewis structure of PCIs
;~
• 1
3 2 ·····CI F
:.... 1- is:
T-.haped F CI CI
CI x.x
. : p ~ CI or
Cl~Cl
2 3 . ..
:t·
CI x.x
CI CICI
Linear
P-atom is surrounded by five bond pairs. To have
minimum energy, the bond pairs of electrons should be as
*
6 o far apart as possible from each other. This is possible if the
Octahedral
molecule· acquires a trigonal bipyiamidal shape. In this
geometry all the bond angles are not equal. The axial bonds
are of 90° and the bond angles in the triangle plane are of
5 6 ~
Sq~~e
1200. Two axial P-Cl bonds are longer as compared to three
equatorial bonds. This is due to the fact that axial bond
pyramidal
experiences greater repulsion from other bonds.
Molecules such as PFS1 SbCIsf etc., have same shape.
4 2
*-
Square
planar
is:
(v) Shape of SF6 molecule: The Lewis structure of SF6
F tetrahedral arrangement. The presence of two lone pairs

F~F brings distortion in the geometry of the molecule. The lone
F~F pairs repel the bond pairs more effectively resulting in the
F decrease of bond angle from 109°28' to 104,50. The actual
shape of the water molecule is V-shape.
5-atom is surrounded by six bond pairs. According to Molecules/ions such as F20, NH 2, SCll! PbCl2, etc.,have
VSEPR theory these bond pairs adopt an octahedral shape similar to water molecule.
geometry. In this geometry, all the bond angles are 90° each.
The molecule is symmetrical and stable, i.e., less reactive. TeF6
~ o .
molecule is also expected to have the same shape.
(B) Molecules containing lone pairs and bond pairs . 104.5°
(1) Molecules containing two bonding electron pairs and Shape of H 20 molecule
one lone pair (AX2E) : The molecule contains three electron
pairs. Thus, it should have a trigonal planar geometry. Due (3) Molecules containing five electron pairs
to the presence of one lone pair, the geometry gets distorted. (a) Molecules containing four bonding electron pairs and .
For example, S02 has a V-shaped geometry. The bond angle one lone pair (AX4E)
is reduced to 119,50. The example is SF4 molecule. The molecule has five
os electron pairs and should have trigonal bipyramidal
geometry in which one position is occupied by a lone pair.
Therefore, SF4 molecule can have either of the following
O~O two structures.
Shape of S02 molecule
(2) Molecule containing four electron pairs
F /p
~~~// I
(a) Molecules containing three bonding electron pairs
and one lone pair (AX~
<:::>---_I~/~::
Shape of NH3 molecule: The Lewis structure of NH3 t--_ I
is:
H;'NxH
.. P -p
(More stable)
.x
H (ii)
N-atom is surrounded by four electron pairs (three bonded
and one lone pair). These four pairs adopt tetrahedral In structure (i) the lone pair is on axial position while in
geometry. Due to presence of lone pair, NH3 has a distorted structure (ii) the lone pair is on equatorial position. The
tetrahedral geometry. The bond angle is not 109°28' but it is structure (ii) will therefore, experience lesser repulsions than
106,50. The actual shape of ammonia molecule is pyramidal. structure (i). Thus the structure (ii) which is described as
distorted tetrahedron or a folded square or see-saw will be
~H
a more stable correct structure of SF4• The bond angles are
890 and 1170 instead of 900 and 1200 respectively.
H~7 . (b) Molecules containing three bonding electron pairs

and two lone pairs (AX3E2)
The example is ClF3. The molecule has five electron pairs
Shape of NH3 molecule and it should have a trigonal bipyramidal geometry in which
Molecules such as PCl3, NF3, H30+, etc., have same shape. two positions are occupied by lone pairs. Therefore, the
(b) Molecules containing two bonding electron pairs and molecule, ClF3, can have either of the following. three
two lone pairs (AX2E2) structures.
Shape of water molecule: The Lewis structure of water
is: r.L~~ F
~~V / I
H
F~~CI
----/\
~--F
": :
O-atom is surrounded by four electron pairs (two bonded

(ii) (iii)
and two lone pairs). These four electron pairs adopt
Structure (i) is most stable as it will experience lesser (1) Bond length (2) Bond energy
repulsions in comparison to structures (ii) and (iii). Thus, the (3) Bond angle (4) Bond order
molecule has a T-shaped structure and bond angle is 87.6°.
(c) Molecules containing two bonding electron pairs and II (1) Bond Length :
three lone pa.ir:8 (AX2E3)
The distance between the nuclei of two atoms bonded
The example is XeF2' It has five electron pairs and it
together is termed bond length or bond distance. It is
should have a trigonal bipyramidal geometry in which three
~xpressed in angstrom (A) or picometre (pm) units:
positions are occupied by lone pairs. If the three lone pairs
are present on the corners of an equatorial triangle, the net [1 A = 10-8 em; 1 pm = 10-12 m]
repulsion will be zero.
Thus, the most correct and stable shape will be linear. BOND LENGTHS
Bond Bond length (A) Bond Bond length (A.)
H-H 0.74 H-F 0.92
(in H 2) (in HF)
Cl--CI 1.99 H--Cl 1.27
(in Cl:z) (in HCl)
Br-Br 2.28 H-Br 1.41
(41 Br2) (inHBr)
I-I 2.67 H-I 1.61
(in 12) (in HI)
(4) Molecules conta~ning six electron pairs F--F 1.42 O-H 0.96
(a) Molecules containing five bonding electron pairs and (in FI (in Hi)
one lone pair (AKsE) . C--C 1.54 0=0 1.21
(in 02)
The example is BrFs. It has six electron pairs and it should
C=C 1.34 C-O 1.43
have an octahedral geometry in which one position is
(in C2~) (in alcohols)
occupied by a lone pair. Since all the six positions in C~ 1.21 C=O 1.22
octahedron are equivalent, the lone pair can be present on (in C2H:z) • (in aldehydes)
any one position. Thus, the molecule has a square pyramidal C-N 1.47 N-H 1.03
geometry. (in amines)
C-H 1.08 S-H 1.35
(inorganic N-O 1.36
molecules) N=O 1.22
Bond lengths are measured spectroscopically or by X-ray

diffraction of solids and electron diffraction of gases. In ionic
compounds, bond length is obtaitled by adding up of the ionic
radii of two bonded ions.
(b) Molecules containing four bonding electron pairs and Bond length in ionic compound = r; + r;
two lone pairs <AX;&E2) Similarly, in a covalent compound, bond length is obtained
The example is XeF4. It has six electron pairs and should by adding up the covalent (atomic) radii of two bonded
have octahedral geometry in which two positions are atoms.
occupied by lone pairs. Bond length in covalent compound (AB)" = r A + rB
The factors such as resonance, electronegativity, hybri-
dization, steric effects, etc., which affect the radii of atoms,
r",{)-7Y also apply to bond lengths, i.e., the values of bond lengths
I/xe I' do not hold good for all the compounds. Bond lengths of
, ~'
.
F--- .--'F" some common bonds are tabulated in the table given above.
When· there is large difference in electronegativity of the
two atoms, the bond length is generally less than the sum of
The shape of the molecule is square planar. the covalent radii of the two atoms.
2.~ BOND CHARACTERISTICS Important features:
(i) The bond length of the homonuc1ear diatomic mole-
Covalent bonds are characterised by the following four
parameters: cules are twice the covalent radii. Bond length increases
with the iI)crease in the size of atoms.
H2 C-H C-Cl the order in which they are broken. Average bond energies
0.74 A 1.09 A 1.77 A of some common bonds are listed below:
(ii) The lengths of double bonds are less than the lengths BOND EN·ERGIES IN kJ mol-1
of single bonds between the same two atoms and triple
bonds are even shorter than double bonds. Bond Bond energy Bond Bond energy
Single bond> Double bond> Triple bond H-H 436 Cl-Cl 242
(iii) Bond length decreases with increase in s-character 0=0 497 Br-Br 193
N"",N 945 I-I 151
since s-orbital is smaller than a p-orbital.
3 2 F-F 158 H-F 563
sp C-H = 1.112 A; sp C-H = 1.103 A;
0 0
H-Cl 431 N-H 389

(25% s-character (33.3% s-character (in NH 3)
as in alkanes) as in alkenes)
H-Br 366 O-H 464
Sp C-H = 1.08 A
(in water)
(50% s-character as in alkynes)
H-I 299 C-C 346
(iv) Bond length of polar bond is smaller than the
C-H 416 C=C 598
theoretical non-polar bond length. (in methane) (in C2H 4)
(v) Bond length is affected by resonance and hyper-
conjugation. Important features:
IIiII (2) Bond Energy or Bond Strength : (i) The magnitude of the bond energy depends on the type
Bond energy or bond strength is defined as the amount of bonding. Most of the covalent bonds have energy
of energy required to break a bond in a molecule. Each between 50 to 100 kcal mol-l (200-400 kJ mol-I).
bond has a characteristic value of this energy and is measure Strength of sigma bond is more than that of a 1t-bond.
of the strength of the bond. It is generally observed that (ii) A double bond in a diatomic molecules has a higher
shorter the bond length, greater is the bond strength or bond bond energy than a sirigle bond and" triple bond has
energy of the bond. a higher bond energy than a double bond between the
same atoms.
H-H(g) ~ 2H(g) Mf = 436 kJ mol-l
(Bond length = 0.74 A) C=C>C=C>C-C
Cl-Cl(g) ~ 2Cl(g) Mf = 242 kJ mol-l (iii) The magnitude of the bond energy depends on the size
(Bond length = 1.99 A) of the atoms forming the bond, i.e., bond length. Shorter
H-Cl(g) ~ H(g) + Cl(g) Mf = 431 kJ mor
l the bond length, higher is the bond energy.
(Bond l~ngth = 1.27 A) (iv) Resonance in the molecule affects the bond energy.
(v) The bond energy decreases with increase in number of
Consider the dissociation of water molecule which lone pairs on the bonded atom. This is due to electro-
consists of two O-H bonds. static repulsion of lone pairs of electrons on the two
H-O-H(g) ~ 2H(g) + O(g); Mf = 926kJ mol-l bonded atoms.
(vi) Homolytic and heterolytic fission involve different
The average bond energy of O-H bond = 9~6 = 463 kJ amounts of energies. Generally the values are low for
Similarly, the average bond energy of C-H bond in CH4 homolytic fission of the bond in comparison to
is equal to one-fourth of the energy of dissociation of <;::Hi heterolytic fission. ,
into (C + 4H). However, the bond energy of each C-H bbnd (vii) Bond energy decreases down the group in case of
in CH4 is different. similar molecules.
C~(g) ~ CH3 (g) + H(g); Mf = 426 kJ mor
l (viii) Bond energy increases in the following order:
CH3(g) ~ CH2(g) + H(g); Mf = 439 kJ mor
l s < p < sp < sp2 < sp3
CH2(g) ~ CH(g) + H(g); . Mf = 451 kJ morl C-C > N-N > 0--0
CH(g) ~ C(g) + H(g); Mf = 347 kJ mol-l 346 163 146.4 kJ mor l
(No lone pair) (One lone pair) (Two lone pairs)
C~(g) ~ C(g) + 4H; Mf = 1663 kJmorl
(ix) Bond energy of covalent molecule can be calculated
1663 -1
Hence, average bond energy C-H = 4 :: 416 kJ mol· using Pauling's formula.
EA - B = T/2 [E A - A + EB-Bl + 23 (XA - XB)2
Thus, the bond energy of C-H bond depends on the order
where EA - B, FA-A and EB- B are the bond energies of the
in which the particular hydrogen atom is lost from the
molecules A-B, A2 and B2 respectively and xA and xB
molecule. A similar situation exists for all molecules with
are the electronegativity of A and B. A more accurate
more than two atoms. The strengths of the bonds depend on
the two bonded atoms. The bonds of this type are called odd
value is obtained when geometric mean ~EA-A xE B_B
electron bonds.
E A - A +EB-B
is used instead of arithmetic mean, 2 An example of one electron bond is found in the hydrogen
molecule ion, Hi:. It has a bond energy of 61 kcal/moL The
• (3) Bond Angles ion is less stable than H2 molecule as a bond length is longer
Angle between two adjacent bonds at an atom in a than two electrons bond in H 2. The excited state of alkali
molecule made up of three or more atoms is known as the metal molecules involve odd electron bonds. Thus, Lit Kt
bond angle. Bond angles mainly depend on the following Na1 are all bound by one electron.
three factors: Hei ion, O2 molecule, nitric oxide molecule, nitrogen
(i) Hybridization: Bond angle depends on the state of
dioxide mole€ule, etc., are the examples of three electrons
hybridization of the central atom. bonds. Hei ion is a resonance hybrid of following two forms:
Hybridization sp3 sp2 sp He~.He+ ~ He+ .~He
Bond angle 109°28' 120° 1800 The normal valence bond structure of oxygen molecule,
•• xx
Example CH4 BC13 BeCl2 : 0 = O~·, fails to account for the paramagnetic nature of
It is observed that as s-character increases in the hybrid oxygen. Thus, structure involving three electrons bond has
bond, the bond angle increases. . . . been suggested by Pauling. The following structure:
(ii) Lone pair repulsion: Bond angle is affected by the
:0 : : : 0:
presence of lone pair of electrons at the central atom. A lone explains the paramagnetic nature and high dissociation
pair of electrons at the central atom always tries torepel the energy of oxygen molecule.
shared pair (bond.edpair) of electrons. Due to this, the bonds
are displaced slightly inside resulting in a decrease of bond III Properties of Odd Electron Bonds
angle. The bond angle in NH3 is 107° and bond angle in H20 (i) The odd electron bonds are generally established
is 105° inspite of the fact that N-atom and O-atom undergo either between two like atoms or between different atoms
sp3 hybridization. which have not more than 0.5 difference in their electro-
•• ••
0: N negativities.
~ ~H
(ii) Odd electron bonds are approximately half as strong
as a normal covalent bond. '
H
. H H 'H (iii) Molecules containing odd electrons are extremely
Water molecule Ammonia molecule reactive and have the tendency to dimerise.
(iv) Bond length of one electron bond is greater than that
(iii) Electronegativity: If theelectronegativity of the
central atom decreases, bond angle decreases. of a normal covalent bond. Whereas the bond length of a
In case the central atom remains the same, bond angle three electron bond is intermediate between those of a double
increases with decrease ill the electronegativity of the and a triple bond.
surrounding atoms. (v) One electron bond is a resonance hybrid of the
follOWing tWo structures:
.. (4) J.Jond order A-B ~A.B
Bond order is defined as the number of bonds or number Similarly, a three electron bond is a resonance hybrid of
of sh~red electron pairs between two atoms in a molecule. the following two structures:
H-H or H :. H Bond order 1 A.:B~A:.B
, 0=0 or 0 :: 0 Bond order 2 ":~iIl
'N=N or N :: N Bond order = 3 2.3~£~ MOLECULAR ORBITAL THEORY

CFO or C :: 0 Bond order = 3 The valence bond theory is based on the assumption that the
Isoelectronic molecules or ions have same bond order. formation of a molecule involves an interaction between the
For example, F2 and O~- (18 electrons) ,have bond electron waves of orily those atomic orbitals of the
order 1. Nz, CO and NO+ (14 electrons)have bond order 3. participating atoms which are half filled., These atomic
, It is observed that with increase in bond order, bond orbitals mix with one another to form a new orbital of greater
enthalpy increases while bond length decreases. stability while all other orbitals on the atoms remain
undisturbed or maintain their individu~l identity. But this
2.33~;~ ODD ELECTRON BONDS cannot be correct pecause the nucleus of one approaching
,it!'fiJ
In 1916 Luder postulated that there are number of stable atom is bound to affect the electron waves of nearly all the
molecules in w1;rich double bonds are formed by sharing of orbitals of the other atom. Besides this, the valence bond
an odd number of electrons, i.e., one, three, five, etc., between theory fails to explain the formation of coordinate bond, the
paramagnetic character of O 2 molecule and the formation of Likewise when two atomic orbitals overlap they can be in
odd electron molecules or ions such as H~ ion where no phase (added) or out of phase (subtracted). If they overlap in
pairing of electron occurs. phase, constructive interaction occurs in the region between
Molecular orbital theory of chemical bonding is more two nuclei and a bonding orbital is produced. When they
rational and more useful in comparison to valence bond overlap out of phase, destructive interference reduces the
theory. This theory was put forward by Hund and probability of finding an electron in the region,between the
Mullikan. According to this theory, all the atomic orbitals of nuclei and antibonding orbital is produced.
the atoms participating in molecule formation get disturbed Antibonding M.O.
when the concerned nuclei approach nearer. They all get repulsive
mixed up to give rise to an equivalent number of new , I
,
, - Subtraction
orbitals that belong to the molecule now. These are called '/'/ A ""'"
molecular orbitals. The electrons belonging originally to the e> ' '
participating atoms are now considered to be moving ~ AtomiC:" )AtomiC
orbital', A ,/ orbital
along the molecular orbitals under the influence of all the ''-'''' "
nuclei. Thus, molecular orbitals are polycentric. Molecular , '.::..- Addition
Bonding M.O.
orbital is defined as the region in space comprising the , attractive
nuclei of the combining atoms around which there is Fig. 2.24 Formation of bonding and antibonding
maximum probability of finding the electron density. molecular orbitals
Molecular orbitals are of varying energies and are This can be shown mathematically'also. Suppose",A and
arranged in the order of increasing energy levels as in the
case of atomic orbitals. The filling of electrons in the
"'B represent the amplitude (or also called wave functions)
of the electron waves of the atomic orbitals of the two atoms
molecular orbitals follows, aufbau principle and Hund's rule. A and B respectively. When these waves overlap, two cases
may arise:
II Linear Combination of Atomic Orbitals
Case I. When the two waves are in phase, i.e., con-
(LCAO) structive interference occurs, the waves are added so that the
Molecular orbitals of a molecule are obtained by the linear amplitude of the new wave is
combination of atomic orbitals of the bonded atoms. The
electron waves that describe the atomic orbitals have positive
• == + "'A "'B
Case II. When the two waves are out of phase, i.e.,
and negative phase or amplitude just as there are ,positive destructive interference occurs, the waves are subtracted from
(upward) and negative <downward) amplitudes associated each other so that the amplitude of the new wave is
with standing wave. When wav~s are combined, they may
interact either constructively or destructively. If the two .'=="'A "'B
The probable electron density is given by the square of the
identical waves are added, they combine constructively to amplitude, therefore we have
produce the wave with double the amplitUde and same
wavelength. Conversely, if they are subtracted, they combine
and
.2.,2 ("'A + "'B)2 2
'" A +
2
"'B2 2
+ '" A"'B
2 2
+ "'B '" "'B
destructively to prod:uce the wave with zero amplitude. This <"'A - "'B)2
has been shown in Fig.2.23. i.e., .2 > "'~ + ",1
whereas .,2 "'~ + ",1
'" A A
Ie .1 <
The above relation shows that the probability of finding
the electrons in the bonding molecular orbital increases
whereas it decreases in the antibonding molecular orbital.
In other words, it can be said that electron density is high
Amplitude 2a
between the nuclei of two bonded atoms due to increased
attraction in case of bonding molecular orbital whereas most
of the electron density is located away from the space
between the nuclei due to repulsion in case of antibonding
molecular orbital. In fact, there is a nodal plane between the
(b) Amplitude two nuclei of antibonding molecular orbital where electron
zero density is zero.
\lJ\J Just as letters s, p, d, etc., are used to denote the atomic
orbitals, similarly Greek symbols, 0', 1t, 0, etc., are used to
Fig. 2.23 denote the bonding molecular orbitals and asterisk symbols
0*, W, ()*, etc., are used to represent antibonding molecular II Conditions for Combination of Atomic
orbitals. Orbitals to form Molecular Orbitals
Note: Crests of the electron waves are given '+' sign and
troughs a '-' sign. Thus, bonding molecular orbital is Theformation of molecular orbitals by linear combination
formed by combination of '+' with '+' and '-' with '-' of atomic orbitals can take place only if the following
part of the electron waves whereas antibonding conditions are fulfilled:
molecular orbital is formed by combination of '+' with
(i) The combining atomic orbitals must have same or
'-' part. of the electron waves.
nearly same energy, i.e., comparable energy. For homo-
The energy of the bonding molecular orbital is always nuclear diatomic molecule,.Au Is atomic orbital of one atom
lower than the energy of the atomic orbitals of the combining can combine with Is atomic orbital of another atom or 2s can
atoms whereas the energy of the antibonding molecular combine with 2s, 2p with 2pand so on. Is cannot combine
orbital is higher than the energy of the combining atomic with 2s or 2s cannot combine with 2p as the energy difference
orbitals as bonding molecular orbital is more stable and is appreciably high. However, such combination can take
antibonding molecular orbital is less stable. However, it place for heteronudear diatomic molecules,.AB, if the energy
should be noted that compared with the energy of the difference is not very high.
combining atomic orbitals, the energy of the antibonding (ii) The combining atomic orbitals must have proper .
molecular orbital is raised by an amount greater than the orientatiQn, i.e., same symmetry about the molecular axis.
amount by which the energy of the bonding orbital is For example, taking z-axis as the molecular axis,2pz orbital
lowered but the sum of the energies of bonding molecular of one atom can overlap with 2pz orbital of another atom but
orbital and antibonding molecular orbital is equal to the sum not with 2px or 2py orbitals because of their different
of energies of the combining atomic orbitals. The lowering symmetries. Similarly 2s orbital of one atom can overlap with
in energy (~) of the bonding inolecular orbital than the 2pz orbital but not with 2px or 2py orbital of another atom on
combining atomic orbital is called stabilization energy while account of improper orientation (Fig. 2.25 a and 2.25 b).
increase in energy (~') of the antibonding molecular orbital
. J
is called destabilizing energy.

-~---z -~--------z
Distinction between Atomic and Molecular Orbitals 2pz 2pz
Atomic orbital Molecular orbital
Proper orientation Proper orientation
1. Atomic orbital is monocentric, Molecular orbital is polycentric, i.e.,
i.e., electron cloud extends the electron Cloud extends around Fig. 2.25 (a)
around the nucleus of a single all the ilUclei of bonded atoms in
atom. the molecule;
2. It is less stable.
3. It has simple shape. .
4. Atomic orbitals are designated
It is more stable.
It has complex shape.
Molecular orbitals are designated
--~----~!
. I
I
I
I
I
I
---z -----~----~,-,
I
as s, p, d, etc. as (J, cr, 1t, n:*,etc. I I I I
2pz ·2px 2px· 2py

Comparison of Bonding and Antlbonding Improper orientation Improper orientation
I
Molecular Orbitals
Bonding molecular
orbitals
Antibonding molecular
orbitals
------~--------,
I
1. It is formed by linear: It is formed by linear combination 2px or 2py
combination of two atomic of two atomic orbitals when their Improper orientation
orbitals when their wave wave functions are subtracted.
functions are added. Fig. 2.25 (b)
2. Its energy is less than the Its energy is more than the
combining atomic orbitals. combining atomic orbitals. . (iii) The combining atomic orbitals must overlap to the
3. It increases the electron density It decreases the electron. density maximum extent. Greaterthe extent of overlap, the greater
between the nuclei. It therefore between the nuclei.· It therefore will be the electronciensity between the nuclei of a molecular
stabilises the molecule. destabilisesthe molecule. orbital.
4. It has no nodal plane (plane It has nodal plane.
where electron density is zero). It is symmetrical about inter- .. Salient Features of Molecular Orbital Theory
S. It is symmetrical about inter-· nuclear axis and about a line
From the above discussion, the main features of the
nuclear axis. perpendicular to it.
,. " ,. molecular orbital theory can be summed up as follows:
6. Designated by (J, 1t, 0, etc. Designated by (J, 11:, 0, etc.
(i) Like valence bond theory, this theory starts with atomic molecular, orbital. '+' lobe interaction with '+' lobe means
orbitals but the atomic orbitals of the atoms approaching addition of wave functions while '+' lobe interactiort with
for bonding overlap to undergo constructive interference as '-' lobe means subtraction of wave functions. Few simple
well as destructive interference to form molecular orbitals. cases of combination of atomic orbitals are discussed:
As a result, the atomic orbitals lose their individual identity (i) Molecular orbitals from s-atomic orbitals: The
and all the electrons in the molecule are associated with formation of molecular orbitals by linear combination of Is
molecular orbitals. atomic orbitals of two atoms is shown in Fig. 2.26.
(ii) When two atomic orbitals overlap, they form two new I
I
orbitals called molecular orbitals .. One of which is called
bonding molecular orbital and other is called antibonding
molecular orbital. These are formed by addition and
GIGO*15
I
!
subtraction of wave functions respectively.
(iii) Molecular orbitals are the energy states of a molecule
in which the electrons of the molecule are filled.
15 15
(iv) Bonding molecular orbital has energy lower than the
combining 'atomic orbitals while antibonding orbital has
Fig. 2.26
higher energy than the combining atomic orbitals.
(v) Only those atomic orbitals can overlap to form The wave functions of two Is atomic orbitals can combine
molecular orbitals which have comparable energies and in two ways:
proper orientation. (a) When both have same sign, i.e., addition of wave
(vi) Electrons present in the bonding molecular orbital functions occur and a Is molecular orbital is formed. This
contribute towards the stability of molecule while electrons ov;~1ap takes place along .the internuclear axis.
present in antibonding molecular orbital contribute to the (b) When both have opposite sign, i.e., subtraction of wave
repulsions between the nuclei of the atoms. functions occur and a* Is molecular orbital (antibonding) is
(vii) The bonding molecular orbitals are denoted as a, 1t, formed. This overlap takes place also along the internuclear
0, etc., while antibonding molecular orbitals are denoted as axis. The dotted line between the two lobes indicates a nodal
0*, 1t*, 0*, etc. plane where the probability of finding the electron density
(viii) A molecular orbital (bonding or antibonding cannot is zero.
accommodate more than two electrons. Both the electrons Each of the two molecular orbitals can accommodate two
must have opposite spins (Pauli's exclusion principle). electrons each and four in all. Similarly, the combination of
(ix) Molecular orbitals are filled in order of increasing two 2s-orbitals forms two molecular orbitals a2s (bonding)
energies starting with the orbital of minimum energy (aufbau b2s (antibonding).
principle). (ii) Molecular orbitals from p-atomic orbitals: The two
(x) In molecular orbitals of same energy (degenerate 2p-orbitals can combine together in either of the two ways,
orbitals), the electron pairing occurs only when all of them i.e., end-to-end or side-by-side.
are singly filled (Hund's rule). (a) End-to-end overlap: Let z-axis be the line joining the
, (xi) The shapes of the molecular orbitals formed depend two nuclei in the molecule. Thus, only 2pz orbitals will
upon the type of the combining orbitals. combine in end-to-end fashion. When 2pz orbitals on two
atoms combine in phase (addition), bonding molecular
III Types of Molecular Orbitals Formed orbital designated as a2pz and when these overlap out of
When the two .atomic orbitals overlap along the phase (subtraction), antibonding molecular orbital O-ZPz come
internuclear axis, the molecular orbitals formed are called a into existence. The formation is shown in Fig. 2.27.
and 0* molecular orbitals and 'when overlap sideways, the (b) Side-by-side overlap: When two 2py orbitals or 2px
molecular orbitals formed are called 1t and 1t* molecular orbitals on two atoms, which have mutually parallel axis,
orbitals. As s-orbitals are spherical symmetrical, their wave mteract to give rise molecular orbitals that are not
function has same' sign in all directions while in case of symmetrical about nuclear axis and are called 1t-molecular
p-orbitals, one lobe is given '+' sign and other a '-' sign. orbitals. These are designated as 1t2py (bonding) and 1a.Py .
Overlapping of '+' lobes or '-' lobes of two p-orbitals forms (antibonding). Similarly, when two 2px orbitals on the two
bonding molecular orbital and overlapping otone '+' lobe atoms interact they form two 1t-molecular orbitals which are
of on~ orbital and '-' lobe of other orbital forms antibonding designated as 1t2px (bonding) and 1Qpx (antibonding). The
I:
,formation has been shown in Fig. 2.27.
(i) The energies of the atomic orbitals involved in the
, formation of molecular orbitals.
Head on approach By addition Bonding molecular For example, pair of molecular orbitals formed by the
orbital
combination of 2s atomic orbitals will have higher energy
a2Pz
than those formed by combination of Is orbitals. Similarly,
, / , Nodal
y.-plane molecular orbitals formed by combination of 2p atomic
~-~-&e:G<3 orbitals will have higher energy than those formed by
Pz By subtraction Antib~nding combination of 2s atomic orbitals. Thus,
molecular orbital
Is molecular orbitals < 2s molecular orbitals
energy energy
- ~ Nodal plane < 2p molecular orbitals
energy
Bonding
2Py 2Py By addition However, within same pair of molecular orbitals, the
(or 2Px) (or 2Px) molecular orbital
11: 2Py (or 11: 2Px) bonding molecular orbital has lower energy than the
Sidewise approach
! No,dal plane
antibonding molecular orbital.
iff
(ii) The extent of overlapping between the atomicorbitals.
2Py 2Py
- , I
,
I
The greater the overlap, the more the bonding orbital is
lowered and the an,tibonding orbi,tdl is raised in energy
relative to atomic orbitals. Therefore, the energy of sigma
By subtraction Antibonding molecular orbital is expected to be lower than pi molecular
(or 2Px) (or 2Px) molecular orbital
orbital.
n2py (or n2p)
2p orbitals form six molecular orbitals between two atoms.
Fig. 2.27 Combination of two 2p atomic orbitals
Bonding orbitals G2pz, 1t2pXI 1t2Py
Thus, in all there are six molecular orbitals arising from Antibonding orbitals Capz, ir,2px, ir2py
two sets of 2p atomic orbitals. Since, 2py and 2px atomic
orbitals on an atom are degenerate (equal energy), the 1t The energy levels of these molecular orbitals have been
molecular orbitals formed by these orbitals will also be determined experimentally by spectroscopic methods.
degenerate, i.e., bonding orbitals, ' 1t2px and 1t2py orbitals have equal energies as these are
degenerate orbitals.
1t2py and 1t2px have same energy.
Similarly ir2 py and ir,2px have same energy. ir,2px and ir2 py orbitals have equal energies as these are
also degenerate orbitals.
It may be noted that whereas 1t2px has otlly one nodal
a2pz has the maximum energy among the six 2p molecular
plane, there are two nodal planes in ir2px molecular orbital. orbitals.
Similar is the situation with 1t2py and ir2py also. The energy of G2pz not definite. For diatomic molecules
Li2, Be2, ~, C 2 and N 2, the energy of G2pz is higher than 1t2Px
Difference between sigma and pi molecular orbitals
or 1t2py while for diatomic molecules O 2, Fu Ne2, the energy
Sigma (0) molecular pi (11;) molecular of G2pz is lower than 1t2px or 1t2py.
orbital orbital
Thus, the energy diagram for first ten molecular orbitals
1. It is formed by end-to-end It is formed by sidewise overlap of for diatomic homonuclear molecules such as Liu Be2, ~, Cu
overlap of atomic orbitals along atomic orbitals perpendicular to
the internuclear axis. internuclear axis.
N2 is:
2. The overlapping is maximum. The overlapping is comparatively
less.
* G2s, a2s,
GIs, GIs, * *
cr2pz
3. The orbital is symmetrical to The orbital is not symmetrical to
rotation about internuclear axis. rotation about internuclear axis.
Energy increases
4. It consists of one electronpoud. i It consists of two electron clouds
one above and other below the For homonuclear diatomic molecules such as Ou F2, N~,
plane passing through the nuclei. the energy diagram is:
III Energy Level Diagr8llls
* G2s, 02s,
GIs, GIs, * G2pzI
for Molecular Orbitals
The relative energies of molecular orbitals depend on the
following factors:
(c) If Nb is equal to Na (Nb = N a), the molecule is unstable.

This is because of the fact that the influence of antibonding
electrons is slightly more than that of bonding electrons
resulting in a net force of repulsion.
(ii) Stability in terms of bond order:
Bond order is defined as one half of the difference
between the number of electrons present in the bonding
>. and the antibonding orbitals, i.e.,
e>
<Il
c 1
<Il Bond Order (B.O.) = 2(Nb -N a )
Ol
c
·iii Number of electrons Number of electrons
III
~
-D- in bonding orbitals in antibonding orbitals
(J *2s
()
c =
-D-
2s
(J
2
The bond order provides the following information.
-D-
(J*1 s
(a) If the value of bond order is positive, it indicates, a
stable molecule or a stable ion. In case, the value of bond
-D- order is negative or zero, it indicates that the molecule or ion
(J1s
Atomic Atomic is unstable or the species does not exist.
orbitals orbitals (b) The stability of the bond, i.e., molecule or ion is
measured in terms of bond dissociation energy. The bond
Fig. 2.28 Energy level diagram of molecular orbitals for dissociation energy is directly proportional to the bond
homonuclear diatomic molecules (02, F2 and Ne2)
order. Higher is the bond order, greater is the bond dissoci-
ation energy, i.e., more is the stability. Thus, a molecule with
.. Rules for Filling up of Molecular
bond order 3 is more stable than a molecule with a bond
Orbitals with Electrons order 2 which in turn is more stable than a molecule with a
(i) The molecular orbitals are filled in increasing order of
bond order of 1 or I!.
their energy (aufbau principle).
(ii) The maximum number of electrons which can be (c) Bond order 1,2 and 3 means single, double and triple
accommodated in a molecular orbital is two (Pauli's bonds respectively. [The difference between chemical bond
exclusion principle). and bond order is that chemical bond is always integral but
(iii) If there are two molecular orbitals having the same bond order can be fractional also.]
energy, the electrons will first enter these singly and when Bond order Stability
both achieve one electron each, pairing will start (Hund's Less than zero The species is highly unstable
rule). or does not exist
Zero The species is highly unstable
[ill Electronic Configuration and or does not exist
Molecular Behaviour + 1/2 The species exists but unstable
The distribution of electrons among various orbitals is +1 A stable single bond
called the electronic configuration. Electronic configuration +2 A stable double bond
of the molecule can give the following information about the +3 A stable triple bond
behaviour of the molecule. (d) Bond length is inversely proportional to the bond
(i) Stability of molecules: A molecule is formed only order. Greater is the bond order, shorter is the bond length.
when the total energy of the system decreases. This is only
possible when bonding electrons are more than antibonding Molecule Bond order Bond dissociation Bond
electrons. Suppose the number of electrons present in the energy (kJ mor1) length (pm)2
bonding orbitals is represented by Nb and the number of F2 (F - F) 1 158 142
electrons present in the antibonding orbitals N a, then O 2 (0 = 0) 2 497 121
(a) If Nb is greater than Na (Nb > N a), the molecule is N2 (N == N) 3 945 110
stable. Stability is due to net force of attraction. (iii) Magnetic nature: If all the electrons in the molecule
(b) If Nb is less than Na (Nb < N a), the molecule is or ion are paired, it is diamagnetic in nature. In case, if the
unstable. Antibonding influence is stronger resulting in a net molecule has any unpaired electron or electrons, it is
force of repulsion. This brings instability. paramagnetic in nature. Paramagnetic behaviour depends
upon the number of unpaired electrons, i.e., greater the (v) Helium molecule, Hez: It is formed by linking two
number of unpaired electrons present in the molecule or ion, helium atoms. Both have Is-orbitals. These will combine to
greater is the paramagnetic nature. It is expressed in terms form two molecular orbitals cr(1s) and crOs). Four available
of magnetic moment which is equal to.Jn(n + 2) B.M. Where electrons are accommodated as crOs)2 and crOs)2.
n is the number of unpaired electrons. 1
Thus, bond order for He2 = 2(2 - 2) = 0
~ Molecular Orbital Configurations of Hence, there can be no possibility for the existence of He2
Some Homonuclear Diatomic Species molecule.
Homonuclear diatomic molecules or ions have two H2 Hz He! Hez
identical atoms linked together. These are A2 type species. cr(1s) 1 it it it it
(i) The hydrogen molecule ion, Hi: This ion has one
hydrogen atom and one H+ ion linked together. Each has
o(ls) 1 1 li
Is-orbitaL Using LACO method two Is-orbitals will combine Bond order 1/2 1 1/2 1/2 0
to give two molecular orbitals. crOs) and cr Os), the only Magnetic nature PDP P D
electron will be accommodated on crls. (P = Paramagnetic
Thus, bond order for Hi ~ 0- 0) ;:;: 1 D = Diamagnetic)

(Vi.) Lithium molecule, (Liz) : The electronic con-
Hz ion can exist but it is unstable. It is paramagnetic in figuration oflithium atom (2 is I i 151. Thus, total number
nature. The bond length is 104 pm. Its bond dissociation of electrons in Li2 molecule would be 6. The electronic
energy is 269 kJ morl. configuration of Li2 molecule may be written as:
(ii) The hydrogen molecule, Hz: It is formed from lsI
crOs)2(;(ls)2cr(2s)2. This may be written as: KK [cr(2s)2]. Where
atomic orbitals of two atoms. The atomic orbitals Osl) will
KK represents fully filled inner K shells in two atoms, i.e.,
combine to form two molecular orbitals cr(1s) and (;(ls). Two
electrons are accommodated on crOs) and (;(ls) remains [crOs)2] [cr(1s)2]. These are also called non-bonding orbitals.
vacant. It is clear from the electronic configuration of Li2 molecule
1 that there are 4 bonding electrons and 2 antibonding
Thus, bond order for H2 2(2 0) =1 electrons.
It is stable and diamagnetic in nature. It has single 4-2
Bond order ~=I
covalent bond. Its bond dissociation energy is 438 kJ morl.
The bond length is74 pm. Thus, Li2 molecule is stable. It has one single sigma bond.
(iii) The hydrogen molecule ion, Hz: It is formed by The bond dissociation energy is 110 kJ mol-1 and the bond
linking hydrogen atom with hydrogen ion, fr. Both have Is- length is 265 pm. As it has no unpaired electron, it is
orbitals. These will combine to form two molecular orbitals diamagnetic in nature. Li2 molecules are found to exist in
cr(1s) and cr(1s). These available electrons are accommodated vapour state.
as cr(1s)2 and crOs)1. (vii) Belt Bz and C z molecules : The electronic
configurations along with bond orders and magnetic nature
Thus, bond order for Hz =~(2 - 1) = ~ of these molecules are given below:
It is unstable and paramagnetic in nature. Molecule Total Configuration Bond order Magnetic
(iv) Helium molecule, He~: It is formed by linking electrons nature
helium atom with helium ion, He+. Both have Is-orbitals.
Be2 8 KK[cr(2s)2] [0<2s)2] !(4-4)=O Does notexi~t
These will combine to form two molecular orbitals cr(1s)
B2 10 KK[cr(2s)2] [0(15)2]
and crOs). Three electrons are accommodated as cr(1sf and
crOs)l. [1t(2p.il [1t(2p/] !(6-4) = 1 Paramagnetic
12 KK[o(2s)2] [0(2s)2]
Thus, bond oJ,'der for Hei ~(2 -1) = ~
Cz
1 Diamagnetic
I [1t(2px)z] [1t(2p/l 2(8-4)=2
The value of bond order indicates that He; can exist but
is unstable. The bond dissociation energy is 242 kJ mol-I. It The bond in B2 is weak 1t bond. The ~nd dissociation
is paramagnetic in nature. Both Hz and Hez have same energy is 290 kJ mol-1 and bond length is 159 pm. Cz
number of electrons in the antibonding orbitals. Both have molecule has double bond consisting both the 1t bonds as 4
same stability, similar bond dissociation energy and similar electrons are present in pi molecular orbitals. Generally, in
bond lengths.
most of the molecules, the double bond consists of one sigma and one pi bond. Like Li2 molecules, C2 molecules also exist in
vapour state.
• Comparison of stabilities of H:z, Lh and B2

The three molecules, i.e., H 2, Li2 and B2 possess the same value of bond order (i.e., 1) but their stabilities are different. H2
molecule. has maximum stability out of these molecules.
This can be explained as follows:
(i) Li-Li bond length is much larger than H-H bond length. -
(il) The overlapping of 25-25 atomic orbitals in lithium is less effective than the overlapping of 15-15 atomic orbitals in
hydrogen.
(iii) Li2 moleCule has two electrons in antibonding orbital while H2 has no electrons in the antibonding orbital.
(iv) In Li2 molecule, the electrons in 0(25) molecular orbital are shielded by inner 0(15) electrons. Thus, there is less attraction
between electrons in 0(25) and the nuclei. .
Because of above reasons, Li2 is less stable than H 2.
Boron atom is smaller in size than Li atom and the B2 molecule has 6 electrons in the bonding orbitals while Li2 molecule
has four electrons in the bonding orbitals. Hence, B2 is more stable than Li2.
Thus, the order of stability is: H2 > B2 > Li2 .
2
(viii) Nitrogen molecule (N2): The electronic configuration of nitrogen is Ii, 25 2l. In nitrogen moleCule, there are 14
electrons of which 4 are in the K shell and are non-bonding. Each atom contributes four atomic orbitals and thus, the molecule
consists of 8 molecular orbitals. Then ten electrons are alloted to molecular orbitals as follows:
KK 0(25)2 0-(2s)2n:(2Px)2n:(2p/ 0(2pz)2
where KK denotes the closed K shell structure 0(15)2 0-(15)2.
Bondorder !(8-2)=3 or =!(10-4)=3.
Thus, nitrogen molecule has three bonds, one sigma and two pi. The molecule is diamagnetic. It has high bond dissociation
energy (945kJ morl ) and bond length is 110 pm. .
(ix) Ni, N2 and N~- ions: The configurations of Ni, N2 and N~- ions along with their bond orders, stability and their
magnetic character are tabulated below: .
Species Total electrons Configurations Bond order Stability Magnetic nature

_. (8 - 2)
Nz 14 KK ('j(2d O(2s)z1t(2Px)2 1t(2p/ ('j(2pz)2 -2- 3 Most stable Diamagnetic
N1" - 13 KK ('j(2d O(2s)2 1t(2Px)2 1t(2p/ ('j(2pz)1 :=:2.5 Less stable Paramagnetic
N z 15 KK ('j(2s)2 O(2s)2 1t(2Px)2 1t(2p/ ('j(2pz)2 n(2px)1 (8;3) =:=2.5 Less stable Paramagnetic
N~- 16 KK ('j(2s)2 o(2s)2 1t(2p,i1t(2p/ ('j(2pz)2 n(2Px)1 n(2Pi

(8-4) . Least stable Paramagnetic
-2- 2
Bond dissociation energies are directly proportional to the bond orders. The order of bond dissociation energies is : N2 > N! = Ni > N~-.
Bond length is inversely proportional to the bond order. The order of bond lengths is: N~- > N2 '" ~ > N2.
2
(x) Oxygen molecule: The electronic configuration of oxygen is Ii, 15 2p4. In oxyg!?n molecule, there are 16 electrons
of which 4 are in the ~ shell and are non-bonding. Each -atom contributes four atomic orbitals and thus, the molecule consists
of 8 molecular orbitals. The 12 electrons are alloted to molecular orbitals as follows:
KK 0(25l 0(15)2 cr(2Pz)2n:(2Px)2n:(2p/ 1t(2Px)l 1t(2pi
Note: cr<2pz) is filled first and then 1t(2p,) and 1t(2py) molecular orbitals are filled.
(8-4)
Bond order =- 2 - 2
. The oxygen molecule has two bonds (one sigma and one pi). The last two molecular orbitals are singly occupied, hence
the molecule is paramagnetic in nature. The molecule is stable. The bond dissociation energy is 497 kJ mol-1 and bond length
is 121 pm. . . .
(xi) 0;, O 2 and O~- ions: The configurations of ot
02: and ~- ions along with their bond orders, stability and their
magnetic character are tabulated ahead:
Species Total electrons Configurations Bond order Stability Magnetic character
O2 16 KK 0"(2s)2 0(28)2 0"(2Pz)2n;(2Px)2n;(2p.i rt(2p)1 rt(2p/ (8;4) =2.0 Most stable Paramagnetic
(8 3) -25
oi 15 KK 0"(2s)2 0(28)2 0"(2pz)2 n;(2Px)2 1t(2p/ rt(2px)1 2 -. Most stable Paramagnetic
f (8-5)_15
O2 17 o KK 0"(2s)2 0<2s)2 0"(2Pz)1n;(2Px)2n;(2p/ rt(2P x rt(2p,/ 2 -. ' Less stable Param€lgnetic
"
(8""6)- .
o~- 18 KK 0;(2s)2 0<18f 0"(2Pz)2n;(2Px)2n;(2p;i rt(2Px)2 n(2p/ -'-2-=1.0 Least . stable Diamagnetic
\
The bond di~od{ltion energies and stability arei!1 the given order: O~ > O 2 > O2 > O~
The bond lengths are in thcl given order: ~- > 02: > O 2 > O!,
~ I .
(xii) Fluorine molE!cule: Electronic configuration qf N2 C2 ' B2
F-atom (Z 9) is Is 22s22pP. Total number of electronsin'F2 ----------------------
molecule is 18 of which 4 are in K shell and are non-bonding., * i
Each atom contributes four atomic orbitals. The 14 electrons rt(2px) 1t(2py) I
are alloted to molecular orbitals as follows: 0" (2pJ it

1t(2px) it '1',1. I 1t(2py) it it 11
cr(2s) it it it
Bond order
8-6
- 1 0"(2s) U U it
2
Bond order 3 2 1
F2 molecule has one single bond. The molecule is dia- Magnetic Diamagnetic Diamagnetic Pui;';':rrlagnetic
magnetic as no unpaired electron is present in the molecule. nature
The bond dissociation energy is 159 kJ mol-1 and bond Fig. 2.29 (b) Molecular occupan?y of homonuclear diatomic
length is 143 pm. molecules of 8 2 ,. C2 and N2
(xiii) Neon molecule (N~) : The electronic confi-
guration of neon atom is Is22i2p6. In Ne2 molecule 20 II Structures of HeteronucJear
electrons are present, out of which four electrons are in K Diatomic Molecules
shell and are non-bonding. The molecular orbital
The principles involved in the distribution of electrons in
configuration of neon molecule is:
the heteronuclear diatomic molecules are the same as in
KK a(2s)2 0(2s)2 a(ZPz)2 n(ZPx)2 n (Zp/n(ZPx)2 n (2p/ O{zpz)2 homonudear diatomic molecules. However, due to .the
difference in the electronegativity of two atoms, the molecular
orbital diagrams will not be symmetrical. The electrons in
Bond order = 8-8
2 =0 bonding molecular orbital spend more time near the more
electronegative atom. On the other hand, electrons in
Thus, Ne2 molecule does not exist.
antibonding molecular orbital are closer to the less electro-
F2 Ne negative atom. Two examples are discussed below:
cr(2pz) li (i) Nimc 'oxide molecule (NO) ;
*
1t (2px) 11 n(2py) it it it it Total valence electrons = 5 + 6 = 11
The distribution of the electrons in various molecular
n;(2px) it '1-1- n;(2py) it it it it
orbitals of NO molecule is done in the following manner:
0" (2pz) it .it it KK a(2s)2 0<2s)2 a(zPzi n(ZPx)2 n(2p/ n(ZPx)l
cr(18) U U it 1
Bond order 2:(8-3) =Z.5
0" (2s) U U it
The presence of one unpaired electron makes the molecule
Bond order 2 1 o less stable. It is paramagnetic in nature.
Magnetic nature P D Does not exist Configuration of NO+ (Valence electrons = 10)
KK a(2s)2 0<2s)2 a(Zpz)2 n(ZPx)2 n (Zp/
Fig. 2.29 (a) Molecular occupancy of homonuclear diatomic
molecules of O2• F2 and Ne2 1
Bond order = 2:(8 2) = 3
Configuration of NO- (Valence electrons = 12) theory, there is increase as well as decrease in electron
KK 0'(2s)2 0<2s)2 0'(2Pz)2 n (2Px)2 n (2p/ n(2px)1 n(2Pi density in the region of orbital overlap.
. l ' (iii) In valence bond theory, resonance plays its part
Bond order = 2(8 - 4) = 2 while in molecular orbital theory resonance has no role to
(ii) Carbon monoxide molecule (CO): play.
(iv) Mathematically, valence bond theory is quite easy to
Total valence electrons = 4 + 6 10 i
apply while molecular orbital theory is difficult to apply.
The distribution of electrons in various moleculctr orbitals
(v) Valence bond theory does not explain paramag-
of CO molecule is done in the following manner:
netic nature of 02 molecule while molecular orbital theory
(0'2s)2 (/t2.s)2 (1tf:P xi (n2p/ (0'2pz)2 ! explains the paramagnetic behaviour of O2 molecule .
. Bond order =~(8-2) = 3 l t(vi) Valence bond theory fails to explain the existence of
H:a. ion while molecular 'orbital theory explains the existellce
It represents one sigma bond and two n-bonds. The +
of;H2 ion:
molecule is stable and diamagnetic in nature.
(iii) eN" ion: 2. METALLIC BONDING
Total number of valence electrons 10 In a metal crystal, one atom is surrounded by 8 or 12 other
The configuration of C~ ion is: metal atoms. (This has been shown by X-ray study of metal
KK 0'(2s)2 O<2sin(2P xf n(2py)2 0'(2P z i crystals.) Since, in metals, the valency electrons are few, it is
not possible for an atom to form 8 or 12 covalent bonds with
Bond order = ~(8 - 2) =3
neighbouring atoms.
The ion is stable and diamagnetic in nature. In a metal crystal, all atoms are identicaL These atoms
(iv) UN molecule: cannot be linked by electrovalent bonds as all have same
Total number of valence electrons = 8 electronegativity. Thus, in metals, the atoms are bonded with
The configuration of BN molecule is: each other with a special type of bonding known as metallic
bonding. A theory was proposed by Drude in 1900 and
KK 0'(2s)2 0<2d n(2px)2 n(2p/
. 1 . modified by Lorentz in 1923, to explain the type of bonding
Bond order =2(6-2)=2 in metals. This theory is known as electron cloud or electron
The molecule is stable and diamagnetic in nature. pool or electron-gas theory. Since, the metals are electro-
positive as the ionisation energies are low, readily lose their
(I Comparison of Valence Bond Theory valence electrons and converted into positive ions. These
electrons move from place to place through the empty valence
and Molecular Orbital Theory
orbitals of the closed-packed metal ions .and are shared
Points of resemblance simultaneously among all of them. Thus, these electrons link
(i) For the covalent bond formation, orbital overlap is
all the atoms together forming a characteristic type of bond,
called the metallic bond. ,As the shared electrons are
necessary in both the theories.
delocalised, the metallic .bond has neither direction nor
(ii) The orbitals responsible for overlapping must have
saturation. There are two essential conditions for metallic
.nearly same energies and proper orientation according to bonding. These conditions are:
both the theories. (a) The metal atoms should have low ionisation energy.
(iii) According to bo+h the theories, the electron density is
(b) There should be sufficient number of vacant orbitals
high in the region between the atomic nuclei. in the valen<;y shell.
(iv) Both the theories account for the directional nature of The bonding which holds the metal atoms firmly
the bond.' together on account of the force of attraction between metal
(v) Both the theories predict the non-existence of He2 and ions and the mobile electrons is called metallic bonding.
Ne2 molecules. The strength of the metallic bond depends on the number
(vi) Both the theories are approximate. of valency electrons and the charge on the nucleus. As these
increase, the metallic bond becomes stronger. It provides an
Points of difference
answer to the fact that alkali metals are soft and have low
(i) In valence bond theory, atomic orbitals of the combin- melting and boiling points while transition metals are hard
ing atoms do not lose their individual character to a great and have high melting and boiling points. The metallic bond
extent but in molecular orbital theory atomic orbitals of the is usually a strong bond. This explains the hardness, high
combining atoms lose their identity and new molecular melting and boiling points and low volatility of metals. The
orbitals come into existence. presence of mobile electrons in the metal crystal explains the
(ii) According to valence bond theory electron denSity main properties of metals such as electrical conductivity,
increases in the region of overlap while in molecular orbital thermal conductivity, metallic lustre, malleability and
ductility.
Problem 1. (a) Why a molecule is more stable in terms of Each bond has part of the character of single bond and part
energy than the uncombined atoms? of character of a double bond. The electrons are delocalised
Solution: over the three atoms.
When the atoms combine together to form a molecule, there
o
is always release of energy. Thus, potential energy of a H-c1~~
molecule is less than that of uncombined atoms and therefore, ~O-
the molecule is more stable. (g) Water can react with hydrogen ion to make the oxonium ion,
(b) Why sodium c~loride does not conduct electricity in solid H30+. What is present in water molecule that allows it to react with
state but does so in molten state? a hydrogen ion? Describe the bonding in the oxonium ion. Draw a
Solution: dot and cross diagram for the molecule.
Solid sodium chloride has crystalline structure in which Solution:
the ions are not free to move. The ions become mobile when it There are two lone pairs, but only one of them makes a
is in molten state and thus, the electricity can be conducted. coordinate bond with an empty Is-orbital on a hydrogen atom.
(c) Why H 20 is a liquid while H 2S is a gas at ordinary There are three bonds in the H30+ ion, all the three are
temperature? identical but two of them are covalent and one coordinate.
Solution:
r
The dot and cross diagram is:
Oxygen has high electronegativity than sulphur. As a result,
H 20 forms hydrogen bonding. Consequently, molecules of
water come nearer to each other through hydrogen bonding.
This results in higher boiling point of water and hence it is a
[HX~XH
liquid. Problem 2. Draw dot and 6ross diagrams for the following
(d) The density of ice is less than that of water or ice floats over molecules. Then, use electron repuJsion theory to predict their
water. Explain. shapes. '
Solution: (i) CCI4, (ii) H 2S, (iii) NF3, (iv) NO, (v) AICI3 .
In ice, water molecule is associated with four other Solution: xx
molecules through hydrogen bonding in a tetrahedral manner, (i)CC4 ~ CI ~
xx • x xx
i.e., it has open-cage like structure in which lesser molecules
~CI; C ~Cg
are packed per mL. When ice melts, the molecules come closer xx ex xx
to one another. Consequently the density of water in liquid ~Cg
xx
state is more than in solid state. Thus, ic~ floats over water.
Four bond pairs + no lone pairs 4
(e) Methanoic acid, HCOOH, has one carbon-oxygen bond of Shape-tetrahedral
length 123 pm, and another of 136 pm. Which bond has which
length? ••
(ii) H2S :S
Solution: • •
l( y"
The structure of the molecule is: H H
Two bond pairs + two lone pairs = 4
Shape-bent like water
x x •• xx
(iii) NF3 ~ F :N: F ~
The double bonded carbon-oxygen bond is shorter than xx ex xx
the other. A double bond between two atoms is always stronger ~ F ~
xx
and shorter than a single bond between the same atoms.
(f) Both carbon-oxygen bonds in the methanoate ion, HCOO-, Three bond pairs + one lone pair = 4
have the same length (127 pm). What does this tell about bonding? Shape-pyramidal like NH3
Solution:
This is due to the presence of resonance in the molecule. (iv) NO
0 0-
H-C
< 0-
~H-C(
~O
Shape-Linear
(All diatomic molecules must be linear)
xx
(v) AICl3 ~ CI ~ The fraction of an electronic charge
xx Al xx 1.2 x 10-10
~CI-l-· ';Cl~ = 4.8 x 10-10 =0:25 =25% of e.
Three bond pairs + no lone pair = 3 (b) The dipole moment of LiH is 1.964 x 1O-z9 cm and the
Shape-triangular planar like BCl3 interatomic distan;ce between Li and H in this molecule is 1.596 A.
. Problem 3. Arrange the following in order of increasing: What is the per cent ionic character in LiH?
(a) dipole moment H20,H2S,BF3 Solution:
The dipole moment of 100% ionic molecule (Li+H-)
(b) covalent character LiCI, LiBr, LiI
(1 electronic charge) (interatomic distance) ;
(c) covalent character NaCl, MgCI 2, AICl3 19 10
= (1.60,2 X 10- C) (1.596 x 10- m)
Solution:
2.557 x 10-29 Cm
(a) BFs is a symmetrical molecule. It has zero dipole Fractional ionic character
moment. Oxygen being more electronegative than S, bond
moment of O-H is more than S-H. So, the dipole moments Exp. value of dipole moment
are in the order of Theoretical value of dipole moment
29
BF3 < H 2S < H 20 = 1.964 x 10- = 0.76$
2.557 x 10-29 .
(b) The anion size in increasing order is
The bond in LiH is 76.8% ionic.
cr < Br'"'<I-
. Hence, LiCI is least covalent and Lil most. The order is Problem 6. Interpret the non-linear shape of H2 S molecule
and non-planar shape of PCIs using valence shell electron pair
LiCl < LiBr < LiI repulsion (VSEPR) theory. [U.T. 1998]
(c) Cation size in decreasing order is Solution:
Na + > Mg2+ > Al3+ In H 2S, two bonded pairs and two lone pairs are present,
Thus, Al3+ ion has maximum polarisation effect and Na+ i.e., sulphur is in sp3 hybridized state. The angle is less than
ion has least. Thus, the covalent order is 109"28' as contraction occurs due to presence of lone pairs.
Thus, HzS has V-shaped structure. In PC13, three bonded pairs
NaCl < MgCl2 < AlCl3
and one lone pair are present, i.e., phosphorus is also in sp3
Problem 4. Write the electron configurations and calculate hybridized state but it has pyramidal structure.
the bond order of Hi, H2 and He2' Explain why bond length in Hi
is longer than in H2?
. Problem 7. Discuss the hybridization of carbon atoms in
Solution:
allene (CsH4) and show the 1t-orbital overlaps. [I.I.T. 1(99)
The number of electrons, their configurations, etc., for the Solution: .
I II III ..
given species an~: Allene isCH2=C=CH2 carbon atoms I and III are in sp2
hybridized state while carbon IT is in sp hybridized state. Two
Species No. of Configuration Bond order
N" Nil unhybridized orbitals of carbon IT overlap sidewise with
electrons = 112[Nb - N a ]
unhybridized orbital of each of carbon I and carbdn III to form
H~ 1 ( oIs}1 1 0 1/2 n-bonds besides it also forms a sigma bond with each of the
H2 2 (old ·2 0 1 carbon atoms using hybridized orbitals. Two hybridized
He2 4 (Ols}2(~}2 2 2 0 orbitals of each of carbon I and III form sigma bonds with
hydrogen atoms.
The bond length in Hi is longer than in H2 because in Hi I II III
only one electron is present to shield the two nuclei from mutual
repulsion. In H2 there are two electrons to hold the two nuclei
thus nuclear repulsion is less than that in Hi. Hence, nuclear
separation in Hi is more than in H 2. a-bond
Problem 5. (a) A diatomic molecule has a dipole moment of
1.2 D. If the bond distance is 1.0 A, what fraction of an electronic
charge, e, exists on each atom? .
Solution:
P . I ch Dipo1e moment 1.2xlO-18esucm Problem 8. Explain why o-hydroxybenzaldehyde is a
artia . arge = Bond distance = 1.0 x 10-8em liquid at room temperature while p-hydroxybenzaldehyde is
= 1.2 x 10-10 esu a high melting solid. U.I.T. 1999)
Solution: o-hydroxybenzald'ehyde show intramolecular hydrogen bonding whereas p-hydroxybenzaldehyde has

intermolecular hydrogen bonding. Thus, p-hydroxybenzaldehyde is an aggregate of a number of molecules and therefore, it is
a high melting solid.
---O=?--@-O-H---O=?--@-O-H---O=?--@-O-H---
H H H
(o-hydroxybenzaldehyde) Interhydrogen bonding (p-hydroxybenzaldehyde aggregate)
Intrahydrogen bonding
Problem 9. In the equation, A + 2B + H20 ~ C + 2D Problem 12. Which d-orbital is involved in dsp2
(A =HN02, B = H2S03, C = NH20H), identify D. Draw the hybridization?
structures of A, B, C and D. [nT. 1999] Solution:
Solution: dx2 _ y2. This is because its four lobes lie along the x-axis
HN02 + 2H2S03 + H 20 ~ NH20H + 2H2S04 and y-axis. The two p-orbitals can combine along these axes.
(A) (B) (C) (0)
Problem 13. What is the hybrid state of BeCI2? What will be
Structures- (A) HN02; HO-N=O, the change in the hybrid state of Be in BeCl2 in the solid state?
(B) H 2S03; HO-S~, (C) NH20H; H-N-OH, [CB.S.E. (P.M.T.) 2005]
I I Solution:
OH 0 H In ,the vapour state, BeCl21 exists as a linear molecule,
(D) H 2SO4; HO-S (
CI- Be - CI, i.e., Be is in sp hybridized state. In the solid state,
it has a polymeric structure. Each Be atom is linked with 4 CI
I ~O
OH atoms, two by covalent bonds and two by coordinate bonds.
Problem 10. Write the M.G. electron distribution of 02' ' " / C I " , /CI", / C I " , /
Specify its bond order and magnetic property. {I.I.T. 2000] Be Be Be Be
Solution:
/ "'CI/ "'CI/"'CI/ '"
O 2 (No. ·of electrons 16) KK(a2s)2(Ozd (a2pz)2 (1t2pl
Thus, Be atom is in sp3 hybridized state. Two empty orbitals
(1t2Px)2(n2py) 1(n2pi
1 an<;i two half filled orbitals, i.e., in all four orbitals undergo
Bond order = 2 (8-4) 2 hybridization.
As two of the orbitals are singly occupied, the molecule is Problem 14. (a) How bond energy varies from Nito Ni and
paramagnetic in nature. why?
Problem 11. Which of the two peroxide ion or superoxide (b) On the basis of molecular orbital theory, what is similarity
ion hils larger bond length? between
Solution: (i) F2 and ~- (ii) CO, N z, NO+? (C.B.S.E. (P.M.T.) 2004]
The bond length in a molecule is dependent on bond order. Solution:
The higher is the bond order, smaller will be the bond length. z
(a) Bond energy of Ni Bond energy of N because bond
Peroxide ion, O~- order is same in both the species. [However, Ni is slightly
O~-: KK(a2s)2(0zs)2(a2Pz)2(i,2p/(1t2p)2(n2p/(1Qpx)2
z
more stable than N as antibonding electrons number is
higher in N2" than in Ni.J
Bond order =
8-6
2 =1 (b) (i) Both Fz and ~- have same bond order same bond
Superoxide ion, 02: length and are diamagnetic.
(ii) These are isoelectronic species, possess same bond
02: KK(a2s)2(a2s)2(a2pz)2(1t2py)2(1t2px)2(n2p/(1QPx)1 order and same bond length.
8 5 Problem 15. Arrange the following compounds in the in-
Bond order 2 1.5
Bond order of superoxide ion is higher than peroxide ion,
°
creasing order of bond length of 0-0 bond in 2, 02[AsF6J, K02.
Explain on the basis of ground state electronic configuration of
hence bond length of peroxide ion is larger. dioxygen in these molecules. {I.I.T. 2004]
122 G.RB. Inorganic Chemistry for Competitions
Solution: The Lewis structure of ICl3 is:

02[AsF6] has O! ion while K02 has 02" ion.
E.C of~ = KKcr(2s)2 cr(2s)2cr(2Pz)2 1t(2Px)2 1t(2py)2
XXXX
Clx I xCl
oX
n(2px)l n(2py)1 Cl
E.C ofO~ = KK cr(2s)2 cr(2s)2 cr(2Pz)2 1t(2Px)2 1t(2py)2 Iodine is surrounded by five electron pairs (3 bonded and
n(2px)1 two lone pairs). Thus, the geometry is trigonal bipyramidal.
The actual shape is T-shape.
E.C of O 2 KK cr(2s)2 cr(2s)2 cr(2pz )2 1t(2px )2 1t(2py)2
n(2Px)2 n(2py)1 Cl-I-Cl
I
B.O. of O 2 ::: 1/2 (8-4) = 2 Cl
B.O. of O~ = 1/2 (8 3) 2.5
The Lewis structure of PbCl2 is:
B.O. of 02 = 1/2(8 - 5) = 1.5
XX
Higher is the B.O., smaller is the bond length. Hence, order CI;PbxCl
of 0-0 bond length is
oi> 02> O2 , i.e., Pb is surrounded by three electron pairs (2 bonded and one
O 2 [AsF6] > O 2 > K02 lone pair). Thus, the geometry is trigonal planar. The actual
shape is V -shape, i.e., bent structure.
Problem 16. Using VSEPR, draw the molecular structures
of OSF4 and XeF4 indicating the position of lone pairs and
hybridization of central atoms. [I.I.T. 2004]
Solution:
F
The Lewis structure of NHt ion is:
F
0
[HX~~,'
FF
Trigonal bipyramidal
(sl d hybridization)
Fttt Xe
•• F
Square planar shape
(sl d 2 hybridization)
Nitrogen is surrounded by four bonded pairs. The shape is
thus tetrahedral.
, Problem 19. Arrange the following in order of (i) increasing
N-O bond length (ii) increasing bond angles.
. Problem 17. Which of the following species have same shape Give reasons .
and same bond order?
Solution:
Type of hybridization of central atom, i.e.! N atom in N01"
Solution: is sp hybridized while in N02' and N03 it is sp2 hybridized.
!
Isoelectronic species possess same shape and same bond Their structures are:
order.
CO2 and N 3' are isoelectronic = 22 electrons
o
II
Similarly, N02: and 0 3 are isoelectronic == 24 electrons N"",
+
Thus, CO2 and N3' have same shape and bond order and o N=O o/ 0-
similarly, N02: and 0 3 have same shape and bond order.
Bond angles 1800 > 1320 > 120"
Problem 18. Apply VSEPR theory to predict the shapes of
SF4, ICI 3 PbCl 2and NH!.
! Bond order 2 2; 1 1.5 2+ ~+ 1 1.33
Solution: The Lewis structure of SF4 is:
Bond lengths NOi < N02' < N03
FxS~F Problem 20. Give reasons for the following observations:
.x .x
F F (a) Sucrose is a covalent compound but it is quite soluble in
water.
S atom is surrounded by five electron pairs (4 bonded and
(b) Hydrogen bonding does not exist in HCI though chlorine is
one lone pair) thus, the geometry is trigonal bipyramidal. The
quite electronegative.
actual shape is see-saw.
(c) o-Nitrophenol has lower boiling point than p-nitrophenol.
Solution: Pr«;»1'lem 22. Explain the shape of ICl z ion.

(a) The molecule of sucrose contains many --4)H groups Sobition:
and hence are capable of forming H-bonds with water. Type of hybridization, H = 1/2 [7 + 2 0 + 1] = 5, i.e.,
(b) This is due to large size of Cl-atom. sp3d-hybridization. The central atom'!, undergoes sp3d hybri-
(c) p-nitrophenol has higher boiling point due to dization, ~ electron configuration of I-atom in ground
intermolecular H-bonding. state is Ssz 5pi5p~ 5P15do.1t undergoes hybridization giving
Problem 21. Indicate the type of bonds present in NH4N03 five hybrid orbitals. Three hybrid orbitals contain l:'>ne pair
and state mode of hybridization of two N-atoms in it. of electrons each and occupy equatorial positions of the
Solution: trigonal bipyramid. One hybrid orbital is half filled, it
NH4N03 is an ionic compound in which cation is NH;t overlaps with an orbital. of chlorine atom and forms a
ion and anion is N03 ion. In NH;t ion, three covalent bonds covalent bond. One hybrid empty orbital accepts an electron
and one coordinate bond is present. The nitrogen is in sp3 pair from Cl-ionto form a coordinate bond. The O-atoms are
hybrid state, i.e., the species is tetrahedral. In N03, nitrogen present on axial positions.
is in. spz hybrid state, i.e., the species is trigonal planar. One
oxygen is linked by a double bond, other by a covalent bond
and third by a coordinate bond.
Cl ]-
.~.
o
t CI .0
aSUMMARY AND IMPORTANT POINTS TO ReMeM~eR b

1. A chemical bond is defined as a force that acts between two 3. Electronic theory of valency was formulated by Kossel and
or more atoms to hold them together as a stable molecule. Lewis and was completed by Langmuir.
2. The term valency has been derived from the Latin word The union of two or more atoms involving redistribution of
'valentia' which means capacity. Each element was said to electrons in their outershells. (either by transference or
have a valency equal to its combining capacity. The number sharing) in such a way, so that all the atoms acquire stable
of hydrogen or chlorine atoms with which another atom noble gas configuration of minimum energy is known as
combines is called its combining capacity. The valency term electronic theory of valency.
is now defined as the number of chemical bonds formed by There are two ways by which the atoms can acquire noble
an atom in a molecule. The modem concept believes that gas configuration.
electrons are responsible for chemical combination. The (a) By losing or accepting electrons
. atoms interact with each other on account of following (b) By sharing electrons.
reasons: There are three types of bonds or linkages which hold the
(a) Decrease in energy: Bonded state has lower potential atoms together in a molecule.
energy than the unbonded state and hence more stable. (i) Electrovalent bond
When two atoms approach the net result should be (il) Covalent bond
attraction to form a chemical bond. No chemical bonding (iii) Coordinate bond.
is possible if net result is repulSion. 4. The chemical bond formed between two or more atoms as a
(b) Lewis octet rule: The noble gases consist of filled result of the transfer of one or more electrons from electro-
outermost shells. Except for helium, whose electronic positive to electronegative atom is called electrovalent bond.
configuration is 1;, the g- and p- subshells of the highest This bond is also called ionic or polar bond.
energy level contain a total of eight electrons. The s~6 . The bond formed between oppositely charged ions is called
configuration constitutes a structure of maximum stability electrovalent bond. This bond is not possible between similar
and therefore, of minimum energy. The atoms of all atoms.
elements when enter into chemical combination try to 5. The energy released when the requisite number of positive
attain noble gas configuration. The tendency to achieve and negative ions are condensed into crystal to form 1 mole
eight electrons in their outermost shell by atoms is known of the compound is called lattice energy. The force of attraction
as Lewis octet rule. This is the basis of electronic theory (F) between two oppositely charged ions in air with charges
of valency.
equal to ql and q2 and separated by a distance d is given by, the two.nuclei. The bond is termed a non-polar bond.
Covalent bond may be single, double or a triple bond. Double
F=_l_ qlq2 or F- 1 qlq2
4n:eoK' d 2 - 4n:eoK' (rA:+1i)2 and triple covalent bonds are called multiple covalent bond.
9. Covalency: It is defined as the number of electrons
where, K is dielectric constant of medium.. contributed by an atom of theelementfor sharing with other
An ionic bond is purely electrostatic in nature. Its formation atoms as to achieve noble gas configuration. The usual
is favoured by (a) low ionisation potential of electropositive covalency of an elen:ent except hydrogen is equal to (8-
metal (b) high electron affinity of electronegative element group number to which the element belongs in Mendeleev's
and (c) high lattice energy. periodic table). This is true for 4th, 5th, 6th and 7th group
The summation of these energies should be negative, i.e., elements. Generally, the covalency of an element is equal to
energy is released. the number of unpaired electrons in s- and p- orbitals of the
I.P. + E.A. + L.E. =-ive or E.A. + L.E. > J.P. valency shell. The elements having vacant d~orbitals in their .
valency shell like P, S, 0, Br; I show variable covalency by .
6. Compounds having electrovalent bonds are called
increasing the number of unpaired electrons under excited
electrovalent compounds. They have following general
conditions. .
properties:
10. Covalent compounds: The compounds containing a
(i) Crystalline nature: Electrovalent compounds have
covalent bond or a number of covalent bonds are termed
closed packed structures and ions have no freedom of
covalent compounds. The characteristics of the covalent
movement. These are not found in liquid or gaseous
compounds are :
states under ordinary conditions of temperature and
(i) These exist as gases or liquids under normal conditions
pressure and exist as solids. They have low volatility
as very weak attractive forces exist between the
and high stability. They have high density and high
molecules, some exist as soft solids if the molecular
melting and boiling points.
masses are high.
(ii) Hard and brittle
(ii) With the exception of few having giant structures, others
(iii) Fairly soluble in polar solvents and insoluble in non-
have relatively low melting and boiling points.
polar solvents'
(iii) Covalent compounds are, in general, bad conductors of
(iv) Electrovalent solids do not conduct electricity
electricity.
(v) Do l10t 'show stereo-isomerism
(iv) Covalent compounds are insoluble in polar solvents
(vi) Show ionic reactions.
and soluble in non-polar solvents. This is based on the
7. Variable electrovalency: Certain elements show more
principle 'Like dissolves .like'.
than one electrovalency in their electrovalent compounds.
(v) Show molecular reactions.
The following are two reasons for variable valency :
(vi) The covalent bond is rigid and directional. Covalent
(3) Instability of the tote: The residue configuration left
compounds show isomerism.
after the loss of valency electrons is called a core or kernel.
11, Coordinate bond is a special type of covalent bond. It is
In the case of the atoms of transition elements, ions formed
defined as a covalent bond in which both electrons of the
after the loss of valency electrons do not possess a stable
shared pair are contributed by one of the two atoms. Such a
core as the configuration of the outermost shell is not
ns2np6 but mlnp6ndl-IO. This shell generally loses one bond is also called as dative bond.This bond is established
between two such atoms, one of which has a complete octet
or more electrons giving rise to metal ions of higher
and possesses a pair of valency electrons (donor) while the
valencies.
other is short of a pair of electrons (acceptor). The properties
(b) Inert pair effect ~ Some of the heavier represen-
of coordinate compounds are intermediate between the
tative elements of third, fourth and fifth groups having
properties of covalent compounds and electrovalent
configurations of the outermost shell ns 2np l, n~ n~ and
compounds.
ns2np3 show valencies with a difference of 2, i.e., (1; 3),
1-2. There are several stable molecules such as BeCI2, BF3, PCl y
(2; 4), (3; 5) respectively. The reluctance of s-electron pair
SF6J IF7, etc., in which octet rule is violated, i.e., atoms in
to take part in bond formation is known as inert pair
these molecules are either short of octet (less than 8 electrons
effect.
in the valency shell) or more than octet.
S. Covalent bond: The second mode of combination was first
13. Lewis dot formulae are used to represent atoms covalently
proposed by Lewis in 1916. There are atoms which attain
bonded in a molecule or a polyatornic ion.
noble gas configuration by sharing one or more electron
Lewis dot formulae show only the number af valency
pairs when each atom contributes equally. The pair or pairs
electrons, the number and kinds of bonds but do not depict
of electrons become a common property of both. Such a bond
the three dimensional shapes of molecules and polyatomic
is possible between similar and dissimilar atoms. In this bond
ions. The formal charge on the atoms in a Lewis dot structure
atoms do not acquire any charge. The electrons which are
of a molecule or polyatornic ion can be calculated by the
shared, occupy such a position in between the nuclei of the
application of following formula :
two atoms where there is maximum force of attraction from
Formal charge on = total number of valency electrons and boiling points whereas intramolecular H-bonding
an atom in the free atom total number of non- results in decrease in melting and boiling points.
bonding electrons 1/2 total number (e) Ice has maximum density at 4"C (277K).
of bonding shared electrons 18. When anions and cations approach each other, the valence
14. A covalent bond, in which electrons are shared unequally shells of the anions are pulled towards cation nucleus and
and the bonded atoms acquire a partial positive and negative thus, the shape of anion is deformed. This phenomenon of
charge is called a polar covalent bond. Bond polarity is deformation of anion by a cation is known as polarization
described in terms of ionic character which usually increases and the ability of the cation to polarize a nearby anion is
with increasing difference in the electronegativity between called as polarizing, power of the cation.
bonded atoms. . Fajan observed that greater the polarization of the anion in
the molecule, more is the covalent character in it.
Percentage of ionic character = [16 (XA - Xs) + 3.5 (XA ~ xsil
19. Valence pond theory: This theory was presented by Heitler
where XA and Xs are electronegativity of atoms A and B. '
and London in 1927 to explain how a covalent bond is formed.
50% ionic character corresponds to (XA - Xs) equal to 2.1.
The theory was extended by Pauling and Slater in 1931.The
15. The polarity of the molecule is indicated in terms of dipole
main points of the theory are:
moment. Dipole moment is defined as the product of the
(j) A covalent bond is formed by overlapping of atomic
distance separating charges of equal magnitude and opposite
orbitals of valency shell of two atoms.
sign with the magnitude of the charge.
(ii) Only half filled atomic orbitals, i.e., orbitals singly
11 = electric charge x bond length qx d occupied with opposite spins can enter into over-
Dipole moment is measured in 'Debye' unit (D). ID 10-18 lapping process. The resultant bond acquires a pair of
esu cm = 3.33 x 10-30 coulomb metre. The value of dipole electrons with opposite spins.
moment increases as the electronegativity difference in , (iii) The atoms with half filled orbitals must come closer to
diatomic molecule increases. Greater the value of dip~le one another with their axes in proper directions for
moment of the molecule, greater the polarity of the bond overlapping.
between the atoms. The overall dipole moment of a polar, (iv) As a result of overlapping, there is maximum electron
molecule depends on the geometry and shape of the density somewhere between the two atoms.
molecule. (v) Greater the overlapping, higher is the strength of the
Linear molecules like CO2, CS2, BeF2 and symmetrical chemical bond. The amount of energy released per mole
molecules like BF3r CH4t CCl4, etc., have zero dipole moment. during overlapping is termed bond energy. This energy
stabilizes the system.
Percentage of ionic character in a bond
(vi) Greater the overlapping, lesser will be the bond length.
Experimental -;alue of dipole moment (vi.i) Electrons which are already paired in valency shell can
= Theoretical value of dipole moment x 100 enter into bond formation if they can be unpaired first
16. The attractive force that binds hydrogen atom of one molecule and shifted' to vacant orbitals.
with electronegative atom of the other molecule of the same (viii) Two types of bonds are formed. These are (a) sigma (0')
or different substance is known as hydrogen bond. Hydrogen and (b) pi (1t) bond. Bond orbital which is symmetrical
bonding occurs when'H-atom is linked to F, 0 or N atoms about the line joining the two nuclei is known as sigma
(i.e., with small size and high electronegativity). H-bond is bond. Itis formed by head on or axial overlap. 1t-bonds '
usually longer than the covalent bond present in the are formed by the sidewise or lateral overlapping of p-
molecule. Bond energy of hydrogen bond is in the range of 3 orbitals.
1t-bond is a weaker bond in comparison to sigma bond. The
t~ 10 kcal mol-1 (10 to 40 kJmor1), i.e., about 1/10 the ~ergy
bond orbitals lie below and above the internuclear axis.
of the covalent bond. Hydrogen bond strength increases with 1t-bonds are formed only when a-bond has already been
the increase in electronegativity and decrease in size of the formed. 1t-bonds are more reactive than sigma bonds. The
atom. shape of the molecule is decided by a-bonds. 1t-electrons are
H-F- -H > H-O- -H > H-N- --H mobile in nature. A double bond consists one a-bond and
Hydrogen bond never involves more than two atoms. All one 1t-bohd while a triple bond consists one a-bond and two
the three atoms X-H - - - X lie in the straight line. 1t-bonds. All single bonds are sigma bonds.
17. (a) In water, each O-atom is linked with four H-atoms, two Bond strength : Single bond < Double bond < Triple bond
by covalent bonds and two by hydrogen bonds. Bond length : Single bond> Double bond> Triple bond
(b) HFi (or KHFi) exists but HOi (or KHCI2 ) does not Reactivity : Single bond < Double bond < Triple bond
because there is hydrogen bonding in HF bu't not in HCl. 20. Hybridization : The valence bond theory explains
(c) Cl has same electronegativity as N, yet there is no satisfactorily the formation of various molecules but fails to
H-bonding in HCI because size of CI is large. account the geometry and shapes of various molecules.
(d) Intermolecular H-bondingresults in increase in melting Hybridization is a hypothetical concept. The process of
mixing or amalgamation of atomic orbitals of nearly same energy to produce a set of entirely new orbitals of equivalent energy
is known as hybridization.
Number of hybrid orbitals formed number of atomic orbitals mixed.
Most of the hybrid orbitals are similar but they are not necessarily identical in shape. They never form x-bonds.
21. Type of No. of hybrid
Shape of molecule Bond angle Examples
orbitals
sp 2 Linear 180" N20, [Ag(CN)2]-; BeC12, BeF2, CO2, C5:2, CZH 2, HgCI2, HCN
sp2 3 . rriangularplanar 120" BF3, BC13, C2H4- CO~-, S03' N03- CH3
sp3 4 Tetrahedral 109.so CH4- CC~ SiF4- NHf~-
dSp2 4 Square planar 90" [PtC4]2-, [Ni(CN)4]2-
dsp3 or sp3d 5 Trigonal bipyramidal 120" and 90" PCls- PFs- [Fe(CO)s1
d2sp3 or sp3d 2 6 Octahedral 90" SF6, UF6< TeF6
d3sp3 or s~d3 7 Pentagonal bipyramidal 72" and 90" IF7
Hybridization and Structures o{Molecules having Lone Pair or Pairs
Type of No. of bonded No. of lone Hybridization Bond angle Expected Actual Examples
molecule pair/pairs of pair/pairs of geometry geometry
electrons electrons
AX2 2 1 sp2 <120 0
Trigonal V-shaperor S02' SnCI2,
planar Bent molecule PbCl2, NOr
AX2 2 2 sp3 <109"28' Tetrahedral V-shape H20, H 2S, NHi, SClz, OF2,
ChO, H 2Se, CIOz, ClOF
AX2 2 3 sp3 d 180" Trigonal Linear XeF z, 13, ICli
bipyramidal
AX3 3 2 sp3d 90" Trigonal bipyramidal T-shaped ClF3, ICl3t BrF3' XeOF2
AX3 3 1 sp3 <109"28' Tetrahedral Pyramidal NH3, PH3, PCI3, BiCl3,AsCI3,
NF3, PF3, xe03t CI03, ~-
P(CH3~' H30+
AX4 4 1 sp3d 120",90" Trigonal Trigonal SF4, SC4, TeC4, Xe02F2
bipyiamidal pyramidal
AX 4 4 2 sp3 d2 Octahedral Square XeF4,IC14
planar
AXs 5 1 sp3 d2 <90" Octahedral Square pyramidal lFS, BrFs, SbF~-
AX6 6 1 sp3d3 Pentagonal Distorted • XeF6, SF6
pyramidal Octahedral
22. (a) The h~bridization of carbon in CH4- C2H 4 and C 2H 2 is mesomeric forms but it is a definite form and has a definite
sp3, sp and sp respectively. The bond angles are 109.5", structure which cannot be written on paper.
120" and 180" respectively. Resonance hybrid has lower energy than any of contributing
(b) The hybridization of O-atom in H 20 and that of N-atom structures and hence is more stable. Resonating structures
in ammonia is st?
The shape of H 20 is V-shape (bent shQuld have same position of atoms, same number of paired
molecule) while that of NH3 is pyramidal. The bond and unpaired electrons, almost equal energy. They differ only
angles are 104.50 and 106.50 respectively. in the arrangement of electrons with a restriction that like
(c) The hybridization of O-atom in H30+ ion and that of charges should not reside on atoms closer together.
N-atom in NH;t ion is sp3. The shape of H30+ is pyramidal 24. Valence shell electron pair repulsion (VSEPR) : The VSEPR
while that of NHt is tetrahedral. model developed by Gillespie and Nyholm in 1957 used for
(d) The percentage of s-character in sp3, sp2 and sp is 25%, predicting the geometrical shapes of molecules is based on
33% and 50% respectively. Order of size of orbitals: sp < the assumption that electron pairs repel each other and
sp2 < sp3. therefore, tend to remain as far apart as pOSSible. The
(e) Diamond involves Sp3 hybridization. It is hard and a bad molecular geometry is determined by repulsions between
conductor of electricity. Graphite involves sp2 hybridi- lone pairs and lone pairs; lone pairs and bonding pairs and
zation. It is soft and a good conductor of electricity. bonding pairs and bonding pairs. The order of these
23. H two or more alternate valence bond structures can be written repulsions is: lp--lp > lp--bp > bp-bp.
for a molecule, the actual structure is said to be a resonance 25. Molecular orbital theory of chemical bonding is more
or mesomeric hybrid of all these alternate structures. Actually rational and more useful in comparison to valence bond
resonance hybrid does not oscillate between the various theory. This theory was presented by Hund and Mullikan.
According to this theory, all the atomic orbitals of the atoms consists of positively charged ions called kernels in a sea of
participating in molecule formation get disturbed when the mobile electrons. The metallic bond is formed due to
concerned nuclei approach nearer. They all get mixed upto simultaneous attraction of mobile electrons by the kernels.
give rise to an equivalent number of new orbitals that belong According to 'valence bond model' or 'resonance model' the
to the molecule now. These are called molecular orbitals. covalent bond present between metal atoms resonates among
The electrons belonging originally to participating atoms the neighbouring metafatoms:
are now considered to be moving along the molecular orbitals According to 'bond model' or 'molecular orbital approach'
under the influence of all the nuclei. The molecular orbitals atomic orbitals merge to form energy bonds. A substance is
are, thus, polycentric. a conductor when the electrons can be readily promoted to
Molecular orbitals of a molecule are obtained by linear the conduction band where they are free to move through
combination of atomic orbitals of the bonded atoms. When the substance. In insulators, the energy gap between the
waves are combined, they may interact either constructively valence band and the conduction band is so large that the
or destructively. When the atomic orbitals overlap in phase, electrons cannot be promoted to the conduction band. In
constructive interaction occurs in the region between the two semiconductors, electrons can cross the eneJ,'gy gap at high
nuclei and a bonding orbital is produced. The energy of temperatures.
bonding orbital is always lower (more stable) than the 27. (a) Isoelectronic species have the same shape and same bond
energies of the combining atomic orbitals. When they overlap order.
out of phase, destructive interference occurs and anti- (b) The d-orbital taking part in dspZ hybridization is
bonding orbital is produced. The energy of antibonding dx2 _ yZ, in stl'd hybridization it is dzz and in stl'd z, the two
orbital is higher (less stable) than the energies of the
combining atomic orbitals. The filling of molecular orbitals d-orbitals involved are dx2 yZ and dz2. In sp3d 3
by electrons follows aufbau principle, Hund's rule and Pauli's hybridization, the d-orbitals involved are dxy' dyz and
exclusion principle. Greek symbols, cr, 1t and 0 are used to dxz·
denote the molecular orbitals.
(c) The bond lengths of O2 and its ions are in the order
The molecular orbitals involved in the formation of most of
the molecules are: O~- > 0"2 > O2 > O~
Bonding orbitals crls o2s cr2pz 1t2py Tt2px as their bond orders are 1, 1.5, 2 and 2.5 respectively.
Antibonding orbitals crls cr2s cr2pz 1t2py 1t2px 1
Bond length 0<: bond order
The sequence of molecular orbitals on the basis of energy for
O2, F2 and Nez molecules is: (d) H-atom always fonns sigma bond.
.• • 1t2py 1t2py ~2 (e) As the s-character increases in hybridized orbitals, the
crls < crIB < cr2s < cr2s < cr2pz < 2 < n* 2 <I~ PZ size becomes smaller of the hybridized orbitals. The bond
1t Px Px
and the sequence of molecular orbitals for B2, C2, N2 length decreases while bond energy increases.
molecules is: (0 Isosteres are molecules containing same number of
p
crls < crls < cr2s < &2s < n 2 y< <52pz <n~22PY < G2pz
atoms and electrons. For example, CO and Nz.
n 2 Px Px (g) There are a number of stable molecules in which the
The maximum number of electrons which can be accommo- bonds are. formed by sharing of an odd number of
dated in a molecular orbital is two. If there are two molecular electrons. Such type of bonds are called odd electron
orbitals having same energy, the electrons will first enter bonds. Some common examples are : .
these singly and both of them have achieved one electron
each, pairing will start.
A molecule is formed only when the total energy of the system
.
·N~O-
- - :0
/ AN-
~ ..
0
decreases. This is only possible when the bonding electrons
are more than antibonding electrons. Nitric oxide
-.
--Nitrogen dioxide
The number of covalent bonds in a molecule is indicated by (NO) (N°2)
bond order.
Bond order
number of electrons in 1_ (number of electrons in)

·O~O·
• ••• • [: O~O
•• ••
:J-
( bonding MO's J antibonding MO's Oxygen Super oxide ion
2 (°2)
(a) Greater the bond order of a diatomic molecule or ion, (h) Electrovalent bonding is strongest while hydrogen
the more stable it will be. bonding is weakest.
(b) Greater bond energy indicates the greater stability of the (i) The stability of N2 and its ions is in the order
bond.
(c) Fractional bond order indicates ion.
N2 > N"2 N2: > N~-
(d) Negative bond order is impossible. It rather indicates as their bond orders are 3, 2.5, 2.5 and 2 respectively.
instability. The species does not exist.
(e) Zero bond order also indicates that species does not exist.
( j) Out of 02, O 2, 02: and ot
the diamagnetic species is
O~-.
26. According to 'electron sea model' of metallic bond, metal
~ PRACTICE PROBLEMS ~
• Subjective Type Questions (iv) Amongst LiP and Lil which has more covalent
character?
1. (a) Write Lewis dot symbols for the following atoms and (v) Amongst o-hydroxybenzaldehyde and p-~ydroxy
ions: benzaldehyde which is more soluble in water?
(i) Sand S2- (ii) AI and AI3+
(vi) Which among the following have highest lattice
(iii) Br and Br- (iv) 0 and 02- energy?
(v). Sr and Sr2+ .
NaCl, KCl, CsCI
(b) Draw Lewis structures for the following ionic
(vii) Which one of the following is non-polar?
compounds:
(i) MgS (ii) AIN (iii) CaBr2 S02' CHCI3J CO2, H 20, NH3
2. (a) Which one has higher lattice energy? (viii) Which one of the following has strongest bond?
NaCl or CsCl HP, HCI, HBr, HI
(b) How is lattice energy related with stability of an ionic 7. Arrange the following in each as instructed:
compound? . (i) 0, F, S, Cl, N in order of increasing strength of hydrogen
(c) Why are MgO, AI20 3, etc., used as refractory materials? bonding (X - - - H-X). [M.L.N.R. 1993]
3. Assign formal charges to each atom in the following
(ii) N 2, Oz, F2, Cl2 in increasing order of bond dissociation
structures. Based on formal charges, which is the preferred
Lewis structure for the molecule, the dinitrogen monoxide? energy.
(a) :N=N=O:
.. (b):N N-O:
(iii) NO~, N02, N03 in order of increasing N-O bond
length. [M.L.N.R. 1993]
4. (a) Identify the compounds in the following in which S does (iv) C=C, C==C in order of increasing bond energy.
not obey octet rule. (v) C-C, C=c, C==C in order of increasing bond length.
S02J SF2, SF 4, SF6
(vi) PH3, AsH3J SbH3, NH3 in order of increasing polarity.
(b) Arrange the following in increasing order of dipole
(vii) H 20, NH3, CH4, SF6J BF3, CO2 in order of increasing
moment.
bond angle.
(i) CH3I, CH3Br, CH 3F, CH 3Cl
(ii) BF3, H 2S, H 20 (viii) MgO, CaO, srO, BaO in order of increasing lattice energy.
5. (a) State whether the following are ionic or covalent: (ix) Arrange the following in order of increasing bond order,
(D Na2S (ii) SnCl 4 (iii) diamond (iv) CaC 2 N z, F2, O2, O2:, O~
(v) NaH (vi) C2H 4 (vii) CaCl 2 (viii) HCI gas (x) NO, NO+ and NO- in increasing order of bond length.
(ix) NH! (x) KBr 8. Answer the following:
(b) Indicate whether the following pairs of elements form
(0 How many electron pairs. are shared in N2 molecule?
ionic or covalent· compounds and write down the
(ii) What is the valency of carbon in C2H4 and C2H2?
molecular formula of the compound formed.
(D sodium and chlorine· (ii) carbon and sulphur
(iii) Which hybridization is predicted for P in PFs and S
(iii) sulphur and oxygen (iv) calcium and hydrogen inSF 6?
(c) What type of bonds are present in the following (iv) What types of bonds and how many of each are present
molecules? in NH!? .
(i) MgF2 (ii) BrCl (iii) CBr4(iv) C2N2 (v) CuS (v) Which hybridization is predicted for CI in CIF3?
(vi) H 20 (vii) H 2SO4 (viii) S02 (ix) HN03 (vi) Why the bond angle in H 20 is greater than 90"?
(x) K4Fe(CN)6 (vii) What is the shape of acetylene molecule?
(d) What type of chemical bond is formed between two (viii) Why zero group elements are inert in nature?
atoms when: (ix) Which type of elements can form electrovalent bond?
(i) electronegativity difference is zero. (x) What type of bond is formed by sharing an electron pair?
(ii) electronegativity difference is small . (xi) Which type of bond exists in molecule NO?
. (iii) electronegativity difference is high. (xii) What type of hydrogen bonding exists in liquid water?
6. (i) Among the following, (xiii) What type of hydrogen bonding exists in ortho-
NaCl, CCI4J HCI and CH4 which is a polar compound? chlorophenol?
(ii) Which among the following, (xiv) How many orbitals are singly occupied in O 2 molecule?
H 20, NH3, BF3 and NH! possesses a coordinate bond? (xv) Why Neon molecule (Nez) is not possible?
(iii) Among the compounds CH3COOH, NH3, HP and CH4
(xvi) What is magnetic nature of O~'-species?
in which maximum hydrogen bonding is present?
9. (a) Two elements A and B combine to' form a compound (iii) PbCl2 or PbCl4 (iv) AICl3 or GaCl3
AB. Under what conditions the bond formed will be (v) LiCI or KCl (vi) BeCl2 or MgCl2
electrovalent? (d) W4ich of the following pairs of bonds contain the larger
(b) Two elements A and B combine to form a compound ionic contribution to the bonding?
AB. Under what conditions the compound formed will (i) ~- r or ~-r (ll) Na+--ej2- or Mi+--ej2-
be covalent? (e) Which of the following species has higher melting point?
(c)· Two elements A and B participate by sharing electrons (i) NaCl or CuCI (ii) CaFz or CaI2
in chemical bonding. B does not contribute any electron (iii) CaClz or CdClz
of its own.' What type of bond is formed? 14. (a) What type of bond is normally expected between:
(d) Atoms A, Band C occur in same period and have one, (i) a' small cation and large anion.
six and seven valence electrons respectivdy. (ii) two electronegative atoms.
(i) Will the bond between B and, C predominently ionic (iii) a highly electropositive and highly electronegative
or covalent? Explain.. . , atoms.
(ii) Write the electronic structure of the compound (iv) an atom with a completed octet and an atom with
formed between B and C. a sextet of electrons?
(iii) Will the bond between A and B predominently ionic (b) Give one example of each:
or covalent? Explain. (i) A molecule with central atom devoid of octet.
(e) .Three elements A, B and C have atomic numbers 2-2, 2 (ii} A molecule, with linear shape.
and 2 + 1 respectively. Of these, B is an inert gas. (iii) An ionic compound insoluble in water.
(i) Which one has the highest value of electro- (iv) Almost a non-polar covalent compound between
negativity? two different atoms.
(ii) Which one has the highest value of ionisation (v) A stable compound formed by combination of two
potential? stable compounds through coordination.
(iii) What is formula of compound between A and C? (vi) A compound which is bad conductor in gaseous
(iv) What will be the nature of the bond between A and state but its aqueous solution is a good conductor
C in the compound formed ? of current.
10. (i) Write the two resonance structures of ozone which (vii) A compound whose central atom undergoes sp3
satisfy the octet rule. II.I.T 1991] hybridization possesses bond angle about 106.5°.
(ii) Write the two resonance structures. of N20 that (c) (i) Which one of them is more ionic and why? LiC
satisfy the ~tet rule. II.I.T 1990] NaCI
(iii) Write the resonance structures of carbonate ion. (ii) Which one of them' is having higher melting point
(iv) Write the resonance structures of N3 ion. and why? AICl3, MgClz
(v) Wdte the resonance structures of N03 ion. (iii) Which one of them is a good conductor of electricity
(vi) Write the resonance structures of Sol,lion. and why? NaCl, CH4
11. Write down the Lewis formula or electron dot formula of (iv) Which one of them is pyramidal and why? Bel3,
the following compounds: NH3
(a) (i) SiCl4 (ii) CO2 POt
(ill) (iv) H20 2 (v) Which one of them is a liquid and why? HF, H2S
(b) (i) 0 3 (ii) C0C12 (ill) N 20 S (iv) SzO~- 15. Explain with suitable examples or write short notes on:
(i) Electrovalency (ix) Octet rule
(v) CI03 ,(vi) CO (vii) S02Cl2 (viii) PzOj
(ii) Covalency (x) Dipole moment
(ix) N20 4 (x) NH! (iii) Coordinate valency (xi) Hybridization
12. Write down the hybridization of the central atom and (iv) Hydrogen bonding (xii) Fajan's rules
geometry of the following molecules or ions: (v) Metallic bonding (xiii) Sigma arid It-bonds
(a) 13 (b) PbCl 4 (c) ICl 4 (d) XeF4 (e) BH4 (vi) Variable valency (xiv) Bond order
(£) CIF 3 (g) HOC!. (vii) Inert pair effect (xv) Lattice energy
13. (a) Which of the following species has greater polarising (viii) Resonance (xvi) Polar and non-polar
power? 'bonds
(i) Fe3+ or F~+ (ii) Cu+ or Na.+ ,(iii) Mi+ or AI3+ 16. Give reasons for the following:
(b) Which of the following species will be most susceptible (i) The boiling point of ethyl alcohol is much higher than
to polarisation? .. that of diethyl ether.
(i) Br- or r (ii) 0 2- or S2- (iii) N3-- or 0 2- [Hint : Hydrogen bonding is present in alcohol. It is an
associated liquid. No hydrogen bonding is present
(c) Which compound of each of the following pairs is more in diethyl ether.]
covalent?
'(ii) Bel3 and BF3 are non-polar.
(i) CuO or CuS (ii) AgO or AgI JHint : Both are triangular planar and synunetrical
molecules. Their dipole moments are zero.]
(iii) Water is good solvent for ionic compounds. (xiii) Though the e1ectronegativities of nitrogen and chlorine
!Hint ~ Water has high dielectric constant and polar in are same, NH3 exists as liquid whereas HCl as gas.
nature. These properties help in the ionisation of Why?
ionic compounds.]
[Hint : The size of nitrogen is less than the size of chlorine.
(iv) MgCl2 is linear but SnCl2 is angular. Therefore, electron density in nitrogen is more than
. [M.L.N.R. 1995J that of chlorine. So, nitrogen forms hydrogen bonding
[Hint : In MgCIz, Mg is sp hybridized while in SnClz, Sn is leading to association of molecules. Hence, NH3 is
Sp2 hybridized.] a liquld. Hydrogen bonding is not possible with
chlorine.] .
(v) NCls does not exist while PCIs does.
!Hint : In N-atom d-orbitals are not present while in P-atom (xiv) Why the repulsions between non-bonded orbitals are
d-orbitals are present and ns electron can be shifted greater than between the bonded orbitals?
to nd-orbital.] [Hint : The non-bonded orbitals relatively occupy more
(vi) Lead prefers to form divalent compounds. space compared to the bonded orbitals and thus
IHint : nsz pair of electrons inert and only two electrons of repulsions are greater. I
np-orbitals participate. This is due to inner (xv) Although COz has no dipole moment, 502 and H 20
penetration of ns-orbital.]
have consi~erable dipole moments.
(vii) Sigma bond is more stronger than 1t-bond. [Hint : CO2 has linear structure while 502 and H20 have
[Hint : In sigma bond greater overlapping takes place.] V-shaped structures;1
(viii) CH4, NH3 and H 20 contain same number of electrons •• ••
s O·
~\J
but their shapes are different.
[Hint : The central atom in each of the three molecules CH4,
o:!=:±c
o
~~0 H H
NH3 and H 20 undergoes sp3 hybridization. In CH4-
no lone pair is present. In NH3 on.e lone pair is Dipole moments 0.0 1.60 1.84
present while in water two lone p~s are present.] (xvi) Nitrogen trifluoride (NF3) and ammonia (NH3) have
g
identical shape and a lone pair of electrons on nitrogen
H
b (Tetrahedral) (Pyramidal structure)
and further the' electronegativity difference between
the elements is nearly the same but the dipole moment
H/1"" H/1""
of NH3 is very high in comparison to NF3.
H H H H [Hint : It is due to different directions of moments of the
Bond angle 109°28' Bond angle 106.5" N-H and N-F bonds.]
(j 0 (V-shape)
(xvii) Although formation of NH3 and H 20 molecules
involve s~ hybridization, their bond angles are shorter
/0"" than the normal tetrahedral angle.
H H [Hint: This is due to the presence of one lone pair of
Bond angle 104.5" electrons on nitrogen atom in NH3 and two lone
pairs of electrons on oxygen atom in H 2O.]
(ix) Calciu:rn fluoride is more ionic than CaI2 . (xviii) Bond order in N2 is 3 whereas it is 2.5 in NO.
[Hint : The size of r ion is bigger than F ions. In CaI:y [M.L.N.R. 1994)
therefore, more polarisation is present. Thus, CaFz [Hint : N z «(jls)2(~s)2(cr2s)2(d2s)2(cr2px>2(1t2pi(1[2Pz)2
is more ionic than Calz.]
Bond order 2:1 (10 4) = 3
(x) Ammonium salts are much more soluble in water than
NO = (ols)2( ~lsr«(j2sY< ~r(cr2:p:cY<rr2pyY<rr2pj( ~2pi
the corresponding sodium salts.
[Hint: Na+ ion is solvated by ion-dipole interaction while Bond order ! (10 5) 2.5]
NH! ion is solvated by H-bonding which is a
stronger attractive force.] (xix) Three carbon-oxygell bonds are equal in carbonate ion.
[Hint : The carbonate ion exhibits resonance and therefore,
(xi) Carbon has two electrons in the outermost, but it is all the tIu:ee C-O bonds are equal.]
tetravalent in organic compounds. (xx) Valency of oxygen is generally two whereas sulphur
[Hint : Since, all the four valencies of carbon are identical,
2s electron is shifted to one of the vacant p-orbital
shows valency of two, four and six.
with the result four unpaired orbitals are present. [Hint : There are no d-orbitals in oxygen hence it cannot
These undergo hybridization and form four hybrid extend its covalency. Vacant d-orbitals are present
orbitals.] in sulphur and paired orbitals can be unpaired by
shifting electrons to d-orbitals, i.e, either making four
(xii) Why BeFz and BF3 are stable though Be and B have orbitals singly occupied ('IT six orbitals singly
less than 8 electrons? Which one is more stable? occupied showing valency 4 or 6 besides 2.]
[Hint : The stability is explained by symmetrical linear (xxi) SnCl2 is ionic but SnCl4 is covalent.
structure for BeFz and triangular planar structure [Hint: The size of Sn 4+ ion is smaller than Sn 2 + ion. Hence,
for BF3. BeFz is more stable because of its greater polarisation or distortion is more in SnC4, so, it is
bond angle 080°).] covalent.]
(xxii) NF3 is weaker base than NH3, NCI3, NBr3 and NI3. 18. Dipole moment of KCl is 3.336 X 10-29 coulomb metre whi!=h
[Hint : It is due to larger electronegativity of F-atoms of indicates that it is highly polar molecule. The interatomic
NF3. The lone pair is most difficult to be donated. distance between K+ and Cl- in this molecule is 2.6 x to-10 m.
(xxiii) BaS04 is insoluble in water. Calculate the dipole moment of KCI molecule if there were
[Hint : Lattice energy is more than hydration energy.] opposite charges of one fundamental unit located at each
(xxiv) NO molecule is paramagnetic. molecule. Calculate the percentage of ionic character of KCl.
[Hint : The molecule contains one unpaired electron in its . lU.T. 1993]
three electron bond.] [Ans. 4.1652 x 10-29 coulomb metre, percentage of ionic character
(xxv) Compounds of normal elements are diamagnetic. 80.091
[Hint : Normal elements acquire .inert gas configuration in 19. The dipole moment of HBr is 2.60 x 10-30 cm and the
compounds, i.e., all the orbitals are doubly occupied
and thus, compounds are diamag!',ciiL.] interatomic spacing is 1.41 A. What is the percentage
ionic character of HBr?
(xxvi) Anhydrous HCI is. bad conductor but in aqueous
[Ans. 11.5%]
medium, it is good conductor of current.
[Hint : HCl is a covalent compound and in gaseous state, 20. Calculate the percentage of ionic character in K-Cl bond
it does not conduct current. In water, however it in KCl molecule. The electronegativity values of K and
reacts to form ions, HCl + H20 ~ H30+ + Cl- 'CI are 0.8 and 3.0 respectively.
and thus conducts current.] [Ans. 52.1 %1
(xxvii) A bond order of 3 is computed for the diatomic 21. Calculate the lattice enthalpy of LiP give that the enthalpy
molecule. It is possible that in the absence of further of (i) Sublimation of lithium is 155.2 kJ mol-I;
information, this triple bond may be made up of two (ii) Dissociation of 1/2 mole of F2 is 75.3 kJ; (iii) Ionization
O'-and one 1t-bonds. Explain. energy of lithium is 520 kJ mol-I; (iv) Electron gain
[Hint :. Not possible. The order of filling orbitals and the
differentiations existing among bonding, antibond-
enthalpy of F(g) is -333 kJ mol-I; (v) Mil
overall is
-594.1 kJ mol-I.
ing and non-bonding electrons, never permit the
[Ans. 1011.6 kJ mol-I]
establishing more than one sigma bond.]
(xxviii) Diamond is a hard solid with a very high melting point
but a non-conductor of electricity.
• Matching Type Questions
[Hint : Diamond is a giant molecule-three dimensional Match the follOwing:
figure as every carbon is sp3 hybridized, i.e., one
carbon atom is linked to four other carbon ato~s (A) (a) C2H2 (i) s'; hybridization
tetrahedrally. Due to continuous covalent bonding (b) S02 (ti) sp3d hybridization
all the atoms are held very closely and .strongly. As
a result, diamond is a very hard solid with high
(c) Scn- (iii) sp3d2 hybridization
melting point. It is bad conductor as free electrons
(d) 13 (iv) sp hybridization
are not available.] (e) SF6 (v) sf hybridization
(xxix) AlCl3 is largely covalent while AlF3 is largely ionic. (f) IF7 (vi) sp3d3 hybridization
[M.L.N.R. 1995] (B) 1. BeCl2 (i) Pyramidal (a) Bond angle 109°28'
[Hint : Due to larger size of Cl- ion than ~ ion, there is 2. HzO (ii) Trigonal (b) Bond angle 180°
greater degree of distortion in AICI3.] bipyramid
17. Give reasons for the following: (iii) Tetrahedral
3. NH3 (c) Bond angle 106.5°
(a) Carbon-oxygen bond lengths in Na2C03 are equaL (iv) Square (d) Bond angle 104.50
4. PCls
[Hint: Bond lengths are equal due to resonance in
carbonate ion.] planar
(b) BeCl2 has zero dipole moment while SnCl2 has a 5. CH4 (v) Linear (e) Bond angle 90°
dipole moment. 6. XeF4 (vi) V-shaped (f) Bond angle 120°, 90°
[Hint : BeCl2 has a linear structure while SnCl2 has angular (C) (a) Zero dipole moment (i) C 2 H 4
shape.] (b) Violation of octet rule (ii) O2
(c) Among planar structures, why the linear structure is (c) Overlapping concept (iii) Kossel andLewis
more stable than trigonal and square planar? (d) Paramagnetic molecule (iv) Ice
[Hint : Among planar stI"Jctures, stability increases with an (e) Five sigma and one 1t-bonds (v) Polar bond
increase in the bond angle. The bond angle is (vi) s'; hybridization
(f) High dielectric constant
maximum (180°) in linear structure.]
(g) Electronic theory of valency (vii) H 2 0
(d) Why do cotton clothes take a long time to dry as
(h) Unequal sharing of electrons (viii) CO 2
compared to synthetic clothes.
[Hint: Cotton fibres form hydrogen bonds with water (0 Hydrogen bonded solid (ix) Heitler and
molecules.] London
(e) Benzene molecule is stable inspite of the fact that it (x) PCI~
consists of three double bond.
[Hint: Resonance exists in benzene molecule.]
Answers : Subjective Type Questions two non-bonded electron pairs are present, i.e., less repulsion than
Cl z and in nitrogen only one electron pair is present, i.e., minimum
1. (a) (i) :$: and [:~:r (ii) ·AI· and [Alt+ repulsion is present. Hence, N z has maximum stability.
(iii) NO~ < NOz < NO:3
(iii) :~r· and [:~r:] (iv) :9: and [:~:r (iv) C-C < C=C < C"",C
(Energy increases with multiplicity.)
• z+ (v) C"",C < C=C < C-C
(v) S.r and [Sr]
(Bond length decreases with multiplicity.)
x---,..
(b) (i) Mg :S:
x...:::........:.
or [Mgf+ [: S
x.
:]2- (vi) Polarity can be decided on electronegativity difference.
PH3 < AsH3 < SbH3 < NH3
x----.,. • < HzO < NH3 < CH4 <
(ii) Al x-'; N: or [AIf+ [~N: ]3- Octahedral Bent Pyramidal Tetrahedral Linear
x~
.x
(90°) (104.5°) (106.5°) (109°28') (180°)
x~ ••
(viii) BaO < srO .( CaO < MgO
[~B;:r
(iii) Ca .Br: or [Ca]2+ 2
.. [Hint : Size of cation in decreasing order.]
x~ ••
..
• Br:
(ix)
Bond order
Fz < O 2 < Oz < O~ < N z
1 1.5 2.0 2.5 3.0
. (x) NO+< NO· < NO-
Bond· order 3 2.5 2
2. (a) NaCI as Na+ ion is smaller in size than Cs+ ion.
(b) Stability is dependent on the magnitude of lattice energy. High Higher the bond order, smaller is the bond length.
negative value of lattice energy gives more stability to an ionic S. (i) thTee; (ii) four; (iii) sp3d, sp3dz; (iv) three covalent and one
compound. coordinate; (v) sp3d (bonding pairs + lone pairs = 5); (vi) sp3
(c) MgO and Al z0 3 are used as refractory materials because they hybridization of oxygen; (vii) lin~ar (both carbon atoms are sp
have high melting. points on account of high lattice energies. hybridized); (viii) possess stable electronic configuration; (ix) highly
3. (a) From left to right -1, +1, 0 electropositive and highly electronegative; (x) covalent; (xi) odd
(b) From left to right 0, +1, -1 • electron; (xii) interhydrogeri bonding; (xiii) intrahydrogen bonding;
Thus, structLire (b) is preferred as negative charge is present on (xiv) two; (xv) bond· order-zero; (xvi) diamagnetic.
more electronegative atom. 9. (a) If the electronegativity differerice is more than 1.7;
4. (a) SF4 and SFtr (b) If the electronegativity difference is less than 1.7;
(b) (i) CH3I < CH3Br < CH 3Cl < CH3F (c) Coordinate. bond; (d) (i) covalent, electronegativity difference
xx •• xx
(ii) BF3 < HzS < HzO
5. (a) Ionic NazS, NaH, CaClz, KBr, CaCz (However covalent bonding
is smaIl, (ii) BC z, ~ C
xx
x••B xxxC ~ (iii) ionic, electronegativity
exists between carbon atoms.) difference is large; (e) Since, B is ~ inert gas, A will be
electronegative non-metal with valency 2 and A will be
Covalent SnCI4- diamond, CZH4- HCl (gas), NH"4
electropositive metal with valency 1. (i) A, (ii) B, (iii) CzA, (iv) ionic.
(b) (i) Ionic NaCl, (ii) Covalent CSz , (iii) Covalent SOz and S03,
(iv) Ionic CaHz. ·0+ 0+
(c) (i) Ionic, (ii) Covalent, (iii) Covalent, (iv) Covalent; (v) Ionic, 10. (i) ./ '\. ~ . / "'-..
(vi) Covalent, (vii) Covalent and coordinate, (viii) Covalent and
coordinate, (ix) Covalent and coordinate, (x) Electrovalent and
-:0•• :0: :0: :0:-
coordinate. (d) (i) Pure covalent bond, (ii) Sernipolar bond, + .••
:N -N-O:-
...
(ii)
(iii) Electrovalent. ••
6. (i) NaCl is the polar compound as the electronegativity difference is ••
maximum, (ii) NH! [NH3~Hl+, (iii) HF (electronegativity of fluorine
:0:- :0:-
is maximum), (iv) The size of 1- ion is larger than P- ion. Hence, more I I
of polarisation by Li+ ion in Lil occurs. Thus, Lil is more covalent, (iii) c c
(v) p-hydroxybenzaldehyde is more soluble in water as it forms
-:11: :0:- :0••/"":0:- /'\.0:
- :0:
hydrogen bonding with water, (vi) NaCI. Charges are same on the ions •• •• •• ••
[:N=N=N:] [:l'!-N=N:]- [:N==N-N:]-

but size of Na+ ion is smaller than K+ and Cs+ ions, (vii) COz is a non-
•• • e· •• ••
polar molecule as it has symmetrical shape, (viii) HF.
(iv) ~
-
~
7. (i) Strength of hydrogen bonding depends on electronegativity of
atom linked with hydrogen. Thus, the order is S < Cl < N < 0 < F
(ii) The increa~ing order is Fz < Cl z < Oz < N z.
Both fluorine and chlorine atoms in Fz and c:Jz possess three non- :O~
.. "- ..
:0""'\. .. :0••
.."'" N=O:.
bonded electron pairs each. Due to smal( size of fl~orine, there is
larger repulsion between non-bonded electron's in comparison to
(v) /N=O: ~
.. ~
/'N-O:- /'
chlorine. Thus, Fz has lesser dissociation energy than Cl z. In oxygen, :0•••• :O~
••
••
-:0
••
Chemical Bonding
•• •• F
0: :0:- :0: I
••- II ..- •• r ••. •• It •• .
:O=S=O: ~ 0= S-O:-
(f) sp3d, T-shaped CI-F; (g) oxygen undergoes sp3
(vi) :O-S-O: ~
•• II •• I •• I •• I
F
:0•• :0:-
••
:0:-
•• hybridization, V-shape structure.
(Tetrahedral structure) 13. (a) (i) Fe3+ (ti) Cu+ (iii) Al3 +
•• (b) (i) r- (ii) (iii) N 3-

:Cl: (c) (i) CuS (ti) AgI (iii) PbCl4 (iv) AlCl3 (v) LiCI (vi) BeCl2
•••• x ••• xx xx (d) (i) K+-F~ (ii) 'Na+-02-
11. (a) (i) :Cl xSi x Cl: (ii) ~O~~C~~O~ (e) (i) NaCI (ii) CaF2 (iii) CaCl2
•• • x ••
14. (a) (il Ionic bond with partial covalent character, (ii) covalent,
:Cl:
•• (iii) ionic, (iv) coordinate.
(iii) See page 87 (iv) See page 86 (b) 0) BF3, (ii) BeCl2 or COl< (iii) BaS04- (iv) CH4,
(v) NH4CI[(H 3N-';I1)+CI-] or (H3N....,.-BF3), (vi) HCl, (vii) -NH3.
(d (D NaCl (very small distortion).
(ii) MgCl2 (more ionic than AlCI3).
(b) (i). Seepage 87 (iD
(iii) NaCI in molten. state (as ions are. present in mobile state).
(iv) NHs, (sp3 hybridization. One lone pair is. present on
xx •• N-atom).
Ox
(iii) See page. 86 (jv)
.. .S.....0:-
:s::
xxx
x
(v) HF (Hydrogen bonding is present. Molecules come nearer to
each other and associate through hydrogen bonds).
• x ••
Answers : Matching Type Questions
-:0:
•• (A) (a-iv); (b-i); (c-v); (d-til; (e-iii); (I-vi)
(B) (1-v-b); (2-vi-d); (3-i-c); (4-ii-f); (S-iii-a);
(v) See page 88 (vi) See page 86
(6-iv-e)
(vii) See page 87 (viii) See page 87 (C) (a-viii); (b-x); (c-ix);.,(d-ii); (e-iJ; (f-vii); (g-iii);
(jx) See page 86 (x) See page 88 (h-v); (i-iv); <i-vi) -
12. (a) sP'd, linear; (b) sp3, tetrahedral; (c) sp3d2, square planar;
(d) sp3d2, square planar (similar to c); (e) tetrahedral, Sp3;
"IUUSTRATIONS OF OBJECTIVE QUESTIONS

1. The electronegativity of Hand Cl are 2.1 and 3.0 respec- 7. The formal charge on the central oxygen atom in 0 3
tively. The correct statement(s) about the nature of HCI molecule is :
is/are: (a) 0 (b) + 1
(a) HCI is 17% ionic (b) 83% ionic (d 1 (d) 2
(c) 50% (d) 100% Ans. (b)
Ans. (a) [Hint : The Lewis dot structure of 03 is :
[Hint : % ionic character 16 (XA - Xi> + 3.5 (XA - XB)2
••
16 (3.0- 2.1) + 3.5 (3.0 - 2.1)2 o
14.4 + 2.835 == 17.235 '" 17%]
/~
2. The order of strength of hydrogen bond is : :0: :0:
(a) CI-H ..... Cl > N-H.... ,N > O-H. ....O > F-H .....F ••
(b) N-H .... ,N > CI-H .....CI > O-H.....O > F-H .....F Formal charge on central oxygen atom Valence electrons -
(c) O-H. ....O > N-H ..... N > CI-H .....CI > F-H .....F
(d) F-H.....F > O-H .....O > N-H ..... N > CI-H ..... CI .~ bonding:- electrons non-bonding electrons
Ans. (d)
[Hint : Hydrogen bond strength increases with the increase of
6 2:1 x 6 - 2 = + I]
electronegativity and decrease in size of the atom. 8. Match List I (species) and List II (bond orders) and select
Electronegativity F > 0 > N '" CI the correct answer :
~re F<O<N<C1] List I List II
3. The electronegativity of 0, F, N, CI and Hare 3.5, 4.0, 3.2, A. N2 1. 1.0
3.0 and 2.1 respectively. The strongest bond will be:
B. O2 2. 2.0
(a) F-O (b) O-CI (c) N-H (d) O-H
C. F2 3. 2.5
Ans. (d)
[Hint : Bond strength oc difference in electronegativity of atoms.]
D. O~ 4. 3.0
4. The carbonyl group has following resonating structures: A B C D
- + (a) 4 2 1 3
(I) > (II) > C-O (III) > C=O
(b) 1 3 4 2
The correct order of stability of these structures is :
(c) 1 2 4 3
(a) I > II > III (b) III > I > II
(d) 4 3 1 2
(c) I > III > II (d) III > II > I
Ans. (a)
Ans. (b)
£Hint : N z : 0'(25)2 G(25)2n;(2Px)2n;(2Pi0'(2pz)Z;
[Hint : The resonating structure with minimum or no charge is
more stable. Thus, the stability of (III) form is maximum. Bond order == 21 (8-2) == 3
The structure (I) is more stable than structure (II) as the O2 : (0'2s)2 (d?s)z (0'2Pz)2(1t;'p;/(1t z2px)Z (\2p/(1t. ZPx)li
negative charge is present on more electronegative atom.]
5. Which combination will give the strongest ionic bond? Bond order == ~ (8-4) 2
(a) Na+ and Cr (b) Mg2+ and CI- F2 : (0'25)2 (d?s)2 (0'2pz)2(1t;.~l(1tzZp]i (\Zpl(1t.Zp,ii
(c) Na+ and 02- (d) Mt+ and 02-
Ans. (d) Bond order '12 (8-6) 1
£Hint : Ionic bond strength depends on the force of attraction O~ : (0'25)2 (d?s)2 (O'ZPz)2(1ty2py)2(1tzZpx>2 (\Zp/i
between cation and anion. F oc q~ 2
]
Bond order== 21 (8-3) Z.5]
6. Number of bonding pairs and lone pairs around the central 9. Which of the following have identical bond order?
atom in the 1:3 ion are :
(I) CN- (II) O 2 (III) NO+ (IV) cW
(a) 2, 2 (b) 3, 2 (c) 2, 3 (d) 4, 3
(a) I, III (b) I, II
Ans. (c)
(d II, IV (d) I, II, III
[Hint : There are two bonding pairs and three lone pairs in the
Ans. (a)
outershell of central atom.
[Hint : Isoelectronic species have same bond order.
CN- = 6 + 7 + 1 =14 electrons i O2 == 8 + 8 + 1
== 17 electrons; NO+ == 7 + 8 -1 == 14 electrons ;
CN+ == 6 + 7 - 1 = 12 electrons]
10. The ratio of cr to 1t bonds in mesitylene is : 15. [In Ag (CN)2r, the number of 1t-bonds is :
(a) 3 (b) 7 [All.MS. 2006]
(c) 5 (d) 6 (a) 2 (b) 3
Ans. (b) (c) 4 (d) 6
(Hint : The structure of mesitylene is : Ans. (c)
H [Hint·: The cyanide ion consists a triple bond, --C==N-, i.e.,
I one sigma and two 1t-bonds are present: thus, two cyanide
o
HI~HH
groups have 41t-bonds.]
16. Which of the following molecules/ions does not contain
unpaired electrons? [Al.E.E.E.2OO6]
~ .. h I (a) 0:[- (b) 132
C fi" C
H/I I'H
H H Ans. (a)
Total number of cr-bonds 21 17. In which of the following molecules/ions are all the bonds
Total number of 1t-bonds 3] , not equal? [A.I.E.E.E.2006]
11. Both 13F3 and NF3 are covalent compounds. 13F3 is a non- (a) SF4 (b) SiF4
polar compound but NF3 is polar. The reason is that: (c) XeF4 (d) 13F;
(a) boron is a solid and nitrogen is a gas in free state Ans. (a)
(b) 13F3 is planar but NF3 is pyramidal in shape (Hint : In SF,.. sulphur undergoes sp3d hybridization. It contains
(c) boron is a metalloid while nitrogen is a non-metal two axial and two equatorial bonds and one position is
(d) atomic size of boron is smaller than that of nitrogen occupied by a lone pair of electrons.]
Ans. (b) 18. H2, Li2, 132 each has bond order equal to I, the order of their
(Hint : BF3 is planar, hence the dipole moment of the molecule is stability is:
zero. NF3 is pyramidal, thus it possesses dipole moment.
(a) H2 = Li2 = 132 (b) H2 > Li2 > B2
Hence, NF3 is a polar compound.)
(c) Hz > B2 > Liz (d) l3:! > Liz < H2
12. Which of the following sets of species does not follow octet Ans. (c)
rule? [Hint : Hz, Liz, Bz are not equally stable. Li atom is much larger
(a) CO, PCIs, PCl31 AlC13 (b) CO, 132H 6, NH3I H 20 in size than H-atom. The bond length in Li2 is much larger
(c) AlCl31 13F3, PCly SF6 (d) H 20, NH3, CO2, AlC13 than bond length in H 2. Moreover, Li2 molecule has two
Ans. (d electrons in the antibonding molecular orbital while has
no electrons in the antibonding molecular orbital. Thus,
[Hint : BFJ, Al03 are electron deficient molecules while in PCl5
Liz is less stable than H2 (Bond energy of Li2 110 kJ
and SF6 molecules P and S possess more than 8 electrons
mol-1 + Bond energy of Hz 438 kJ mol-I). Boron atom
in their valence shells.]
is smaller than lithium atom but larger than hydrogen
13. Which of the following species is diamagnetic in nature? atom. The Bz is more stable than Liz but less stable than
[A.I.FhE.Fh 2005] H2 (Bond eJ)ergy of Bz 290 kJ mol-1).)
(a) He; (b) H2 19. Which of the following pair is expected to have the same
(c) H~ (d)H"2 bond order?
Ans. (b) (a) O 2, N z (b) O~! N z
(Hint : Hei: (crls)2(Gls)1one unpaired electron paramagnetic (c) 02, N1 (d) 02, Ni
Hz : (crI8)2 no unpaired electron diamagnetic Ans. (b)
Hi : (cr15)1 one unpaired electron paramagnetic [Hint : 02, N 2:
= 2.5) .
Each has 15 electrons. Bond order = 1
(10 5)
Hz : «nd(Gls)1 one unpaired electron - paramagnetic]

20. Pick out the incorrect statement:
14. The number and type of bonds between two carbon atoms (a) In PCIs P atom is sp3d hybridized and has trigonal
!
in calcium carbide are : IA.I.KE.E. 2005] bipyramidal geometry

(a) one sigma, one pi (b) one sigma, two pi (b) PCIs on hydrolysis forms oxychlOride
(c) two sigma, one pi (d) two sigma, two pi (c) PCl5 acts as a Lewis acid
Ans. (b)
(d) In PC15 the axial chlorine atoms are closer to central P
!
(Hint : Calcium carbide is an ionic compound having anion

atom than equatorial chlorine atoms
[:C""",c:]Z- . It has one sigma and two pi bonds.]
Ans. (d)
... -
I OBJECTIVE QUESTIONS -
1. When two atoms combine to form a molecule: (a) Sand Q o (b) P and R o
(a) energy is released 0 (c) Sand R o (d) Sand P o
(b) energy is absorbed 0 [Hint: As Q is chlorine and S is potassium, so they form
(c) energy. is neither released. nor absorbed 0 KCl which is an ionic compound.]
(d) energy may either released or absorbed 0 11. The electronic configurations of four elements are :
2. Valency expresses: A : Ii, 2? 2p6, 3i 3p4 B : Ii, 2i 2p6, 3i 3p5
(a) total electrons in. an atom 0 C : Ii, 2i sp6, 3s1 n: 152,152 2p6, 3i
(b) atomicity of an element 0 The formulae of ionic compounds that could be formed
(c) oxidation number of an element 0 between them are :
(d) combining capacity of an element 0 (a) A2C, DA, CB, D2B 0 (b) C2A, DA, CB, DB 0
3. Electronic theory of valency was presented by: (c) AC, D2A, C2B, DB 0 (d) C2A, DA, CB, D~ 0
(a) Pauling 0 (b) Werner 0 12. Among sodium phosphate, sodium sulphate and sodium
(c) Kossel and Lewis 0 (d) Heitler and London 0 chloride the solubility in water decreases as :
4. The combination of atoms occur because they want: (a) sulphate > phosphate > chloride 0
(a) to decrease number of electrons in the outermost" orbit (b) chloride> sulphate> phosphate 0
o (c) chloride> phosphate > sulphate 0
(b) to attain an inert gas configuration 0 (d) phosphate> chloride> sulphare 0
(c) to increase number of electrons in the outermost orbit [Hint: For the same cation, as the magnitude of charge on
o the anion increases, the lattice energies increase and
(d) to attain 18 electrons in the outermost orbit 0 thus, solubility will decrease.]
5. An electrovalent bond is formed between: 13. Lattice energy of an ionic compound depends on :
lA.l.E.E.E. 2005)
(a) two electronegative atoms o
(b) two metals o (a) charge on the ion only o
(c) electropositive and electronegative atoms 0
(b) size of the ion only o
. (d) two electropositive atoms 0
(c) packing of the ion only o
6. Most favourable conditions for electrovalent bonding are:
(d) charge and size of the ion o
14. In covalency:
. lD.P.M.T. 2005)
(a) low ionisation potential of one atom and high electron
(a) transfer of electrons takes place o
(b) one atom acts as donor and other acts as acceptor o
affinity of the other atom 0
(c) the electrons are shared by only one atom o
(b) high electron affinity and high ionisation potential of
(d) equal sharing of electrons takes place between two
both the atoms 0 atoms o
(c) low electron affinity and low ionisation potential of 15. A covalent bond is possible between:
both the atoms 0 (a) similar atoms o
(d) high ionisation potential of one atom and low electron (b). dissimilar atoms o
affinity of the other atom 0 (c) similar and dissimilar atoms o
7. The crystal lattice of electrovalent compound is composed (d) similar molecules o
of: 16. Multiple covalent bonds exist in a molecule of:
(a) atoms 0 (b) molecules o (a) F2 0 (b) N2 0
(c) oppositely charged ions o (c) CH4 0 (d) H2 0
(d) both molecules and ions o 17. Which of the following statements is not true about covalent
8. The electro negativity of cesium is 0.7 and that of fluorine compounds?
is 4;.0. The bond formed between the two is: (a) They may.exhibit space isomerism 0
(a) covalent 0 (b) electrovalent 0 (b) They have low melting and boiling points 0
(c) coordinate 0 (d) metallic 0 (c) They show ionic reactions 0
9. Electrovalent bond is formed by: (d) They show molecular reactions 0
(a) sharing of electrons 0 (b) donation of electrons 0 18. Element X is strongly electropositive and Y is strongly
(c) transfer of electrons 0 (d) none of these 0 electronegative. Both are univalent. The compound formed
to. Four elements P, Q, R, S have atomic numbers Z - 1, Z, would be:
Z + 1 and Z + 2 respectively. If Z is 17, then bond between (a) X+y- o (b) X-Y o
which pair of elements will be most ionic ? (c) X-y+ o (d) X--+Y o
19, In a triple bond there ,is sharing of : 32. A molt~cule possessing dipole moment is:
(a) 3 electrons . 0 (b) 4 electrons 0 (a) CH 4 o (b) H 20 0
(c) several electrons 0 (d) 6 electrons', 0 (c) BF3 0 (d) CO 2, 0
20, Element A has 3 electrons in the outermost orbit and 33. In which of the following molecules the· bond angle is
element B has 6 electrons in the' outermost orbit The maximum?
formula of the compound formed between A and B would (a) CH 4 o
be: (c) NH3 o
(a) A2B3 o (b) A2B6 o 34. C02 is isostructural with:
(c) A2B o (d) A3B2 o (a) 502 0 (b) HgCl 2 0
21, The formula of the compound is A 2Bs.The number of (c) C 2H 2 0 (d) SnCl2 0
electrons in the outermost orbits of A and B respectively 35. Both ionic and covalent bonds are present in:
are: (a) CH 4 0 (b) NaOH 0
(a) 6 and 3 o (b) 5 and 6 o (c) KCI 0 (d) 502 0
(c) 5 and 2 o (d) 2 and 3 o 36. The compound with the highest boiling point is:
22. Which shows the highest lattice energy? (a) CH30H 0 (b) CH3Br 0
(a) RbF 0 (b) CsF o (c) CH 3Cl 0 (d) CH 4 0
(c) NaF 0 (d) KF o 37. The bond between carbon atom (1) and carbon atom (2) in
23. Polarisation is the distortion of the shape of an anion by compound,
the cation. Which of the following statements is correct? N==C-CH=CH 2 involves the hybrid as:
(a) Maximum polarisation is done bya cation of high (1) (2)
charge 0 (a) sp and sp2 0 (b) sp2 and Sp3 0
(b) A large cation is likely to brinK large degree of (c) sp and Sp3 0 (d) sp and sp 0
polarisation 0 38. The bonds present in N 20 S are:
(c) A smaller anion is likely to undergo a high' degree of (a) only ionic 0
polarisation 0 (b) covalent and coordinate 0
(d) Minimum polarisation is done by a cation of small size (c) only covalent D. (d) covalent and ionic 0
o 39. The hydrogen bond is strongest in: [A.I.E.E.E.2007]
24. Variable valency is shown by: (a) O-H - - - S 0 (b) O-H - - - H 0
(a) s-block elements 0 (b) d-block elements 0 (c) F-H - - - F 0 (d) O-H - - - 0 0
(c) p- and d-block elements 0 40. The sigma andn:-bonds present in benzene ring are:
(d) all elements 0 (a) three sigma three pi o
25. The most covalent halide is: (b) six sigma and three pi o
(a) AIF3 0 (b) AICl 3 0 (c) six pi and three sigma o
(c) AlBr3 0 (d) A1I3 0 (d) nine sigma and three pi o
26. A n:-bond is formed by the overlap of : 41, Hydrogen bonding is maximum in:
(a) s-s orbitals 0 (b) s-p orbitals 0 (a) ethanol 0 (b) diethyl ether o
(c) p-p orbitals in end to end fashion 0 (c) ethyl chloride 0 (d) triethyl amine o
(d) p-p orbitals in sidewise manner D. 42. The hybridization of S in 502 is:
27. In the formation of ethylene molecule, the carbon atom (a) sp 0 (b) Sp2 0
makes use of: (c) Sp3 0 (d) dsp2 0
(a) Sp3 hybridization 0 (b) Sp2 hybridization' 0 43. Molecule in which the distance between two adjacent carbon
(c) sp hybridization 0 (d) none of these 0 atoms is largest, is:
28. Which of the following has a giant covalent structure? (a) benzene o (b) ethyne o
(a) CCl 4 0 (b) Si02 0 (c) ethene o (d) ethane o
(c) SiCl 4 0 (d) CO 2 0 44. . Which of the following compounds of N group elements
29. Which one of the following has pyramidal structure? would you expect to be most ionic in character?
(a) NH3 0 (b) SiF 4 0 (a) CCl 4 0 (b) SiCl 4 0
(c) H 20 0 (d) BF3 0 (c) PbCl 2 0 (d) PbCl 4 0
30. Which one of the following molecules are formed by p-p 45. The octet rule is not valid for the molecule:
overlapping? (a) CO 2 0 (b) H 20 o
(a) Cl 2 o (b) HCI o (c) O 2 0 (d) CO o
(c) H 20 o (d) NH3 o 46. The compound which contains both ionic and covalent
31, 104.50 is the bond angle present in: bonds is:
(a) H 20 0 (b) BF3 o (a) CH 4 o (b) H2 o
(c) NH3 0 (d) BeCl2 o (c) KCN o (d) KCI o
t38 GR.B. Inorganic Chemistry for Competitions
47. The type of bonds present in CuS04'5HzO are: 60. Which is the weakest among the following types of bonds?
(a) electrovalent, covalent and coordinate 0 (a) Ionic bond 0 (b) Covalent bond 0
(b) electrovalent and covalent 0 (c) Metallic bond 0 (d) Hydrogen bond 0
(c) electrovalent and coordinate 0 61. In a series ethane, ethylene and acetylene, the C-H bond
(d) covalent and coordinate 0 energy is:
48. The ion that is isoelectronic with CO is: (a) the same in all the three compounds 0
(a) CN- 0 (b) O~ 0 (b) greatest in acetylene 0
(c) 0"2 0 (d) N~ 0 (c) greatest in ethylene 0
49. The types of bonds present in NH4Cl are: (d) greatest in ethane 0
(a) electrovalent, covalent and coordinate 0 62. The high boiling point of water is due to:
(b) only ionic 0 (a) its high specific heat 0
(c) only covalent 0 (b) hydrogen bonding between the molecules 0
(d) covalent and coordinate 0 (c) weak dissoCiation of water molecules 0
50. On hybridization of one s- and one p-orbitals, we get: (d) its high dielectric constant 0
(a) two mutually perpendicular orbitals 0 63. The strength of sigma bonds formed by axial overlap of s-
(b) two orbitals at 1800 0 or p- orbitals of 2nd shell of participating atoms decreases
(c) four orbitals directed tetrahedrally 0 as.
(d) three orbitals in the plane 0 (a) s--s > p-s > p-p 0 (b) s-s > p-p > s--p 0
51. If a molecule MX3 has zero dipole moment, the sigma (c) p--s > s--s > p-p 0 (d) pop > s-p > s--s 0
bonding orbitals used by Mare: [Hint: p-orbitals afford maximum axial overlap and s-orbitals
(a) pure p D ' (b) sp hybrids 0 have minimum.]
(c) spz hybrids 0 (d) sp3 hybrids, 0 64. The triple bond in ethyne is made cif:
52. The species in which the central atom uses sp2 'hybrids in (a) three sigma bonds 0
its bonding is: ' (b) three x-bonds 0
(a) PH3 0 (b) AsH3 0 (c) one sigma and two x-bonds o
(c) NH3 0 (d) CH~ 0 (d) two sigma and one x-bond o
53. The molecule that has linear structure is: 65. The linear structure is assumed by :
(a) C02 0 (b) N02 0 A : SnClz B : NCO-
(c) 50z 0 (d) Si02 0 C:N~ D:CS2
54. The Cl-C-CI angle is I, I, 2, 2-tetrachloroethene and (a) A, Band C 0 (b) B, C and D o
tetrachloromethane respectively will be about: (c) A, C ,and D 0 (d) none o
(a) 109.50 and 900 0 (b) 1200 and 109,SO 0 66. Which of the following is diamagnetic?
(c) 90 and 109.5
0 0
0 (d) 109.50 and 1200 0 (a) O 2 0 (b) O 2 o
55. Coordinate linkage is formed: (c) 0"2 0 (d) O~- o
(a) by transfer of one electron from one atom to another 67. Acetylene molecule' contains:
o (a) 5 sigma bonds 0 (b) 4 sigma and lx-bond 0
0
(b) by the loss of one electron each from both the atoms (c) 3 sigma and 21t-bondsD (d) 2 sigma and 31t-bonds 0
(c) by sharing of one electron from each atom 0 68. Which one of the following has a coordinate bond?
(d) when contribution of one electron pair is made by one (a) NaCl 0 (b) Cl 2 0
atom and both the atoms sha:J,"e equally 0 (c) N.fI4Cl 0 (d) AICl 3 0
56. The' molecule which has highest dipole moment amongst 69. The number of o-and 1t-bonds in l-butene-3-yne are:
the following is: , ' (a) 5 sigma and 5 pi 0 (b) 7 sigma and 3 pi 0
(a) CH 4 o (b) CHCl 3 o (c) 8 sigma and 2 pi 0 (d) 6 sigma and 4 pi 0
(c) CCl 4 o (d) CHI 3 o 70. Which of the following is paramagnetic?
57. The number of unpaired electrons in an 02 molecule is: (a) O 2 0 (b) CN- 0
(a) zero 0 (b) 1 0 (c) CO 0 (d) NO+ 0
(c) 2 0 (d) 3 0 71. Which molecule has zero dipole moment?
58. The bond order of individual carbon bonds in benzene is: (a) CH 2 Cl 2 0 (b) BF3 o
(a) one 0 (b) two 0 (c) NF g 0 (d) CIO z o
(c) between one and two 0 72. NzO is isoelectronic with C02 and N3, which one is the
(d) one and two, alternately 0 structure of NzO ?
59. Which of the following would have a permanent dipole (a) N-O-N 0 (b) N==N-+O 0
moment?
(a) SiF 4 o (b) SF4 o o
(c) XeF4 o (d) BF3 o
73. Number of bonds in benzene: [D.P.M.T.2005] (a) dsp3 hybridisation 0 (b) d2sp3 hybridisation 0
(a) 6 cr and 3 1t 0 (b) 3 cr and 12 1t 0 (c) dsp2 hybridisation 0 (d) sp3d hybridisation 0
(c) 12 cr and 3 1t 0 (d) 6 cr and 6 1t 0 86. Which among the following compounds does not show
74. The shape of sulphate ion is: hydrogen bonding?
(a) hexagonal 0 (b) square planar 0 (a) Phenol 0 (b) Ethyl alcohol 0
(c) trigonal bipyrarnidal 0 (d) tetrahedral 0 (c) Acetic acid 0 (d) Diethyl ether' 0
75. Structure of ammonia is: 87. How many resonating forms can be written for nitrate and
(a) pyramidal 0 (b) tetrahedral 0 chlorate ions respectively?
(c) trigonal 0 (d) trigonal bipyramidal 0 (a) 3, 2 0 (b) 3, 3 0
76. Oxygen molecule is paramagnetic because: (c) 2, 3 0 (d) 3, 4 0
(a) bonding electrons are less than antibonding electrons
o
(b) bonding electrons are more than antibonding electrons
o
(c) it contains unpaired electrons 0 ,
(d) bonding electrons are equal to antibonding electrons
88. A molecule may be represented by three structures having
o energies Ev E2 and E3 respectively. The energies follow the
77. Resonance structure of a molecule should not have:
order E3 < E2 < E1. If the actual energy content of the
(a) identical arrangements of atoms 0
molecule is Eo, the resonance energy is :
(b) nearly same energy content 0
(a) (E 1 + E2 + E3) - Eo 0 (b) E3 - Eo 0
(c) the same number of paired electrons 0
(c) E3 - E1 ;0 (d) Eo - E2 0
(d) identical bonding 0
89. On the basis of resonating structures of CO~- ion, the
78. The bond order of a molecule is given by:
C-O bond order is :
(a) total number of electrons in bonding and antibonding
(a) 1.5 0 (b) 2 0
orbitals 0
(c) 1.33 0 (d) 3 0
(b) the difference between the number of electrons in
90. Which carbon atom is most electronegative?
bonding and antibonding orbitals 0
(a) Unhybridised carbon 0 (b) sp hybridised carbon 0
(c) twice the difference between the number of electrons
(d sp2 hybridised carbonO (d) sp3 hybridised carbon 0
in bonding and antibonding orbitals ' 0
[Hint: Higher s-character in hybridization brings more electro-
(d) half the difference between the number of electrons in
negativity.]
bonding and anti bonding orbitals 0
91. The maximum possible number of hydrogen bonds in
79. Which one is electron deficiellc compound?
which a water molecule can participate is:
(a) ICI 0 (b) BCl3 0
[CE.T. (Karnataka) 2008]
(d NH3 0 (d) PCl3 0
(a) 1 0 (b) 2 0
80. A sp3 hybrid orbital contains:
(c) 3 0 (d) 4 0
(a) 1/4 s-character 0 (b) 1 /2 s-character 0
92. Which of the following statements is true about
(d 2/3 s-character o (d) 3/4 s-character o [Cu(NH3)4J S04?
81. Identify the incorrect statement : (a) It has coordinate as well as covalent bonds 0
(a) There are two 1t and one sigma bonds in N 2. o (b) It has only coordinate bonds 0
(b) The hybridisation of oxygen in H 20 is sp3. o (c) It has only electrovalent bonds 0
(c) Solid NaCl is a bad conductor of electricity. o (d) It has electrovalent, covalent as well as coordinate bonds
(d) Hydrogen bond is a chemical bond. o o
82. Metallic lustre is explained by : [D.CE. 2005] 93. Which of the following is not a linear molecule?
(a) oscillations of loose electrons o (a) CO 2 0 (b) C 2H 2 0
(b) diffusion of metal ions o (c) HCN 0 (d) H 20 0
(c) excitation of free protons .0 /94. The bond angles of NH3, NHt and NH2: are in the order:
(d) existence of bcc lattice 0 (a) NH2: > NH3 > NHt 0 (b) NHt> NH3 > NH2: 0
83. A molecule, which contains unpaired electrons is: (c) NH3 > NH2: > NH! 0 (d) NH3 > NH! > NH2: 0
(a) CO 2 0 (b) N2 0 95. As compared to covalent compounds, electrovalent com-
(c) O 2 0 (d) H 20 2 0 pounds generally have:
(a) low melting points and low boiling 'points 0
84. Which has the bond order ~? (b) low melting points and high boiling points 0
(a) O2 0 (b) N2 0 (d high melting points and low boiling points 0
(c) F2 0 (d) H'2 0 (d) high melting points and high boiling points 0
85. The maximum number of 90° angles between bond pair- 96. Coordinate covalent bond is formed by:
bond pair of electrons is observed between : (a) transfer of electrons 0 (b) sharing of elections 0
[A.I.E.E.E. 2004] (c) donation of electrons 0 (d) none of these 0
97. The molecule which does not' exhibit dipole moment is: (a) (D and (ll) 0 (b) (i) and (iv) 0
(a) NH3 0 (b)CHC1 3 0 (c) (D and (ill) 0 (d) (ll), (ill) and (iv) 0
(c) H 20 0 (d) CCl 4 0 111. Which one of the following molecule is trigonal bipyra-
.. ~/
midal?
98. How many bonds are there in LQJ .'?

(a) BF3
(c) PCIs
0 (b) CH4
0 (d) SF6
112. Ammonia molecule is fonned due to the following
0
0
[D.C.E. 2005} hybridized orbitals:

(a) 14 cr, 8 1t o (b) 18 cr , 81t o (a) dsp2 0 (b) sp3 0
(c) 14 cr, 2 1t o (d) 14 cr , 4 1t o ~~d 0 ~d~ 0
99. Hybridisation of the atom changes in : 113. The electronic structure of four elements a, b, c and dare:
(a) AlH3 to AlH4 ' 0 (b) H:z.Q to H30+ 0 (i) ls2 (ll) I;, 2sz 2p2 (ill) I;, 2ps (iv) I;, 18z 2p6
(c) NH3 to NH4 0 (d) all of these 0 The tendency to form electrovalent bond is greatest in:
100. In which of the following the central atom does not use sp3 (a) (i) 0 (b) Oi) 0
hybrid orbitals in its bonding? (c) (iii) 0 (d) (iv) 0
(a) BeF 3 . 0 (b) OH,3 0
114. Hydrogen bonding is maximum in:
(c) NH"Z .D (d) NF3 0 (a) ethanol 0 (b) diethyl ether 0
101. The hybridization of carbon atoms in C-C single bond of (c) ethyl chloride 0 (d) triethylamine 0
HC==C-CH" CH2 is: 115. The central atom assumes sp3 hybridization in:
(a) sp3_sp3' 0 (b) sp2_sp3 0
(a) PCl3 0 (b) 503' "0
(c) sp_sp2 0 (d) sp3-sp 0
(c) BF3 0 (d) NO"3 0
102. The type of hybrid orbitals used by the chlorine atom in 116. NH3 and BF3 fonn an adduct readily because they fonn:
CIO"2 is: (II.) an ionic bond 0 (b) a covalent bond . 0
(a) sp3 0 (b) sp2 0
(c) a hydrogen' bond 0 (d) a coordinate bond 0
(c) sp 0 (d) none of these 0 117. NH3 has a much higher boiling point than PH3 because:
103. Amongst LiCI, BeCl2J MgCl2'and RbCI the compounds with (a) arrimonia has larger molecular weight 0
greatest and least ionic character, respectively are: (b) ammonia undergoes umbrella inversion . 0
(a) LiCl and OCI' 0 (b) RbCl and BeCl2 0 (c) ammonia contains ionic bonds whereas PH3 contains
(c) RbCl and MgC12 0 (d) MgCl2 and. BeCl2 0 covalent bond 0
104. BeFz has zero dipole moment whereas H20 has a dipole (d) ainmonia fonn hydrogen bonds 0
moment because: 118. In S02 molecule, the observed bond lengths of two
(a) water is linear 0 S-O bonds are exactly the same and the length is
(b) H20 is bent 0 somewhere in between single and double bond length. It
(c) F is more electronegative than 0 0 is because of:
(d) hydrogen bonding is present in H20 0 (a) hybridization 0 (b) resonance
105. Which of the following geometrical configurations (c) coordinate bonding 0 (d) geometry 0
correspond to dsp2 hybridization? 119. The molecule which has pyramidal shape is:
(a) Tetrahedral 0 (b) Pentagonal bipyramid 0 (a) 503 0 . (b) PCl3 0
(c) Square planar 0 (d) Trigonal bipyramid 0 (c) coj- 0 (d) NO"3 0
106. Which one of the following bonds has the highest average 120. The compound in which C uses its sp3 hybrid orbitals for
bond energy? bond fonnation is:
(a) S=O 0 (b) C==C 0 (a) HCOOH 0 (b) (HzNh CO 0
(d C==N 0 (d) N==N 0
(c) (CH3h CH 0 (d) CH3 CHO 0
107. Which one of the following is not paramagnetic?
121 ....... cation and .......... anion favour least covalent character.
(a) O 2 0 (b) 02 0 (a) Small, large 0 (b) Large, small . 0
(c) 02: 0 (d) O~- 0 (c) Large, large 0 (d) Small, small 0
108. Which of the following has a tetrahedral structure? 122. T-type shape is exhibited by the molecule:
(a) NH3 0 (b) ~Fe(CN)6 0 (a) CIF3 0 (b) CHCl3 o
(c) NH"4 0 (d) [NHCN)4]Z- 0 (c) CCl 4 0 (d) PCIs o
109. Among the following ions which one has the highest 123. An example of molecule having a three centre bond is:
paramagnetism? (a) BN 0 (b) H3B03 0
(a) [Cr(H ZO)6]3+ 0 (b) [Fe{H zO)6]z+ 0 (d NaBH4 0 (d) B2H6 0
(c) [Cu(H20)6f+ 0 (d) [Zn(HZO)6] 0 124. The geometry of the molecule with 25% s-character in
110. Pick out the isoelectronic structures from the following? hybrid orbital is:
(i) CH3. (ti) H30+ (iii) NH3 {iv)CH3"
(a) plane triangular o (b) linear o.
(c) tetrahedral o (d) octahedral o
125. Knowing that Na+ > Mgz+ and 5z- > cr, predict which (c) square planar 0
compound will be least soluble in polar solvent? (d) distorted trigonal bipyramid 0
(a) MgS 0 (b) NazS 0 136. The shape of CIO) according to VSEPR model is:
(c) MgCl 2 0 (d) NaCl 0 (a) planar triangle 0 (b) pyramidal 0
126. Which of the following elements shows the capacity to form (c) tetrahedral 0 (d) square planar 0
hybrid orbitals by using S,P and d-atomic orbitals? 137. The correct order of increasing C-O bond length of CO,
(a) B 0 (b) C 0 CO~~ CO2 is: [I.I.T. 1999; C.B.S.E.2007]
(c) N 0 (d) 5 0 (a) CO~- < CO2 < CO 0 (b) COz < CO~- < CO 0
127. Molecule showing angle greater than observed in (c) CO < C~- < COz 0 (d) CO < CO2 < CO~- 0
tetrahedral structure is: 138. The geometry of H 2S and its dipole moment are:
(a) NH3 0 (b) ChO 0 (a) angular and non-zero 0
(c) HzO 0 (d) OF z 0 (b) anguIar and zero 0
128. The correct order of the b-O .bond length in 0 21 H2~ and (c) linear and non-zero 0
0 3 is: (d) linear and zero 0
(a) 0 3 > H202 > O2 0 (b) Oz> H202 > 0 3 0 139. In the compounds of type ECl3 where E B, P, As or Bi the
(c) ~> 0 3 > H 20z 0 (d) H202> 03> O2 0 angles Cl-E-Cl for different E are in the order:
[Hint: Bond between --0-0--- in H 20 Z is a single bond (a) B > P = As = Bi 0 (b) B > P > As > Bi 0
[1.48 A]. Bond between 0-0 in 03 is intermediate (c) B < P = As = Bi 0 (d) B < P < As < Bi 0
between single and double bonds due to resonance 140. The formal charges on three oxygen atoms of ozone
0.278 A) while bond between O2 molecule is a molecule are respectively :
double bond 0.21 A).] (a) +1,0,+1 0 (b)O,O,O 0
129. BCl3 is a planar molecule whereas NCl3 is pyramidal (c) +1,0, -1 0 (d) -I, +1, -1 0
because: 1 z 3 4 5 6
141. In the compound CHz=CH-CHz-CHz-C==CH, the
(a) nitrogen atom is smaller than boron atom 0 2 3
. (b) BCl3 has no lone pair of electrons whereas NCl3 has a C -C bond is of the type:
lone pair of electrons 0 (a) sp_spz 0 (b) sp3_sp 3 0
(c) N-Cl bond is more covalent than B-CI bond 0 (c) sp_sp3 0 (d) spZ_sp3 0
(d) B-Cl bond is more polar than N-Cl bond 0 142. In XeF:z, XeF4 and XeF6 the number of lone pairs on Xe is
130. Which of the following molecules is planar? respectively: [A.I.E.E.E.2002]
(a) XeF4 0 (b) NF3 0 (a) 2,3, I 0 (b) 1,2,3 0
(c) SiF4 0 (d) 5F4 0 (c) 4, I, 2 0 (d) 3, 2, 1 0
131. Which one is the correct statement with reference to 143. Number of sigma bonds in P40 lO is: [A.I.E.E.E. 2002]
solubility of MgS04 in water? (a) 6 0 (b) 7 o
(a) Hydration energy of MgS04 is higher in comparison to (c) 17 0 (d) 16 o
its lattice energy 0 144. Which of the following does not contain coordinate bond?
Mi+
(b) Ionic potential of is very l o w . 0 [P.M.T. (Raj.) 2002]
(c) soi- ion mainly contributes towards hydration energy (a) BH4 0 (b) NH2 0
o (c) CO~- 0 (d) H~O 0
(d) Sizes of Mgz+and soi- are similar 0 145. Which of the following has p1t-iht bonding? [CB.S.E. 2002]
132. Which of the following compounds has a 3 centre bond? (a) N03 0 (b) SO~- 0
(a) BF3 0 (b) NH3 0 (c) BO~- 0 (d) CO~- 0
(c) BzH 6 0 (d) C02 0 146. In N03 ion, number of bond pairs and lone pairs of electrons
133. Which of the following phenomenon will occur when two on nitrogen atom are: [C.B.S.E. 20021
atoms of same spin will react? (a) 2, 2 0 (b) 3, 1 0
(a) Bonding will not occur 0 (c) 1, 3 0 Cd) 4, 0 0
(b) Orbital overlap will not occur 0 147. In OF2, number of bond pairs and lone pairs of electrons
(c) Both (a) and (b) 0 are: [D.P.M.T. 2002J
(d) None of the above o (a) 2, 6 0 (b) 2,8 0
134. Which bond angle e would result in. the maximum dipole (c) 2, 10 0 Cd) 1, 9 0
moment for the triatomic molecule 148. A square planar complex is formed by hybridization of
(a) e 90 0 0 (b) e 120" 0 which atomic orbitals? [A.I.E.E.E. 2002)
(c) e 1500 0 (d) e 180" 0 (a) s, Px, Py' pz, dyz 0 (b) s, Px, Py, di i 0
135. The structure of 1C12 is: (c) s, Px , Py , dz2 0 (d) s, Px , Pz, dxy 0
(a) trigonal 0 149. Match List (I) (molecules) with List (II) (bond order) and
(b) octahedral 0 select the correct answer using the codes given in the lists:
[S.C.R.A. 2000]
,142 G.R.B. Inorganic Chemistry for Competitions
List I List II (c) BF3 > NF3 > PF3 > ClF3 0
1. Liz A.3 W~>~>~>~ 0
II. N2 B. 1.5 [Hint: Bond angles are : BF;r-120", NF3-106°, PF;r-101°,
IlL Bez C. 1.0 CIF3-90" ]
IV. O 2 D. 0 158. In an octahedral structure, the pair of d-orbitals involved
E. 2 in isp3 hybridization is: [C.B.8.E. (P.M.T.) 2004]
Codes: (a) dx2 _ y2, dz2 0 (b) dxz, dx2 y2 0
(a) I - B ; II - C; III A; IV - E o (c) dz2, dxz 0 (d) dxy' dyz 0
(b) I - C ; II - A; III - D; IV - E o 159. According to molecular orbital theory which of the
(c) I - D ; II A; III - E; IV - C o following statements about the magnetic character and bond
(d) I - C ; II B; III - E; IV A o order is correct regarding O~ ? [U.T. (8) 2004]
150. The correct order of hybridization of the central atom in (a) Paramagnetic and bond order < Oz 0
the following species; NH3, [Pt(Cl.vl z-, PCls and BCl3: (b) Paramagnetic and bond order> O 2 0
[I.I.T. (8) 2001; B.H.U. 2005] (c) Diamagnetic and bond order < Oz 0
(a) dsp2, dsp3, sp2 and sp3 0 (d) Diamagnetic and bond order > O 2 0
(b) sp3, dsp2, dsp3, sp2 0 160. Which is the correct order of increasing dipole moment ?
(c) dspz, spz, sp3, dsp3 0 (a) ClF < BrCl < NO < HCl < Lil 0
(d) dsp2, sp3, sp2, dsp3 0 ~w<~<~<rn<~ 0
(c) BrCl < NO < HCI < CIF < LiI 0
151. The common features among the species CN-, CO and NO+
(d) NO < BrCl < HCI < LiI < ClF 0
are: [U.T. (8) 2001]
[Hint : Electronegativity Li = 1.0, H 2.1, N = 30, 0 3.5,
(a) bond order three and isoelectronic 0 F 4.0, Cl = 2.9, Br = 2.8, I = 2.2
(b) bond order three and weak field ligand 0 Electronegativity difference BrCl = 0.1, NO 0.5,
(c) bond order two and 1t-acceptors 0 HCI = 0.8, CIF 1.1, Lil = 1.2
(d) isoelectronic and weak field ligands 0 Dipole moment <x: Electronegativity difference]
152. Which of the following molecular species has unpaired 161. Which of the following has highest melting point?
electron(s)? [U.T. (8) 2002] [P.E.T. (Raj.) 2003]
(a) Nz 0 (b) 0 (a) BeCl z 0 (b) MgCl z 0
(c) O 2 0 (d) O~- 0 (c) CaCl z 0 (d) BaCl z 0
162. Maximum bond angle is present in: [n.p.M.T. 2003] .
153. Which of the following hydrocarbons has the lowest dipole
(a) BF3 0 (b) 'BCl3 0
moment? U.I.T. (8) 2002]
.. CH3) <CH3
(c) BBr3 D (d) same for all
163. Pick out the isoelectronic structures from the following:
0
W C 0
[A.M.U.2003]
H H
(I) CH~ (II) H~ 0 (IlI) NH3 (IV) CH 3
(b) CH3~C==C-CH3 0
(a) I and II 0
(c) CH3-CHz-C-C-H 0
MIII~IV 0
(d) CH 2 =CH-C=C-H 0
(c) II, III and IV D
154. The nodal plane in the 1t-bond of ethene is located in:
(d) III & IV and II, III & IV D
[I.I.T. (8) 2002]
(a) the molecular plane 0 164. Which of the following is a correct set? [E.A.M.CE.T. 2003]
(a) H 20 sp3 angular 0
(b) a plane parallel to molecular plane 0
(b) H 20 sp2 linear 0
(c) a plane perpendicular to the molecular plane which
(c) NH! dsp2 square planar D
bisects the carbon-carbon sigma bond at :right angle 0
(d) C~ dsp2 tetrahedral 0
(d) a plane perpendicular to the molecular plane which
165. Which of the following compounds has the smallest bond
contains the carbon-carbon a-bonds 0
angle in its molecule? [A.I.E.E.E. 2003]
155. The shape of OzF2 is similar to: [A.I.I.M.8. 2004]
(a) 5 0 2 ' 0 (b) H 20 0
(a) C 2F2 0 (b) H 20 2 0
(c) 0 (d) NH3 0
(c) 0 (d) C2H2 0
156. The ONO angle is maximum in: [A.I.I.M.8. 2004] 166. Which of the following pairs of molecules will have
(a) N03 0 (b) N0 2 0 permanent dipole moments for both members?
(c) N02 0 (d) NO z 0 [A.I.E.E.E.2003]
[Hint: In NOt nitrogen atom is sp hybridized.] (a) Sif4 and N0 2 0 (b) NOz and COz 0
157. The correct decreasing order of bond angles is : (c) NOz and 0 3 0 (d) Sif4 and CO2 0
.(a) ClF3 > PF3 > NF3 > BF3 0 167. If the molecule of HC] is considered. as totally polar, the
(b) BF3 > PF3 > NF3 > ClF3 0 expected value of dipole moment is 6.12 D but the
experimental value of dipole moment is 1.03D. What is the of hybridization : [CE.E. (Kerala) 2004]
percentage ionic character in HCI? (a) BF3 and NCl3 0 (b) H 2S and BeCl2 0
(a) 17 0 (b) 83 0 (d SF4 and NCl3 0 (d) NCl3 and H 2S 0
(c) 50 0 Cd) 90 0 179. Pair of species having identical shapes for molecules is:
obs. dipole moment x 100
[D.CE. 2005]
[Hint : % ionic character (a) CF4, SF4 0 (b) BF3, PC13 0
cal. dipole moment
(c) XeF2 , CO 2 0 (d) PF5, IF5 0
= 1.03 x 100 171
[Hint : Both XeF2 and CO2 have linear shapes.]
6.12
168. Which of the following shows isostructural species? 180. The d-orbital involved in sp 3d hybridization is:
[A.F.M.C 2003] lCE.T. (J&K) 2005]
(a) NH! and NH2 0 (b) CH"3 and CHj 0 (a)dxz_y2 0 (b)d xy 0
(c) SO~-,P~- and BF4 0 (d)NH~ and NH3 0 (c) dzz 0 (d) dzX 0
181. Which of the following is planar? [CE-T. (J&K) 2005]
169. The ion which is not tetrahedral in shape is:
(a) XeF 2 0 (b) Xe03F 0
[A.U.M.S. 2003]
(c) XeOzF 2 0 (d) XeF4 0
(a) BF4 0 (b) NH~ o 182. The species having bond order different from that in CO is:
(c) [Cu(NH3)41 2+ 0 (d)NiClt o [I. LT. 2007]
170. Which of the following has dspz hybridization? o (b) NO+ o
[P.E.T. (M.P.) 2003] o (d) N o
(a) NiCl~- 0 (b) SCl4 0
z
183. Which of the following species exhibits the diamagnetic
(c) NHt 0 (d) PtCl ~- 0 behaviour? [A.I.E.E.E. 2007]
171. In which of the following pairs of molecules have bond (a) NO 0 (b) O~- 0
order three and are isoelectronics? [P.E.T. (M.P.) 2003] (d 02 0 (d) Oz 0
(a) CN- , CO 0 (b) NO+ ,CO+ 0
184. The charge! size ratio of a cation determines its polarizing
(c) CN- , O~ 0 (d) CO, 0:2 0
power. Which one of the following sequences represents
172. Paramagnetism of oxygen is explained on the basis of its
the increasing order of the polarizing power of the cationic
electronic configuration of : [P.E.T. (Kerala) 2003] species K+, Caz+, Mg2+, Be2+? lA.I.E.E.E. 2007]
(a) (2crPx)\21tp/ 0 (b) (2crp)1(21tpl 0 (a) Ca2+ < Mgz+ < Be2+ < K+ 0
(d (2crPz)1(21tp/D (d) (21tpl(2rcPz)1 0 (b) ~2+ < Be2+ < K+ < Caz+ 0
173. Which of the following is .not correct? (d Be + < K+ < Ca 2+ < Mg2+ 0
[E.AM.CE.T. (Medical) 2004] (d) K+ < Ca z+ < Mgz+ < Be2+ . 0
(a) One of the favourable conditions for the formation of 185. In which of the following ionisation processes, the bond
cation is low ionisation potential 0 order has increased and the magnetic power has changed?
(b) Coordination number of Cs in CsCl is 8 0 lAJ.E.E.E. 2007]
(c) Ionic bond is directional 0 (a) N z ----? Nz o (b) Cz ----? C z 0
(d) Ionic compounds have high melting and boiling points (c) NO ----? NO+ o (d) Oz ----? 02 0
o 186. In which of the following pairs, two species are iso-
174. Covalent bond exists in: [D.CE. 2004] structural? [CB.S.E. 2007]
(a) Na2S 0 (b) AICl 3 0 (a) SO~- and N0 3 0 (b) BF3 and NF3 0
(c) NaH 0 (d) MgCl 2 0 (c) Br03 and Xe03 0 (d) SF4 and XeF4 0
175. In which of the following the central atom has maximum 187. Match List I with List II and choose the correct matching
number of lone pair of electrons? [U.T. 2005] codes from the choices given: [P.E.T. (Kerala) 2007]
(a) SF4 0 (b) XeF4 IJ List I List II
(c) ClUJ 0 (d) 13 0 A. PCl5 . 1. Linear
176. Bond energies in NO, NO+ and NO- are such' as: B. 1F7 2. Pyramidal
[CE.T. (Punjab) 2004] C. H30+ 3. Trigonal bipyramidal
(a) NO- > NO > NO+ o (b) NO > NO- > NO+ 0 D. Cl0 2 4. Tetrahedral
(c) NO+ > NO > NO- o (d) NO+ > NO- > NO 0 E. NHt 5. Pentagonal bipyramidal
177. Molecular orbital electronic configuration for 'x' anion is 6. Angular
KK· (cr15)z (015)z(1t2Px)2(1t2p/(cr2P zf(1r2Px)1 (a) A-3, 8-5, 0-1, E-1 0
The anion 'x'is: [AM.D. 20041 (b) A-3, 8-5, C-4, D-1, B-2 0
(a) N2 0 (b) O2 0 (c) A-3, 8-5, C-6, D·}, E-2 0
(d N i- 0 (d) O~- IJ (d) A-3, 8-5, C-2, 0-6, E-1 0
178. Among the compounds BF3, NCI3, SF4, H 2S and BeClz, (e) A-3, 8-5, C-2, D-i, E-l 0
identify the one in which the central atom has the same type
t44 G.R.B. Inorganic Chemistry for Competitions
188. Which of the following is paramagnetic with bond order (a) Antibonding n:-molecular orbital 0
0.5? [P.E.T. (KeraIa.) 2007] (b) Bonding n:-molecular orbital 0
(a) F2 0 (b) Hi 0 (c) a-bonding molecular orbital 0
(c) N2 0 (d) 02' 0 (d) a-antibonding molecular orbital 0
189. Among the following, the pair in which the two species are 196. Four diafomic species are listed below in different
not isostructural is: [P.E.T. (Kerala) 2007] sequences. Which of' these represents the correct order of
(a) 103 and Xe03 0 (b) PF6" and SF6 0 increasing bond order? [CB.S.E. 2008]
(c) BH4 and NHt 0 (d) CO~- and NOi 0 (a) C~- < Hei < NO< 02: 0
[Hint : CO~- Trigonal planar; N02: - Angular] (b) Hei < 02: <NO < d- 0
190. The correct order of bond order values among the following (c) 02 < NO < C~- < Hei 0
is: [P.M.T. (Kerala) 2007] (d) NO < C~- < 0'2 < Hei 0
(i) NO- (ii) NO+ (iii) NO (iv) N02+ (v) Nd- [Hint : Bond order He~ = 0.5; 02: = 1.5; NO = 2.5; 3]
(a) (D < (iv) < (iii) < (ii) < (v) 0 197. Which one of the following pairs of species has the same
(b) (iv) (ii) < (i) < (v) < (iii) 0 bond order? [A.I.E.E.E. 2008]
(c) (v) < (D < (iv) (iii) < (ii) 0 (a) NO+ and CN- 0(b) C~ and NO+ 0
(d) (v) < (i) < (iv) < (iii) < (ii) 0 (c) C~ and CN+ 0(d) 02' and C~ 0
191. The bond lengths and bond angles in the molecules of [Hint : CW and NO+ are isoelectronic. Both ha~e 14 electrons
each.]
methane, ammonia' and water are given below:
198. The <;alculated bond order of superoxide ion (02') is:
[CE.T. (Karnataka) 2008]
~091lIIi ~Olnm ~96nm (a) 1.5 [] (b) 1 0
H 109.5
0
H H 107 H
0
H 104:5° H
(c) 2.5 o (d) 2 0
This variation in bond angle is a result of 199. Molecular shapes of SF4, CF4 and XeF4 are:
(i) the increasing repulsion between hydrogen atoms as
[P.M.T. (Kerala) 2008]
the bond length decreases (a) the same with 1, 1 and 1 lone pair of electrons
(ii) the number of non-bonding electron pairs in the respectively on the central atom 0
molecule (b) the same with 1, 0 and 2 lone pairs of electrons
(iii) a non-bonding electron pair having a greater repulsive respectively on the central atom 0
force than a bonding electron pair. (c) different with 0, 1 and 2 lone pairs of .electrons
[P.M.T. (Kerala) 2007] respectively on the central atom 0
(a) (i), (ll) and (iii) are correct o (d) different with 2, 0 and 1 lone pairs of electrons
(b) (i) and (ii) are correct o respectively on the central atom 0
(c) (ii) and (iii) are correct o (e) different with 1, 0 and 2 lone pairs of electrons
(d) (i) only is correct o respectively on the central atom 0
192. Match the compounds in the List I with that in List IT: 200. Which of the following does not have a coordinate bond?
List I List II [CP.M.T. 200S]
(a) 502 0 (b) HN03 0
A. xe03 i. Planar triangular
B. XeOF4 ii. T-shape (c) H 2503 0 (d) HN02 0
C. BOt iii. Trigonal pyramid 201. Which of the following represents the Lewis structure of
D. CIF3 iv. Square pyramid N2 molecule? [A.F.M.C 200S]
xx xx
E. Ii(aq) v. Linear (a) ~N N~ 0 (b) ~N"""'N~ o
vi. Bent LP.M.T. (Kerala) 2007] xx xx xx xx
(a) A-i, B-iv, C-iii, D-ii, E-v o (c) ~N-N~

xx xx
0 (d) ;N=N~
xx
o
(b) A-ii, B-iv, C-i, D-iii, ,E-vi o 202. Shape and hybridization of IPs respectively are:
(c) A-iii, B-iv, D-ii, E-vi 0 [J.E.E. (Orissa) 200S]
(d) A-iii, B-iv, D-ii, E-v 0 (a) trigonal bipyramidal, sp3d o
193. WhiCh of the following two are isostructural? (b) see-saw, sp3d • o
[B.H.V. 2007~ (c) square pyramidal, sp3d2 o
(a) XeF:z, 0 (b) NH3,BF3 0 (d) pentagonal pyramidal, t!id2 o
(c) cot SO~- 0 (d) POs, lCls 0 203. Cl-P-Cl bond angles in pels molecule are :
194. Planar structure is shown by: [A.U.M.S. 2007] IV.I.T.E.E.E. 2MS]
(a) CO~- 0 (b) BCl 3 0 . (a) 1200 and 900 D (b) 60" and 90 0 0
(c) N(SiH3h 0 (d) all of these 0 o (d) 120 and 30° 0
0
195. N2 accepts electron and converts into Ni, where the electron 204. According to MO theory which of' the lists ranks the
, goes? [D.CE. (Engg.) 2007] nitrogen species in terms of increasing bond order?
[CO.S.E. CP.M.T.) 20u':}i
(a) N~- < N2 < N2 0 (b) N2 < N~- < N z 0 [Hint: The B.O. of both Hi and H2 are 1/2 but Hi is more stable
(c) N2 < N~- < N2 0 (d) N2 <·N2 < N~- 0 as it does' not have antibonding electron.]
10-4 _ 10-5 211. Arrange the following in the increasing order of their bond
[Hint: B.O. N 2 =-2-=3; B.O.N 2 =-2-=2.5.
order: O2, oi, Oz and O~-. [CE.T. (Karnataka) 2009]
2- 10-6
B.0.N2 =-2-=2.Q ] (a) O~-, Oz, oi, O 2 0 (b) oi, Oz, Oz, O~- 0
205. In which of the following molecules lions BF3, NO z , NH z (c) O2, oi, Oz, O~- 0 (d) O~-, Oz, O2, oi 0
and H 20, the central atom is sp2 hybridised? . 10-6 10-5
[HInt: B.O. of O 2 =-2-=2.0; B.O. of Oi=-2-=2.5;
[CS.S.E. (P.M.T.) 2009J
(a) NHz and H 20 0 (b) NOz and H20 [] B.O. of Oz = 10-7 =1.5; B.O. of
2
O~- = 10-8 =1 ]
2
(c) BF3 and NOz 0 (d) NOz andNHz 0
212. Out of N 20, SOz, It, 13", H 20, NO z and N3", the linear species
z
[Hint : BF3 ~ sp2; NO ~ sp2; NH ~ sp3; H 20 ~ sp3 ]z are: [J.E.E. (Orissa) 2009]
206. The correct stability order of the following resonance
(a) NOz, It, H 20 0 (b) N 20, It, N3" 0
structures is: [I.LT. 2009]
+ . + - (c) NzO, 13", N3" 0 (d) N3, It, S02 tJ
(i) H 2C=N=N (ii) H C-N . N
2 213. The energy required to break one mole of Cl-CI bonds in
(iii) Hi:-N=N (iv) H 2C-N=N Cl2 is 242 kJ mol-I. The longest wavelength of light capable
(a) (i) > (ii) > (iv) > (iii) 0 (b) (i) > (iii) > (ii» (iv) 0 of breaking a single Cl-CI bond is : [A.I.E.E.E. 2010]
(c) (i) > (ii) > (iii) > (iv) [] (d) (iii) > (i) > (iv) > (ii) 0 [c = 3 x 108 ms-I and NA = 6.02 x 1023 morI ]
[Hint : Number of 7t-bonds oc Resonance energy oc stability (a) 494 nm 0 (b) 594 nm 0
In contributing structures, like charges should not reside (c) 640 nm 0 (d) 700 nm 0
on atoms closer to each other and unlike charges should 3
not be widely separated.]

· t : Energy requITe
[H In . d to break one bond of Cl-Cl = 242 x 10 J
NA
207. Using MO theory predict which of the following speCies has 242 x 10 3
the shortest bond length? [AJ.E.E.E.2009] 6.02 x 1023 J
(a) O~+ 0 (b) oi 0 Applying the formula, E = ~ or A. = he
A. E
(c) O2 0 (d) O~- []
6.63 X 10-34 x 3 x 108 x 6.02 x 10 23
[Hint : Bond length oc B 1 ; B.O. of 0 22+ O +2 O 2- and 0 2
2- 242 x 10 3
ond order ' , = 494 x 10-9 m = 494 nrn]
are 3.0, 2.5, 1.5 and 1 respectively.] .
214. In which of the following molecules, the central atom does
208. The bond dissociation energy of B-F in BF3 is 646' kJmorI
not have sp3-hybridization? [CB.S.E. (P.M.T.) 2010]
whereas that of C-F in CF4 is 515 kJ morl. The correct reason
(a) CH 4 0 (b) SF4 0
for higher B-F bond dissociation energy as compared to that
(c) BF4 0 (d) NHt 0
of C-F is: IA.I.E.E.E.2009]
215. Some of the properties of two species N03". and H30+ are
(a) smaller size of B atom as compared to that of C atom []
described below. Which one of them is correct? .
(b) stronger (J bond between Band F in BF3 as compared to that
[CS.S.E. (P.M.T.) 2010]
between C andF in CF4 . []
(a) Dissimilar in hybridization for the central atom with
(c) significant p7t-p1t interaction between B and F in BF3
different structures 0
whereas there is no possibility of such interaction
(b) Isostructural with same hybridization for the central
between C and F in CF4 0
~m 0
(d) lower degree of p1t-p1t interaction .petween B and F in
(c) Isostructural with different hybridization for the central
BF3 than that between C and F in CF4 0
~m 0
[Hint : In BF3, B is sp2 hybridized and has a vacant 2p orbital
which. overlaps laterally with a filled 2p orbital of F (d) Similar in hybridization for the central atom with
forming strong pn-p7t bond. However, in CF4 the C does different structures 0
not have any vacant p-orbital.] [Hint : N03 has sp2 hybridization while H30 + has sp3 hybridi-
zation] .
209. A covalent molecule AB3has pyramidal structure. The
216. The bond energy (in keal morI ) of a C-C Single bond is
number of lone pair and bond pair electrons in the molecule
are respectively: ICE.T. (Knrnataka) 2009] approximately: (I.I.T. 2010]
(a) 1 * 0 (b) 10 0
(a) 0 and 4 0 (b) 3 and 1 0
(c) 1 and 3 0 (d) 2 and 2 0 (c) 100 0 (d) 1000 0
217. The speCies having pyramidal shape is : [I.I.T. 2010]
210. The correct statement with regard to Hi and Hz is :
rCE.T. (Karnataka) 2009] (a) S02 0 (b) Br.F3 o
(a) both Hi and Hz do not exist .. 0 (c) SiOj- 0 (d) OSF2 0
(b) Hz is more stable than Hi 0
·218. In which of the following pairs ot
molecules/ions, the
central atoms have. sp2-hybridizationy -""-.
(c) Hi is more stable than Hz 0
rCB.S.E. (P.M.TJ Prel. 20101
(d) both Hi and Hz are equally shi.ble 0
146 , G.R.B. Inorganic Chemistry for Competitions
z
(a) NO and NH3 0 (b) BF3 and NO z 0 227. N z and O 2 are converted to monopositive cations N and z
(c) NH2: and HzO 0 (d) BF3 illld NH z 0 O2 respectively.
+..
Which
-
is incorrect? [P.E.T. (Kerala)
.
2010J
219. Which one of the following species does not exist under (a) In N z, the N-N bond is weakened 0
normal conditions? [CB.S.E. (P.M.T.) PreL2010] (b) In O2, the bond order increases 0
(a) Be; 0 (b) Bez 0 (d In O 2, the paramagnetism decreases 0
'(c) ~ 0 (d) Liz 0 z
(d) N becomes diamagnetic 0
220. In which one of the following species the central atom has z
(e) Both O 2 andO are paramagnetic
[Hint : M.O. configuration of N2 :
0 '
the type of hybridization which is not the same as that in
the other three? [CB.S.E. (P.M.T.) Prel. 2010} (cr1d«nd(cr2s)2(cr2d(n2Px)2(n2py)2(cr2Pz)2 , B.O. =: 10; 4 = 3
(a) SF 4 0 (b) 13' 0
(c) SbCl s .
0 (d) PCls 0 M.O. configuration of Ni :
[Hint: In SF4, 5 has d5p3 hybridization (cr1d<cr 15)Z(025)2 (cr 2S)2 (1t2px )2(1t2P. / (cr2pz) I B.O. 9-4
2
In Ii, I has dsp3 hybridization
M.O. configuration of Oz :
In PCls, P has dsp3 hybridization
(cr1s)2(cr ls)z(cr2s)2(cr 2s)2(02pz )z(1t2Px)2 (1t2py )2(ic 2px)1 (1t2py)1
In SbCI; Sb has 5ldZhybridization]
221. The bond order of CO molecule is : [J.E.E (W:B.) 2010] , 10-6
B.O. --=2
(a) 2 0 (b) 2.5 0 2
(c) 3 0 (d) 3.5 0 M.O. configuration of oi:
222. For which element the ,inertness of the electron pair will (cr1s )2(cr Is)2(cr25)2 (cr2S)2( cr2pz)2 (1t2px )2( 1t2py)2 (1t2px) I (1t2p y)O
not be observed? [J.E.E. (W.B.) 2010] 10-5
B.O. =-2-=2.5
(a) Sn 0 (b) Fe 0
(c) Pb 0 (d) In 0 Bond order "" Bond energy "" strength of the bond]
223. Non-zero dipole moment is shown by : 228. A neutral molecule XF3 has a zero dipole moment. The
[J.E.E. (Orissa) 2010] element X is most likely : [P.E.T. (Kerala) 2010J
(a) CCl 4 0 (b) CO z 0 (a) chlorine 0 (b) boron 0
, CI (c) nitrogen 0 (d) carbon 0
(c) HzO 0 (d) CD 0 229. Match the following :
List-I List-II
CI
224. Which of the following has a regular geometry? (Molecule) (Number of lone pairs
[J.E.E. (Orissa) 2010] on central atom) .
(a) CHCl 3 0 (b) SF4 0 (A) NH3 (i) Two
(c) XeF6 0' (d) PC Is 0 (B) H2O.' (iD Three
225. Which of the following is non-existent? (C) XeF 2 (iii) Zero
'lA.M.U. (Engg.) 2010] (D) CH 4 (iv) Four
(a) AIFg- 0 (b) CoFg- ' 0 (v) One
(c) BFg-:- 0 (d) 0 The correct answer is : '[E.A.M.CE.T. (Engg.) 2010]
226. Which of the following statements is false? (A) (B) (e) (D)
[P.E.T. (Kerala) 2010] (a) (v) (i) (iii) (ii) 0
(a) Hz molecule has one sigma bond 0 (b) (iii) (i) (ii) (v) 0
(b) HCI'molecule has one sigma bond 0 (c) (v) (i) (it) (iii) 0
(c) Water molecule has two sigma bonds and two lone pairs (d) (i) (v) (iii) (iv) 0
, 0 F H
(d) Ethylene molecule have five sigma bonds and one pi . I -.. I
[Hint: N -(5- .Xe. ' C
b~ 0 /1"- /"- I • /1"-
(e) Acetylene has three pi bonds and three sigma bondsD HHH H H F HHH
Set II : This s~ contains questions with two or more correct answers.

230. Which of the kllowing have identical bond order? I' (d cis-3-hexene' 0
[l.LT. 1992) (d) 2, 2, 3, 3-tetramethylbutane 0
(a) CN- 0 (b) 02: 0 I 232, Species having same bond order are:
(c) NO+ 0 (d) CN+ 0 ,i (a) N2 0 (b) Ni 0
231. The molecules that will have dipole moment: [I.I.T.1992J (c) N2: 0 (d) N~- 0
(a) 2, 2-dimythylpropane 0 iI' 233. Which of the following species are paramagnetic?
(b) trans-2-pentene 0 (a) 02 0 (b) N~- 0
(c) N z 0 (d) O~- 0
234. Molecules having distorted geometry are: 242. Which of the following molecules have a bond angle smaller
(a) H 20 0 (b) NH3 d than tetrahedral bond?
(c) N3H 0 (d) XeF 2 0 (a) NH! o
235. The linear struel:u!e is assumed by: [I.I.T. 1991] . (c) NH3 o
(a) SnCl2 0 (b) NCO- 0 243. Identify the species which are non-planar :.
(c) NO; 0 (d) CS2 0 (a) tHj. 0 (b) NH! 0
236. Which of the following hybridization results in non-planar (c) BF4 0 (d) C2H2 0
orbitals? . . 244. The nitrogen oxide(s) that contain(s) N-N bond(s) is (are):
(a) sp3 0 (b) dSp2 0 . [I.I.T. 20(9)
(c) Sp2 tJ (d) dsp3 0 (a) N20 0 . (b) N203 0
237. Which' statement(s) is! are correct? (c) N 20 4 0 (d) N 20 S 0
(a) A sigma bond is stronger thann-bond 0 [Hint : N 20 : N' N=O f------7 N==N-O
(b) A sigma bond is weaker than n-bond 0
(c) Hydrogen bonding is weaker than covalent bonding N20 3: ~N_N(°
. . . 0 o
(d) A triple bond is weaker than double bond 0 O~ /,0
N 20 4: ,/~~
238. Which combination of the compounds and their geometry o 0
are correct?' .
245. Molecules with see-saw shape are :
(a) HgCl2"': linear 0 (b) ClF3 V-shaped 0 .(a) XeOF4 0 (b) SF4 0
(d ClF3 - T-shaped 0 (d) IC1 4 - square planar 0
(c) XeOF2 0 (d) Xe02F2 0
239. In the following ease(s), hybridization of the underlined
246. The molecules in which the central atom is sp3d 2 hybridised
atom is affected: . . .
are:
(a) ~05' (solid) dissociates into pa~ and P06 0
(a) XeF4 o (b) XeF6 0
(b) liB reacts with AlH3 forming Li.Alltt 0 (c) SF 6 0 (d) 13' 0
(c) NH3 is protonated 0
247. Which of the following elucidate molecular 6rbital theory
(d) H~2 is heated forming PH3 and H 3P03 0 rightly?
240. sp3 hybridization is present in:
(a) Number of MO'~ are equal to the number of AO's from
(a) SO~- 0 (b) C2H2 0 which they are formed [,
(c) BOr 0 (d) NH! 0
(b) BMO's increase electron density between the nuclei C
241. Which of the following has tetrahedral struel:u!e and the
(c) ABMO's have a region ot zero electron density 0
e~ntral atom is sp3 hybridized?
(d) Number of electrons in BMO's are more than in ABMO's
(a) BF:! 0 (b) IF:! 0
(c) Si~ 0 (d) PF 4 0
o
1. (a) 2. (d) 3. (d 4. (b) 5. (c) 6. (a) 7. (c) 8. (b) 9. (d 10. (a)

11. (d) 12. (b) 13. (d) 14. (d) 15. (c) 16. (b) 17. (d 18. (a) 19. (d) 20. (a)
21. (b) 22. (c) 23. (a) 24. (c) 25. (d) 26. (d) 27. (b) 28. (b) 29. (a) 30. (a)
'31. (a) 32. (b) 33. (d) 34. (b,c) 35. (b) ,36. (a) 37. (a) 38. (b) 39. (c) 40. (b)
41. (a) 42. (b) 43. (d) 44. (c) 45. (d) . 46. (d 47. (a) 48. (a) 49. (a) 50. (b)
51. (e) 52. (d) 53. (a) 54. (b) 55. (d) 56. (b) 57. (c) 58. (c) 59. (b) 60. (d)
61. (b) . 62. (b) 63. (d) 64. (c) 65. (b) 66. (d) 67. (c) 68. (c) 69. (b) .70. (a)
,71. (b) 72. (b) . 73. (c) 74. (d) 75. (a) 76. (c) 77. (d) 78 .. (d) 79. (b) 80. (a)
81. (d) 82. (a) 83. (c) 84. (d) 85. (b) 86. (d) 87. (b) 88.' (b) 89. (c) 90. (b)
91. (d) 92. (d) 93. (d) 94. (b) 95. (d) . 96. (c) 97. (d) 98. (d) 99. (a) 100. (a)
101. (c) 102. (a) 103. (b) 104. (b) 105. (c) 106. (d) 107. (d) 108. (c) 109. (b) 110. (d)
111. (c) 112. (b) 113. (c) 114. (a) 115. (a) 116. (d) 117. (d) . ·11S. (b) 119. (b) 120.. (c)
121. (b) 122. (a) 123. (d) 124. (c) 125. (a) 126. (d) 127. (b) 128. (d) 129. (b) 130. (a)
131. (a) 132. (c) 133. (c) 134. (a) 135. (d) 136. (b) 137. (d) 138. (a) 139. (b) . 140.(d
141. (d) 142. (d) 143. (d) 144. (c) 145. (b) 146. (d) 147. (b) 14S. (b) . 149. (b) 150. (b)
151. (a) 152. (c) 153. (b) 154. (a) " 155. (b) 156. (b) 157. (c) ISS. (a) 159. (b) 160. (c)
161. (d) 162. (d) 163. (d) 164. (a) 165. (c) 166. (c) 167. (a) 16S. (c) 169. (c) 170. (b)
171. (a) 172. (d) 173. (c) 174. (b) 175. (d) 176. (c) 177. (a) 17S. (d) . 179. (c) 180. (c)
181. (d) 182. (a) 183. (b) 184. (d) 185. (c) 186. (c) 187. (d) 18S. (b) . 189. (d) 190. (c)
191. (c) 192. (d) 193. (a) 194. (d) 195. (a) 196. (b) 197. (b) 19S. (a) 199. (e) 200. (d)
201. (a) 202. (c) 203. (a) 204. (a) 205. (c) 206. (b) . 207. (a) 208 .. (c) 209. (c) 210. (c)
211. (d) 212. (c) 213. (a) 214. (b) 215. (a) 216. (c) 217. (d) 218. (b) 219. (b) 220. (c)
221. (c) 222. (b) 223. (c) 224. (a) 225. (d 226. (e) 227. (d) 22S. (b) 229. (c) 230. (a/c)
231. (b,c) 232. (6,c) 233. (a,b) 234. (a,b,c,d) 235. (b,c,d) 236. (a,d) . 237. (a,c) 238. (a,c,d) 239: (a,b) 240, (aid)
241. (a,c,d) 242. (c,d) 243. (b/c) 244. (a,b,c) 245. (b,d) 246. (a,c) 247. (a,b,c)
Chemical Bonding 1'49
~t Objective Questions for liT ASPIRANTS •

1. Which of the following halides has different bond lengths? (d) Hydrogen bonding exists in p-nitrophenol but no
(a) BCl 3 (b) CCl 4 hydrogen ~onding is present in a:-nitrophenQI.,
(c) BeCl 2 (d) PCl 5 [Hint: IntramoleO,uarH-bonding is present in o-ttittophenol
[Hint : Pas has two types of bonds axial and equatorial. These which lowers its boiling point while intermolecular H-
two types of bonds have different bond lengths.] bondjng .is preSent in p-nitrophenol which increases its
boiling point.] .
2. Which among the following has highest boiling point?
(a) H2 (b) He 8. N02 and N 20 4 are two forms of nitrogen dioxide. One exists
(c) Ne (d) Xe in gaseous state while other in liquid state. The nature of
[Hint : Xenon has highest boiling point because it has maximum N02 and, N 20 4 forms are:
van der Waals' forces due to the possession of more ... (a)· both· are paramagnetic
electrons.] (b) both are diamagnetic
3. In which solvent NaCl has maximum solubility? (c) N0 2 is paramagnetic while N 20 4 is diamagnetic
(a) H 20 (b) C 2H sOH . (d) N02 is diamagnetic while N 20 4 is paramagnetic
(c) CH 3COCH3 . (d) C2H::;OC2HS
[Hint : NaCl is an lOmc compound. Solubility of· an ionic IHint : N02 is an odd electron molecule .....--N~ .The dimer,
compound depends on the value of dielectric constant of a 0
the solvent. Higher the value of dielectric constant of the N 20 4t has no ut:lpaired electron.
solvent more is the solubility of the ionic compound. 0, /0
Solvent H20 C2HsOH CH3COCH 3 C2HsOC zHs ,N-N~ ]
Dielectric constant 80 27 21 4.1]
° of 0
4. Which has maximum covalent character? .
(a) NaCI
(c) AICl 3
(b) SiCl4
(d) MgCl 2
[Hint : Polarisation in the molecule increases with increase of
9. The
[:0
(a) -2
formal
N 0: r
charge
is:
the
(~) -1
O"atoms in the ion
charge and decreases in size of the cation when the anion (c) 0 1diy'+
. is same.] . . [Hint: Formal charge = total vidence electrons in free atom
5. If PI and P2 are the two dipole moments in the molecule number of non-bonding electrons
with an angle 9 between them, then the resultant dipole - 1/2 number of bonding electrons
moment will be : 6 - 4 - 1/2x4 = 0 ]
(a) P = pj + p~ + 2P1P2 cos 9 10. Among the following compounds the one that is polar and
(b) P = pj + p~ - 2J11P2 cos 9 has the central atom with sp2 hybridization is :
I
(a) H 2C03 (b) SiF4
(c) 11 = (P1 + p~ + 2P1P2 cos 9) 2"
(c) BF3 (d) HCI02
2 2 .. ! [Hint: H2CO:! is polar asH2CO~~ 2H~ + Coj-. Carbon in
=
(d) P (PI + P2 + 2P1P2 cos 9) 3
CO~- ion is in sp2 hybridized state.]
6. The dipole moment of HBr is 2.6 x 10-30cm and the
interatomic spacing is 1.41 A. The percentage 6f ionic 11. Which of the followl!"!; hydrocarbons has the lowest dipole
character in HBr is : moment?
(a) 10.5 (b) 11.5
(c) 12.5 ' (d) 13.5 (b) CH 3C==CCH 3
. Observed dipole moment. 0
[Hint : % ionic character = Theoretical dipole moment x 1 0 (d) CH2=CH-C==CH
Theoretical dipole moment of a 100% ionic character [Hint : Symmetrical with linear structure will have zero dipcle- .
moment.]
= e x d =(1.6 X 10-190 x (1.41 X 10-10 m)
= 2.256 x 10-'29 ern] 12. C~ is isostructural with :
Ca) HgCl 2 (b) SnCl2
7. The boiling point of p-nitrophenol is higher than that of 0-
nitrophenol because :, . (c) C 2 H 2 (d) N0 2
(a) p-nitrophenol has intermolecular hydrogen bonding. [Hint : The structure of CO2 is linear O=C =0, similarly the
structures of HgCl2 and C]H2 are linear, CI-Hg-Cl;
while o-nilrophenol has intramolecular hydrogen
HC!lEC-H. SnCl2 and NO:! have angular structures.]
bonding.
(b) p-nitrophenol has intramolecular: hydrogen bOnding 13. Which one of the following arrangements of molecules is
while d-nitrophenolhas intermolecular hydrogen correct on the basis of their dipole moments ?
bonding. . ·(a) ·BF3 > NH3 > NF3 (b) BF3 > NF3 > NH3
". ,
(c) -N0 2 group at p-position behaves in a different way (c) NH3 > BF3 > NF3 (d) NH3 > NF3 > BF3
i'hall ~t~:n~ (If n·-r-~'-i'::;~:.
'it.
\.
[Hint : Both NF3 and NH3 have identical sh!'lpe.and·alone pair [Hint : Ethane H3C-CH3 (2sp3carbons);
.of electrons on,nitrogen. The dipole moment of NH3 is. J, J,
'higher than NF3due to different directions of moments . Sp3 sl
of .the N-F and N-H bond. BF3 is. iii symmetrical Ethylene H2C . CH2 (2sp2 carbons)
mole<;ule. It has.zero dipole moment:} . J, J,
sp2 sp2
14,. Lattice energy of BeC03 (I), MgC03 (II) iriid CaC03 (III} is
Acetylene HC==CH (2sp carbons)
ill order: J, J,
(a) 1< II< III (b) I> II > III sp sp
(c) I < III < II (d) II < I < III- 2
. 'hC-::;::sp 2
[Hint : Lattice energy decreases with increase in of the ions. si_c r C-sp
The size of the cations Be2+ < Mg2+ <
. . '
15.. Which Of the following have undistorted octahedral

Benzene
sp2....
,
t
.:::::.C/
~-si
structures? t2
1. SF6 2. PF(; 3. SiFl- 4. XeF6 sp .
Select the correct answer Using the codes given below: .(6 si carbons)
(a) 2,3 and 4 (b) 1,3 and 4 19. The structure of diborane (~~) contains :
(d 1,2 and 3 (d) 1, 2 and 4 (a) four 2C-2e bonds and two 3C-2e bonds
[Hint :XeF6 has distorted octahedral structure. Xenon in XeF6 (b) two 2C-2e bonds and four 3C-;-2e bonds
. undergoes sp3d3 hybridization giving pentagonal bipyra- (c) two 2C-2e bonds and two 3C-2e bonds
mid with one axis is occupied by a lone pair.]
(d) four 2C-2e bonds and four· 3C-2e bonds
16.' Sulphur reacts with chlorine .in 1:2 ratio and forlllS X. [Hint : The structure of B2~ is :
Hydrolysis of X gives a sulphur compound Y. What is the
hybridization state of central atom in the anion of Y?
(a) sp3 (b) sp (c) Sp2 (d) spzd
[Himt : S + 2Cl2 ~SC4; SC4 + 3HzO ~ HZS03 + 4HCl
(X) .(y) Each boron atom is in Sp3 hybrid state. Each boron has
In SO~-, sulphur has sp3 hybridization.] three orbitals associated with one electron each and one
17. Identify the correct sequence of increasing number of empty orbital. Two of orbitals to each boron atom overlap
with hydrogen atoms (terminal) to form normal sigma
It-bonds in the structures of the following molecules :
bonds. Thus; fourbondsare'2C-2e bonds.
(I) H2~06 (II) H 2S03 (III) H 2S20 S Two hydrogen atoms overlap with rest of the four orbitals
(a) I, II, III (b) II, III; I forming two 3C-2e bonds as two empty orbitals are
involved.]
(dIl, I, III (d) If ill, II
20. Molecular shapes of SF4, CF4 and XeF4 are .:
o 0 o (a) the same with 2, 0 and 1 lone pair of electrons
II II II
[iBirit :: H~06 HO~ S - S -OH 41t-bonds i H2~ HO-S (b) the same with 1, 1 and 1 lone pair of electrons
II II I (c) different with 0, 1 and 2 lone..pair of electrons
o 0 OH
o 0 (d) different. with 1, 0 and 2 lone pair of electrons
II' II. . [lIlIiiIit :: The. structures are :
. F.
In-bond; H2Sz0sHO-S-S-OH 31t-bonds
SF4 - sp3d hybridization - trigonal bipyrarnidal
~
·.·~F
18. Match the following lists : F F
List I List II CF4 sp3 hybridization - tetrahedral
F
(A) Ethane 1. . 2 sp carbons
(B) Ethylene 2. 6 sp2 carbons f&F F
(C) Acetylene 3. 2 sl carbons XeF4 sp3d2 hybridization- octahedral
(D) Benzene
The correct answer is:

4. 2 sp2 carbons
5. 1 sp and 1 sp2 carbons F$F]
(A) (B) (C) (D) 21. Which of the following is correct ?
(a) 3 4 1 2 (a) The number of electrons present in the valence shell in
(b) 4 5 3 2 SF6 is 12.
(c) 3 1 2 5 (b) The rates of ionic compounds are very slow.
(d) 2 3 4 5 (c) According to VSEPR, SnCl2 is a linear molecule.
(d) The correct order. of ability to form. ionic compounds
among Na+, Mg2+ ~d Al3+ is Al3+ > Mg2+ > Na +.
22. Which of the following is not isostructural with SiC4? 25. Which of the following is not a correct statement?
(a) pot (b) NHt (c) SCl4 (d) SOi- (a) Every ABs molecule does in fact have square pyramidal
[Hint ; S in SCt. undergoes hybridization. Thus, the molecule structure.
has see-saw structure whereas SiC4 is tetrahedral. (b) Multiple bonds are always shorter than corresponding
:~CI
single bonds.
. (c) The electron deficient molecules act as Lewis acids.
(d) The canonical structures ~ave no real existence.
~Cl [Hint : ABs molecule can be either square pyramidal as IFs or
CI trigonal bipyramid as PCl s.]
23. The electronegativity difference between Nand F is greater 26. Specify the coordination geometry around and hybridization
than that between Nand H, yet the dipole moment of of Nand B atoms in the 1 : 1 com:plex of BF3 and NH3:
. NH3 (1.5 D) is larger than that of NF3 (O.2 D). This is because: (a) N : tetrahedral, Sp3, B : tetrahedral, sp3
(a) in NH3 as well as in NF3, the atomic dipole and bond (b) N : pyramidal, Sp3, B : pyramidal, sp3
dipole are in opposite directions (c) N : pyramidal, Sp3, B : planar, Sp2
(b) in NH3, the atomic dipole and bond dipole are in the (d) N : pyramidal, Sp3, B : tetrahedral, s~
opposite directions whereas in NF3, these are in the [Hint: The lone pair present on nitrogen in ammonia molecule
same direction is donated to boron as. BF3 is an electron deficient molecule
forming a coordinate bond.
(c) in NH3 as well as in NF3' the atomic dipole and bond
dipole· are in the same direction H F
I I
(d) in NH3' the atomic dipole and bond dipole are in the H:"""'N--->B-F
same direction whereas in NF3' these are in the opposite I I
directions H F
Both N and B are in sp3-hybrid state, i.e., two tetrahedral
•• t ··t are joined with each other.]
t N
[Hint; H/+"'H F/ t'F'" 1 27. Identify the correct order of decreasing bond strength in
H F the bonds formed by 2p-2p and 2s--2p overlappirig:
(a) Zs-2s > 2s-2p > 2p-2p .. ~) 2s-2s > 2p-2p > 2s-2p
24. In which of the follOWing molecules are all the bonds not (c) 2p-2p > 2s-2p > 2s-2s (d) 2p-2p > 25-2s > 2s-2p
equal? [Hint : Bond strength depends on the extent of overlapping.
(a) AIF3 (b) NF3 Maximum overlapping occurs in the case of p-orbitals.]
(c) CIF3 (d) BF3 28. The hybridization of I in 1Cl2: is:
[Hint: CI in ClF3 is in sp3d hybridi- (a) sp (b) sp2
zation. The molecule has (c) Sp3 (d) dSp2
T-shape structure.] . F . [Hint ~ State of hybridization, H '" 1/2[7 + 2 1 + 0] = 4
or sp3 -hybridized]
1. (d) 2. (d) 3. (a) 4. (b) 5. (c) 6. (b) 7. (a) 8. (c) 9. (c) 10. (a)
11. (b) 12. (a,e) 13. (d) 14. (b) 15. (c) 16. (a) 17. (b) 18. (a) 19. (a) 20. (d)
21. (a) 22. (c) 23. (d) 24. (c) 25. (a) 26. (a) 27. (c) 28. (c)
Matrix Matching Questions for liT A5pirant§

1. Match list-I with List-II: 4. Match. the orbitals in list-II with the hybridization in
List-I Li~t-II List-I and shape in List-III:
(a) Molecule with sp hybrid (p).H-:-C==C-H List-I' 'List-II List-III
ca.rbon (a)sp3d (p) dxy, dyv dzr (u) Octahedral
(b) Allene (q) CH 2=C=CH 2 (b)'sp3d2 (q) dx2 _ y2, dz2 (v) Pentagonal
(c) Electron deficient (r) PCls bipyramidal
(d) Expanded octet (8) BeCl2 (w) Trigonal
2. Match list-I with list-II: bipyramidal
List-I List-II S. Match the molecular species in list-I and their magnetic and
(a) PCls (p) Two axial bonds + tlu'ee lone pairs molecular orbital properties in list-II:
(b) XeF 2 (q) Two axial + two equitorial bonds List-I List-II
(c) SF 4 (r) Two axial + one equitorial bonds (a) O2 (p) Bond order = 2
(d) CIF3 (s) Threeequitorial + two axial bonds (b) N2 (q) Diamagnetic
3. Match the molecular species in List-I with their shape in (c) H2 (r) Bond order:;; 3
list-II: (d) O~- (s) Paramagnetic
List-I List-II
(a) Linear shape (p)CS 2 .
(b) sp hybridization (q) XeF2
(c) sp3d hybridization (r) C 2H 2
(d) CO2 is isostructural to (s) NCO-
1. (a-p, q) (b-q) (c-s) (d-r) 4. (a-r-w) (b-q-u) (c-p-v)

2. (a-s) (b-p) (c-<) (d-r) S. (a-p. 's) (b-q. r) (c-<) (d-<)
3. (a-q, r, p, s) (b-p" r~~) (c-q) (d-p)

The questions given below consist of an Assertion (A) and 4. (A) Nitrogen is inreactive at room temperature but becomes
Reason (R). Use the following key to choose the.correct answer. reactive at elevated temperature (on heating or in the
(a) If both (A) and (R) .are correct and (R) is the correct presence of catalysts).
explanation of the (A). (R) In nitrogen molecule, there is extensive delocalization
(b) If both (A) and (R) are correct but (R) is not the correct of electrons. IA.I.LM,S. 1996J
explanation of the (A). S. (A) Water is a good solvent for ionic compounds but poor
(c) If (A) is correct but (R) is incorrect. one for covalent compounds.
(d) If both (A) and (R) are incorrect. (R) Hydration' energy of ions releases sufficient energy to
1. (A) Bond order in a molecule can assume any value, positive overcome lattice energy and break hydrogen bonds in
or negative, integral or fractional including zero. water while covalent bonded compounds interact so
(R) It depends upon the number of electrons in the bonding weakly that even van der Waals' forces between mole-
and antibonding orbitals. (A.l.LM.s. 1994) cules of covalent compounds cannot be broken.
2. (A) Ionic compounds tend to· be non-volatile. lA.I.I.M.S. 19%]
(R) Intermolecular forces in these compounds are weak. 6. (A) Na2S04 is soluble in water while BaS04 is insoluble.
fA.tLM.S. 19941 (R) Lattice energy of BaS04 exceeds its hydration energy.
3. (A) The atoms in a covalent mcilecule are said to share [A.I.l.M.S.1997]
electrons, yet some covalent molecules are polar. 7. (A) NO'3 is planar while NH3 is pyramidal.
(R) In polar covalent molecule, the shared electrons spend (R) N in N03 is sp2 and in NH3 it is sp3 hybridized.
more time on the'j!verage near one of the atoms. [A.U.M.S. 1997]
""'' ' . ..;.~. "~. ~...... :~\ . " "
/.:- - " [A.I.I.M.S. 19%}

8. (A) N2 and NO+ both are diamagnetic substances. 13. (A) The dipole moment helps to predict whether molecule
(R) NO+ is isoelectronic with N 2. [A.I.LM.S. 1997] is polar or non-polar.
9; (A) The bond angle of PBr3 is greater than PH3 but the bond (R) The dipole moment helps to predict the geometry of
angle of NBr3 is less than NH3. molecules. IA.LI.M.S. 1999]
(R) Electronegativity of phosphorus atom is less than that 14. (A) The 0-0 bond length in H20z is shorter than that of OzFz.
of nitrogen. [A.I.I.M.S. 1997] (R) H20 Z is an ionic compound. [A.I.I.M.S. 2003]
+ 15. (A) All F-S-F angles in SF4 are greater than 90° but less
10. (A) The electronic structure of 0 3 is
/0\ than 180°.
o 0- (R) The lone pair-bond repulsion is weaker than bond pair-
(R) /~ Structure is not allowed because octet around bond repulsion. [A.I.I.M.S. 2004]
16, (A) B2 molecule is diamagnetic.
o 0
(R) The highest occupied molecular orbital is of G type.
'0' cannot be expanded. [I.I.T. 1998]
[Hint : Tn B2, total number of electrons are 10 (cr1s)2«.hS)2
11. (A) LiO is predominantly a covalent compound. (0'25)2«hs)2(1t2p/(1t2Pi -paramagnetic. The highest
(R) Electronegativity difference between 'Li' and '0' is too occupied orbital is of 1! type.]
small. [I.I.T. 1998] 17. (A) The S-S-5 bond angle in 58 molecule is 105°.
12. (A) Bond order can assume any value including zero. (R) 58 has V-shape. fA.I.I.M.S. 2008]
(R) Higher the bond order, shorter is the bond length and 18. (A) Fluorine molecule has bond order one.
greater is the bond energy. [A.I.LM.S. 1999] (R) The number of electrons in antibonding molecular
orbitals is two less than in bonding molecular orbitals.
[A.I.I.M.S. 2008]
1. (a) 2. (c) 3. (a) 4. (d 5. (a) 6. (a) 7. (a) 8. (a) 9. (b) 10. (b)
11. (c) 12. (b) 13. (a) 14. (d) 15. (c) 16. (d) 17. (c) 18. (a)
11111111 : , ,
THOUGHT TYPE QUESTIONS ~ 11111111 . ,
THOUGHT 1 1. Considering BeCl21 MgCI2, CaCl2 and BaClz, predict which

When anions and cations approach each other, the valence of the following statements is true?
shell of anions are pulled towards cation nucleus and thus, (a) Be02 is least ionic out' of the given chlorides
shape of anion is deformed. The phenomenon of deformation (b) Covalent character increases as the atomic number of
of anion by a cation is known as polarization and the ability the metal atom increases
0
of the cation to polarize the anion is called as polarizing (c) BeCl2 has the highest melting point among the given
power of cation. Due to polarization, sharing of electrons chlorides
occurs between two ions to some extent and the bond shows (d) All are highly ionic compounds
some covalent character. 2. In which of the halides, there is maximum polarization?
The magnitude of polarization depends upon a number (a) AIF3 (b) AICl3
of factors. These factors were suggested by Pajan and are (c) A1Br3 (d) A1I3
knownas Pajan's rules.
3. Which is most covalent in nature? 00
(i) Greater is the polarization in a molecule, more is 0
(a) NaCl (' MgCl 2

covalent character. .
(c) AICl3 (d) CaCl 2
(ii) As the charge on cation increases, its tendency to
polarize the anion increases. 4. Non-aqueous solvent like ether is added to the mixture of
(iii) As the size of the cation decreases or size of the anion LiCl, NaCl and KCI. Which will be extracted into ether?
increases, the polarization increases. (a) NaCI (b) LiCI
(iv) ,The cations with 18 electrons in the outermost shell (cJ KCI (d) None
bring greater polarization of the anion than those 5. Which has the minimum mel~g point?
with inert gas configuration even both the cations (a) CaF2 (b) CaCl 2
have same size and same charge. (c) CaBr2 (d) CaI2
154 G .RB. Inorganic Chemistry for Competitions
m-dichlorobenzene (III) and p-dichlorobenzene(IV) :

(a) IV < I < II < III (b) I <IV < II < III
Covalent molecules formed by heteroatoms bound to (c) IV < 1< m < n (d) IV < II < I < III
have some ionic character. The ionic character is due to 5. The dipole moment of NF3 is very much less that of NH3
shifting of the electron pair towards A or B in the molecule because:
AB. Hence, atoms acquit:e small and equal cHarge but (a) number of lone pairs in NF3 is much greater than in
opposite in sign. Such a bond which has some ionic. NH3
character is described as polar covalent bond. Polar covalent (b) unshared electron pair is not present in NF3 as in NH3
molecules can eXhibit dipole moment. Dipole moment is
equal to the product of charge separation, q and the bond (c) both have different shapes
length, d for the bond. The unit of dipole moment is Debye. (d) of different directions of moments of N-H and
One Debye is equalto 10-18 esu cm. N-F bonds
Dipole moment is a vector quantity. It has both magni- 6. A covalent molecule, x-y, is found to have a dipole moment
tude and direction. Hence, dipole moment of molecules of 1.5 x 10-29 em and a bond length 150 pm. The percentage
depends· upon the relative orientation of the bond dipoles, of ionic character of the bond will be:
(a) 50% (b) 62.5%
but not on the polarity of bonds alone. A .symmetrical
. (c) 75% (d) 90%
structure shows zero dipole moment. Thus, dipole moments
help to predict the geometry of the molecules. Dipole moment [Hint : Jiail = 1.602 X 1O-19C x 150 X 10-12 m 2,,4 x 10-29 cm
29
values can be used to distinguish between cis- and trans- Jlobs = 1.5 X 10-
29
isomers; ortho-, meta- and para-forms of a substance, etc. The % ionic character = 1.5 x 10- x 100 62.51
percentage of ionic character of a bond can be calculated by 2.4 x 10-29
the application of the following formula: THOUGHT 3
% ionic character According to the concept of resonance, whenever a single
_ Experimentalvalueofdipolemoment 100 Lewis structure cannot describe a molecule accurately, a
- Theoretical value of dipole moment x number of structures with almost same energy and similar
1. Which of the following compounds have zero dipole
positions of nuclei, bonding and non-bonding pairs of
moments?
electrons are taken as canonical structures of the resonance
hybrid which describes the molecule accurately. In general,
CI Cl
the reson(lllce stabilizes the molecule as the energy of
~
CI resonance hybrid is less than the energy of any single
(a)
C1'©r (b) canonical structure and resonance averages the bond
characteristics as a whole. Actually resonance hybrid does
Cl not oscillate between the canonical forms but it is a definite
CI Cl form and has a definite structure which can.not be written
~CI ~.
on paper. The contributing structures should be such that
negative charge resides on more electronegative and positive
(c) (d)
charge on the electropositive. Like charges should not reside
c l M cl on atoms close together in the canonical forms.
CI As a result of resonance, the bond order changes in many
[Hint; Symmetrical· forms have zero dipole moments.]· molecules or ions.
2. Which are non-polar molecules? Total number of bonds between two atoms
(a) XeF4 (b) BF3 in all the structures
(c) NH3 (d) H 20 Bond order Total number of resonating structures
3. A ruatomic molecule has a dipole moment of 1.2D. If the
Formal charges on atoms in the molecule helps in selecting
bond length is 1.0 x 10-8 em, what fraction of charge does·
exist on each atom? . .
most. favourable canonical form to the hybrid form.
1. Consider the following statements about the resonating
(a) 0.1 (b) 0.2
structures of benzene.
(c) 0.25 (d) 0.3
18
[HiI\t .: Charge = Dipole moment 1.2 x 10- = 1.2 x 1O-10esu
Bond length 1.0 x 10-8
1.2 x 10-10
Fraction of electronic charge = 4.8 x 10-10 0.25] Kekule's Dewar's
4. Arrange the following compounds in increasing order of The correct statement(s) is/are:
dipole moments, toluene 0), o-dichlorobenzene (II), (a) Two Kekule's structures. contribute 80% while
remaining three Dewar's structures 20% only,
Chemical Bonding , " 155
(b) Because of the resonance, all C-C bonds in benzene interference giving molecular orbitals; i.e., two atomic orbitals
become identicaL overlap to form two molecular orbitals, one of which lies at
(c) Resonance decreases the bond length of C-C single a lower energy level (bonding molecular orbital) than the
bond and increases the bond length of C=C bond. other at higher energy level (antibonding molecular orbital).
(d) Benzene becomes less stable and more reactive due to Each mol@cular orbital can hold one' or two electrons in
resonance. accordanc;e. with Pauli's exclusion principle and Hund's
2. The bond order of C-O bond for CO~- ion is: rule of maximum multiplicity. For molecules upto N:u the
(a) 1.25 (b) 1.33 order of filling of orbitals is:
(c) 1.5 (d) 1.0 ... ... ' ' "
?(ls), a,:ls),a(2s), (;(2s), 1t(2px) = 1t(2py), a(2pz), n(2px)
[Hint : The resonance structures of carbonate ion are : = n(2py), a(2p~) , . ,
and for molecules after N2J the order (}f filling is:
a(1s), o.(1s), a(2s), 0.(25), a(2pz), 1t(2px) = 1t~2py), 1t(2px)
== n(2py), O(2pz) ,
Bond order = ~ [bonding electrons - antibonding electrons1

2+1+1
B.O.' = - 3 - 1.331
Bond order gives the following information:
(i)If bond order is greater than zero, the molecule/ion
3. Which is not true for resonan~? exists otherwise not '
\a) Identical bonding", (ii) Higher the bond order, higher is the bond dissociation
(b) Identical arrangement of atoms energy.
(c) Same number of paired, electrons
(iii) Higher the bond order, greater is the bond stability.
(d) Structure with nearly same energies
4., The, most unlikely representation of resonance structure of (iv) Higher the bond order, shorter is the bond length.
p-rutrophenoxide ion is: 1. The relative stabilities of CN, CN+ and CN are in the order
of:
-O"N~~O -0 "N+/O- (a) CN > CW > CN- (b) CN- > CN > CN+
(c) CN- > CN+ > CN (d) CN+, > CN > CN-
(a)
¢
0-
(b)
¢ 0
2.
CN+=S'--4=2]
2
9-4
[Hint ,; Bond order: CN = -2- = 2.5, CN- 3,
Molecular orbital theory is preferred over valence bond

theory as it can explain:
(a) bond strength
O~N+~O (b) geometry of molecule
-O"N+~O (d the magnetic nature of the molecule
(c)
¢
0-
( c~)
Q 0
3.
(d) none of the above
~- will have:
,(a) ,bond order
(b) bond o~der
(d bond order
lower than O 2
higher than Oz
equal to 02
5. Which resonance structure of N20 is more favourable than (d) bond order equal to H2
others?' 4. Which of the following molecule is paramagnetic?
+ •• + (a) F2 (b) 02
(a) -N=N 0 (b) :N=N-Q:
(d N2 (d) H2
..+ +'
(d 2-:N-N 0: (d) None 5. In which set of molecules all the'species are paramagnetic?
(a) B2/ Oz, N z (b) Hz, Oz, NO
tH:int:: Negative charge should be present on more electro-
(c) Bz, F2, Oz (d) B2' O2,
, negative atom.]
6. Which one of the following statements is correct?
(a) Bonding molecular orbital is lowered by' the same,
Molecular orbital theory is based on the principle of amount of energy' by which antibonding molecular
linear combination of atortrlc orbitals. According to this orbital is raised.
approach when atomic orbitals of the atoms come closer, they (b) Bonding molecular orbital is lowered by greater amount
undergo constructive interference as well as destructive of energy than the amount by which antibonding
molecular orbital is raised.
(c) Bonding molecular orbital is lowered by lesser amount (d) Any Qne of the above is possible.
of energy than the amount by which antibonding
molecular orbital is raised.
Thought 1 1. (a) 2. (d) 3. (e) 4. (b) 5. (d)

Thought 2 1. (b,d) 2. (a,b) 3 •. (e) 4. (e) 5. Cd) 6. (b)
Thought 3 1. (a,b,e) 2. (b) 3. (a) 4. (e) 5. (b)
Thought 4 1. (d) 2. (c) 3. (a,d) 4. (I;» 5. (b) 6. (c)
The answer to each of the following questions is a sillgle 7. Dipole moment of certain diatomic molecule X-Y is
digit integer, /'allging from 0 to 9. 0.38 D. H the X-Y distance is 158 pm, the percentage of
1. What is the % ionic character in HI? Given electronegativity electronic charge developed on X-atom is :
of H = 2 and I = 2.5. 8. How many electrons are present in antibonding MO's in
2. The number of orbitals involved in the hybridisation of eN+ ion?
XeF2 is: 9. How many carbon atoms of l,3-butadiene have sp2-hybrid
3. The formal charge on the. carbon atom in the carbonate .ion state? .
is: 10. The number of pi bonds present in tetracyanoethylene
4. In SF4, S atom has dspx hybridisation. What is the value of moleCUle is :
x? 11. The number of lone pairs on Xe in XeF6 is :
5. How many total bonds (sigma and pi bonds) are present in 12. The maximum number of hydrogen bonds that a molecule
ozone molecule? of water can have is :
6. A complex ion [Fe(H20)6]2+. is found to be paramagnetic.
Its magnetic moment is 4.89 BM. How many unpaired
electrons are present?
1. (7) Percentage ionic character = [16(XA Xs) +3.5 (XA-Xs)2j 5. (3) 2 sigma and one pi bonds
= 16 )( 0.4 + 3.5 x (0.4)2 = 7
6. (4) Magnetic moment = In(n +2) = 4.89 8M
2. (5) H '" 1/2 (V + M -C + AI
where H '" N\lII'Iber of orbitals involved in hybridisation ;;:.J4 x6 = 4.89 8M
V = Valence electrons of central atom 0'" = Ill<)' - 0.381<'.10-:: 2.4 x 10-11
.7. (5)
M ;;: Number of monovalent atoms linked with ~x-y . 158 x 10
central atom . 24xlO-11
% electron charge =' 10 X 100 = 5
, C = Charge on the cation 4.8><10 .'
A = Charge on the anion 8. (4) Configuration of CN+ ion is I<K(G2s)2(o2s)2(1t2Px)2(1t2py)2
H = 1/2[8 + 2 0 + 01 5 9. (4) CH 2 CH - CH = CH2.
3. (0) Formal charge = Valence electrons - lone pair elections All the carbon atoms are sp2. hybridist!d.
1/2 bonding electron!; 10. (9) The structure of tetracyanoethylene is :
o 4 0 1/2 x 8 0
II
C
-0/ "0-
4. (3) H = 1/2 [V + M - C + AJ 11. (1) XeF6.
;;: Number of orbitals involved The molec1,lle haspentagonai bipyramidal geometry with one
= 1/2 [6 + 4- 0 + OJ .5 apexQccupi~d by a lone pair, .
dspx = 1 + 1 + 3.::;: 5
Contents:
3~1 Introduction
:3.2 Arrhenius Concept
3.3 Bronsted-Lowry Concept
CHAPTER 3
3.4 Lewis Concept
3.5 The Lux-Flood. Concept
3.6 Usanovich Concept
.Acids and Bases
3.7 Hard and Soft Acids and Bases
3.8 . Some General Trends m: Acidic
and Basic Properties
~,IINTRODUCTION An acid is a compound which contains one or more

hydrogeilatoms replaceable partially or completely by
Acids and .bases were first recognised as specific clas~es of
a inetal or a positive radi,cal to produce a salt.
compounds because ofthedistinctiv~ properties exhibited by their
Several theories (conceptS) have been proposed to
aqueous solutions. The properties of acids and bases are listed
explain the behaviour of acids and bases on the basis of
below:
structure and composition, but no single theory explains
Propelties ofands.. Properties of bases the overall behaviour of acids and bases; Each of the
.
theOry or concept can be applied with advantage in
1. Sour* intast~. Bitterness in. taste.
appropriate circumstances. In a given situation, the
2. Change colours of indicators, Change coloUrs of indicators,e.g.,
e.g., litmus turns from blue to litmus tunis from red to blue; chemist uses that concept which .best suits his purpose.
red; phenolphthalein turns phenolphthalein turns from The most popular theories or concepts are described
from .pink to colourless. colourless to pink. in this chapter. .
3. Elec!:r0lytic conductivity in Electrolytic conductivity in
aqueous solution. aqueous solution. 3:.
e._.,} .. ;;~
ARRHENIUS CONCEPT
4. React with active metals to give .Soapy touch and slippery in
hydrogen; nature. This concept was presented in 1887. According to this
5. Acidic properties disappear Basic properties disappear when concept all substances which give H+ ions when
when react with bases react with acids (Neutralisation). dissolved in water are called acids while those which
(Neutralisation). ionise in water to furnish OH- ions are called bases.
6. Decon:tpose carbonates,
Warer
In 1783, Lavoisier suggested that acids(lte the oxy"'Compounds. HA H+ + A-
Acids
of non-metals. This view was soon reject~d by Davy as a result
of his studies on muriatic acid (hydrochloric acid). The search (or
a common factor in acids came to light when the German chemist, BOH B+·+ OH-
Liebig, proposed the following definition of an acid in 1830. ·Base
* The
word acid isa Latin word-acidus meaning sour.
Wamrng: The chemicals in the laboratory should never be tasted as these can be poisonous and prove fatal sometimes.
Water H20 ~ H+ + OH-

HCI H+ + Cl- H+ + H 20 H30+
Acid
H 20 + H 20 ~ H30+ +' OH-
Water
H2SO4 ~ 2H+ + SO~ Water is also neutral in nature, i.e., H30+ and OH- ion
Acid
concentrations are equal.
NaOH [HgO+] =>'[9]-n
Base
The substances which intrease the concentration of
Water
NH40H ~ NHt + OH- H 30+ions in water act as acids while those which increase
Base the concentration of OH- ions act as bases. S02 increases
The reaction between an acid and a base is termed neutra- H30+ ion concentration. Hence, it is an acid. .
lisation, i.e., neutralisation involves the reaction between H+
Water
and OH- ions to form water.
. ---',; -,- " -," .• - ,:::;' :;' '-':'. .: ~ 'J., S02 + H 20 ~ H 2SOg ~ HgO+ + HS0 3
NaOH>* JiG ~"'>i,N~Cl .t:H20 (Neutralisation)
$
Base 'ACid Salt Water Similarly, NH3 behaves as a base as it increases OH- ion
OH- + H+ ~ H2O concentra tion.
Actually free H+ ions do not exist in water. They combine . NH3 + H 20 ~ NH40H, > NHt + O~-"
with solvent molecules, i.e., hydrated to form hydronium or
hydroxinium (H30+) ions. BasiCity or Protoclty of an"Acid
H+ + H 20 ~ H30+ (aq) The basicity of an acid is the number of hydrogen ions
Thus, the ionisation of acids in aqueous solutions should which can be furnished by one molecUle oftlte acid upon
be represented as: dissociation. An acid liberating 1, 2 or3 H+ ion,S are respec-
HCl + H 20 ~ H30+ (aq) + Cnaq) tively known as monobasic, dibasic and tribasic (monoprotic,
H 2SO4 + 2H 20 ~ 2H30+ (aq) + SO~-(aq) diprotic and triprotic). Polyprotic acids usually dissociate in
Evidence for Arrhenius theory comes from the heat of steps.
reaction, MIo,for the neutralisation of a strbngacld by a
Acid Dissociation. Basicity
strong· base. This neutralisation is essentially the reaction of
H30+(aq) with OH-(aq) and shoUld, therefore, always give tIO HO ~ Ii+ + 0- . l[Monoprotic]
the same MIo per mole of water formed. Experimentally, it is HN"03 IiN03 ~ H+. + .N~3 . lrMonQprotic]
found that all neutralisation between strong acids and strong CH3COOH CH3COOH ~ H+ + CH3COO- 1 [Monoprotic] ..
. bases have the same MIo (-55.90 kJ per mole of H+) .. H2S04 ~ H+ + HS04'
. HS04' ~. H+ + s6l- .
~~ , Limitations of Arrhenius .Concept
H2S04 ~ 2H+ + so.i- 2 [Diprotic]
(i) It is applicableonly to <'lqueo~ solutions. For the acidic
or basic properties, the presence of water is. absolutely H3P04 ~ H+ + HiP04'
necessary. Dry HCl shall not act as an acid., . ' H 2P04' ~ H+ + HPO~~
(ii) The concept does not explain acidic or basic properties HPO~:- ~H+ + poi':'.
of acids and bases in non-aqueous solvents respectivf!ly.
HiiP0 4 ~ 3H+ + pot 3lTriptoticl
(iii) It fails to explain the acidic nature of the non~protic
compounds such as S02, N02, CO:h P20s, etc.; which do not Hio3 ~ H+ + H zP03"
have hydrogen ror furnishing H+iohs. '.:' ·'HzPO'3 ~ H+,+HP01- ,
(iv) It fails to' explain the:basicnature of compounds 'like H3P03 ~ 2H+ + HP01- 2.[Diprptic]
NH 3, Na2C03! etc., which do not ha:veOH in the molecule to
furnish OH- ions. H3PO~ :;;:=: H+ + 'H2POi . 1 [M6noprotiC]
(v) It fails to explain the acidic nature of certain salts such . It is clear, from the above table that- baSiCity of an acid is
as AICl3 in aqueous solution. not necessarily the nUmber of hydrogen atoms present in one
molecule of the acid but the number of hydrogen ions
Modified Arrhenius Concept furnished by one molecule. An acid is generally termed as
The modified concept rectifies most of the limitations. polybasic or polyprotic when a moleCule of it produces more
Water is a weak electrolyte and ionises to a very small extent. than one H+ ion in aqueous solution.
Acids and Bases 159
'~C' Acidity or Hydroxicity of a Base CH3COOH + H 20 ~ H30+ + CH3COO-

The acidity or hydroxicity of a ,base is the number of . CO2 + 2H20 ~ H30+ + HC03"
hydroxyl ions produced from one molecule of the base on NH.! + H 20 ~ H30+ + NH3
dissociation. A base liberating 1, 2 or 3 OH- ions are HS04 + H 20 -;:-:--"" H30+ :+- SO~
respectively known as monoacidic or monohydroxic, diacidic Consider the reaction,
or dihydroxic, triacidic or trihydroxic. Sodium hydroxide NH3 + H 20 ~ NHt + OH-
(NaOH), ammonium hydroxide (NH40H), potassium
In this reaction, water acts as an acid as it donates a
hydroxide (KOH) are monoacidic or monohydroxic bases
proton to NH3 molecule and NH3 behaves as a base as it
while calcium hydroxide [Ca(OHh]' barium hydroxide
accepts a proton. Some other examples are:
[Ba(OHh] are diacidic or dihydroxic bases.
OH- + H+ ~ H29
[Acidity may also be considered as the number of H+ ions
that can be accepted by one molecule of the base.] CN- + H 20 ~ HCN + OH-
N02: + H 20 ~ HN0 2 + OH-
f,:~' Strength of Acids and Bases It is evident from above examples that H 20 can act
The strength of an acid or a base in Arrhenius concept is both as an acid and a base~ H 20 is thus regarded as
based on the extent of ionisation or the equilibrium constant. amphiprotic.
The equilibrium constant, Ka for the acid, HX, is : -H+ +H+
H 20 ~ OH- H 20 ~ H30 +
[H+][X-] Acid Base
Ka = ' [HX]
NH3 and CH3COOH also act as amphiprotic.
The equilibrium constant, Kb for the acid, BOH, is : +H+
, [B+] [OH-] NH3 ...,........::. NH.!
Kb= " [BOH] Base
The acids which are highly ionised in aqueous solutions, When an acid loses a proton, the residual part of it has a
i.e., giving large number of hydrogen ions are known as tendency to regain a proton. Therefore, it behaves as a ba:se.
strong acids. The value of Ka for strong acids is higher than Acid ~ H+ + Base
0.1. HCI04, HN03, H 2SO4, HCl, etc., are very strong acids. The acid and base which differ by a proton are known to
The value of Ka is very small for weak acids such as form a conjugate pair. Consider the following reaction:
CH3COOH~ H 3P03, H 2C03, H 3B03, etc. For example, Ka value
CH3COOH + H 20 -;:-:--"" H30+ + CH3COO-
of CH3COOH is 1.8 x lO-s at 252C. In other words, in the
It involves two conjugate pairs. The acid-base pairs are :
case of weak acid, the ionisation is only slight and the major
~H+ +H+
part remains as undissociated molecules. CH3COOH ~ CH3COO- H 20 ~ H 30+'
The bases which are highly dissociated in aqueous solu- Acid +H+ Base Base -H+ Acid
tion to produce large number of OH- ions are called strong
If in the above reaction, the acid, CH3COOH is labelled
alkalies. The value of Kb for strong alkalies is higher than
acid r and its conjugate base, CH3COO- as basel and the H 20
0.1. NaOH, KOH, Ba(OH)2, etc., are strong bases. The value
is labelled as basen and its conjugate acid, H30+ as acid u,
of Kb is low for weak bases such as NH40H, Al(OHh,
the reaction can be written as :
Fe(OH)3, etc.
Acid r + Baseu ~ Baser + Acid u
3.1 BRONSTED-LOWRY CONCEPT Thus, any acid-base reaction involves two conjugate pairs,
i.e., when acid reacts with a base, another acid and base is
The ·concept was proposed independently by Bronsted and formed. Some more examples are given below:
Lowry in 1923. According to this concept acids are the
Acid r + Basen ~ Acid u + Baser
species capable of donating the proton in a reaction while
H 20 + NH3 ~ NHt + OH-
bases are the species capable of accepting the proton in a
HCN + H 20 ...,........::. H30+ + CN-
reaction, i.e., acids are proton donors (protogenic) and bases
are proton acceptors (protophilic). Consider the reaction, NH3 + NH3 ~ NHt + NH2:
H 20 + H 20 ~ H30+ + OH-
HCl + H 20 ~ H30+ + Cl-
HCl + NH3 ~ NHt + Cl-
In this reaction, HCl acts as an acid because it donates a BF + CH3COOH ~ CH3COOHi + F
proton to the water molecule. Water, on the other hand, HC03" + H20 ~ H30+ + CO~-
behaves as a base by accepting a proton from an acid. Some HN03 + N2H4 ~ N2HS + N03"
other examples are: HF + HN03 ~ H 2NOt + F-
[Fe(H20)6]3+ + H 20 ~. H30+ + [Fe(H20)s(OH)f+
Thus, every acid has its conjugate base and every base has Strength of Acids and Bases
its conjugate acid. Some commonly occurring conjugate acid-
base pairs are .listed below : . The strength of an acid depends upon its tendency to lose
its proton and the strength of the base depends upon its
Acid Conjugate base Acid Conjugate base
tendency to gain the proton.Ka, the equilibrium constant, of
HN03 N0 3 H 2S0 4 HS04 the following reaction gives a quantitative measure of the
HCI cr HS0 4 SO~- strength of the add,
HBr Br- H 2C03 HC0 3
HA + H 20 ~. H30+ + A-
H20 OH- HC03 coj-
NH4 NH3 H 2S HS-
. [H3 0 +][A-]
CH3COOH CH3COO- HS- Sz-
Ka = [HA]
HCN CN- H 3P04 H2P04 Larger the value of Ka indicates that the add is stronger .
NH3 NHi HzPO.i HPO,i- in nature.
H3P02 H 2P0Z: HPO~- PO~- Similarly, Kb of the following reaction. gives the
It is clear from the given table that Bronsted-Lowry acids quantitative measure of the strength of the base.
and bases can be molecular, cationic or anionic as listed in B. + H 20 ~ BH++ OH-
the following table:
K [BH+][OH-]
Type Arid Base b [B]
Molecular HCl04, HN03, H 3P04, H ZS04, NH3t N2H4t PH3,
Larger the value of Kb indicates that the base is stronger
CH3COOH, HCl, H 20 amines alcohols.
t
in nature. .
Cationic NHt N 2H S' PHt [Fe(H20 )50Hf+,
[Fe(H20)6]3+, Na +, Ba 2+ [Al(H20 )sOH]2+ It is further observed that strong acids have weak
Anionic HC0 3, HS0 4, HS0 3, CC Br-, CN-,NHi, conjugate bases while weak adds have strong conjugate
. HS-, H zP04: I C03,2- 50 2- OH-
4,
bases .
There is an advantage of Bronsted-Lowry concept that HCl

Strong acid Weak base Weak add Strong base
besides water any other solvent, which has the tendency to
accept. or lose a proton may decide the acidic or basic Acid-Base Chart Containing Some Common
behaviour of the dissolved substance in that· solvent. Conjugate Acid-Base Pairs
Moreover, it can be said· that the term acid or base is .
Conjugate
comparative. A substance may act as an acid in one solvent Acid Ka pKa
base
while it behaves as a base in other solvent. Acetic acid acts
as an acid in water but behaves as a base in HF. HI r 1011 -11
1010
CH3COC)H +H20 .,......2. H30+. + CH3C(XT HCI04
HBr
CI04
Br- 1 ()9
-10
-9
. (Acid) (Base) (Acid) (Base) . <.;.
CH3COOH + HF CH3COOHi + F- HCl cr 107 -7

(Base) . (Acid) (Add) (Base) H 2SO4 HS04 10 2 -2
H30 + H 2O 1 0.0
On the basis of proton interaction, solvents can be
fo ..s00
H 2S03 HS0 3 1.5 x lO-z 1.81
~
classified into four types :
(i) Protophilic solvents: Solvents which have the ~ HS04 soI- 1.2 x 10-2 1.92
'" u
... .
'lj
7.5 x 10-3
'Uj
tendency to accept protons, e.g., water, alcohol, liquid '0
<IS
H 3P04 H 2P04 <IS 2.12
..0
ammonia, etc. Cl HF F- ""'0 3.5 x 10-4 3.45
(ii) . Protogenic solvents: Solvents which have the ~ (Il
'E0 CH3COOH CH3COO- 1.8 x 10-5 4.7
tendency to donate protons, e.g., water, liquid hydrogen ]
00 H 2S HS- bl) 1.0 x 10-7 7.0
chloride, glacial acetic acid, liquid hydrofluoric acid, etc. .~ .S<Jl
(iii) Amphiprotic : Solvents which have both the NH4 NH3 <IS ·5.6 x 10-10 9.3
tendencies to accept or donate pro.tons, e.g., water, liquid j HCN CW b
.E 4.0 x 10-10 9.4
ammonia, alcohol, etc. H 2O OH- I.O x 10-14 14.0
(iv) Aprotic: Solvents which neither donate nor accept CH30H CH 3O- Very small Large
protons, e.g., benzene, carbon tetrachloride, carbon NH3 NH:2 Very small Large
,I
disulphide, etc.
Note: In order to avoid writing negative powers of 10, Ka or Kb are generally converted into pKa (-]oglo Ka) or pKb HoglO Kb) respectively,
Smaller the value of pKa indicatE)s the stronger adds. .
Acids and Bases 161
The strength of an acid also depends upon the solvent. 502 + 502 ~ 502+ + SO§-
The acidsHCl04, HCI, H2SO4 and HN03 which have nearly Acidj Basen Addu Basej
same strength in water, will be in the order of, Thus, the protonic definition cannot be used to explain
HCI04 > H2S04 > HCl > HN03 the reactions occurring in non-protonic solvents such as
COCI2, 502, N204, etc.
in acetic add, since the proton accepting tendency of acetic
Example 1. Identify the Bronsted acid and its conjugate base
acid is much weaker than water. HCl acts as a stronger acid
in the following:
in NH3, weak acid in CH3COOH, neutral in benzene and a
weak base in HF. (a) POr + H20 ~ HPO~- + OH-
(b) H2Fe(CO)4 + CH30H ~ [HFe(CO)4r + CH30H2
Levelling and Differentiating Effect (c) HN0 3 + H20 ~ H30+ + NOs
Water is a strong base as it has a great tendency to accept (d) NH3 + H2S ~ NHt + HS-
protons from strong acids. Thus, all strong adds such as Solution:
HCl04, HBr, HI, H 2SO4, etc., almost completely react with In (a), H 20 transfers a proton to Por, thus, H 20 is
water and they appear to be equally strong in water. This Bronsted acid and OH- is its conjugate base. In (b), H 2Fe(CO)4
effect of water and other strong bases to level all the strong is an acid as it donates a proton to CH30H. Its conjugate
acids to the same strength is known as levelling effect. base is [HFe(CO)4r. In (c), HN03 is an acid as it donates a
Consequently, no acid significantly stronger than H30+ can proton to H 20. N03" is its conjugat!:' base.
survive in water. So, relative strengths of strong acids cannot
In (d), H 2S is an acid as it transfers a proton to NH3. Its
be determined in water.
conjugate base is HS-.
An analogous limit can be found for bases in water. Any
base B that is strong enough to undergo complete protonation Example 2. A bottle is marked with 'Acid' pH = 5. Whether
by donation from water, leaving OH- ions in solution in the aCid is strong or weak? Explain.
place of every B molecule added, will be levelled. The OH- Solution:
ion is the strongest base that can exist in water because It cannot be predicted on the basis of pH alone whetl1er
anything stronger immediately forms OH- ions by reaction the acid is strong or weak. pH depends on concentration.
with water. Thus, alkali metal amides and methartides cannot
Example 3. (a) Liquid NH3 like water is an amphiprotl
be studied in wat.er because both anions generate OH- ions
quantitatively and are fully protonated to NH3 and CH4. solvent. Write the equation for the autoionisation of NH3'
(b) Aniline is a weak organic base in aqueous solution. Suggest
KNH2 + H 20 ~ K+(aq) + OH-(aq) + NH3(aq) a solvent in which aniline would become a stronger base.
LiCH3 +' H20 ~ Li+(aq) + OI-I:-(aq) + CH 4 (g) Solution:
When strong acids are dissolved in a weak acid or a weak (a) NH3 + NH3 ~ NH~ + NH2
base, all are not equally ionised and their relative strengths (b) Any solvent which has appreciably stronger addic
can be differentiated. It is called differentiating effect. For properties than water would render aniline as a stronger
example, acetic acid instead of water as a solvent can be used base. Acetic acid is one such solvent.
for the grading of strong acids. This is because of the poor
proton accepting character· of acetic acid. The acidic 3.4)< LEWIS CONCEPT
character of a number of acids when dissolved in glacial
A more general and fundamental concept of acid-base
acetic acid (solvent) has been determined by measuring
behaviour was proposed by G.N. Lewis in 1923 (the same
degree of dissociation. The addic character has been found
year in which Bronsted concept was introduced). However .
to be in the following order:
the concept became influential only in 1930 onwards.
HCl04 > HBr > H 2SO4 > HCI > HN03. According to this concept, a base is a substance which can
furnish a pair of electrons to form a coordinate bond
Limitations whereas an acid is a substance which can accept a pair of
(i) A substance is termed as an acid or base if it reacts with
electrons. A Lewis acid is a substance that acts as an
some other substance, i.e., if it donates proton to other electron acceptor or electrophile while a Lewis base is a
substance, it is an acid and if it accepts proton from other substance that acts as an electron donor or nucleophile.
substance, it is a base. Neutralisation reaction involves the formation of a
coordinate bond.
(ii) There are number of acid-base reactions in which no
proton transfer takes place, e.g., A simple example of an acid-base is the reaction between
a proton and a hydroxyl ion.
162 G .R.B. Inorganic Chemistry for Competitions
H++
..
:O:H-~H:O:H
..
Acid Base (ii) Negatively charged species or simple anions :
Some other examples are: For example, chloride, cyanide, hydroxide ions, etc., act as
H3N: + BF3 H3N -4 BF3 Lewis bases.
Base Acid CN"', CC
H+ + :NH3:=: [H f- NH31+ (iii) Multiple bonded compounds: The compounds
Acid Base which form coordination compounds with transition metals
such as CO, NO, ethylene, acetylene, etc., can act as Lewis
BF3 + : f.: :=: [: f. -4 BF3]- bases.
Acid Base
According to Lewis concept, the given species can act as
Lewis acids :
(i) Molecules in which the central atom has
incomplete octet : Lewis acids are electron deficient It may be noted that all Bronsted bases are also Lewis
molecules such as BF3, AICl3, GaCl3, etc ... bases but all Lewis acids are not Bronsted acids.
H3N: + AICl3 ~ H3N ~ AICl3
(ii) Molecules in which the central atom has empty
51 Limitations of Lewis Concept
d·orbitals: The central atom of the halides such as SiX4, (i) Lewis theory fails to explain the relative strength of
GeXt, TiC4, SnCl4, PX3, PF5, SF4, SeF4, TeC4 etc., have vacant acids and bases as different types of reactions are
a-orbitals. These can, therefore, accept an electron pair and involved.
act as Lewis acids. (ii) Acids such as HCI, H2SO4 do not form coordinate
bonds with bases.
Lewis acid Lewis base Complex (iii) All acid-base reactions are fast. However, the
(iii) Simple cations: All cations are expected to act as formation of coordinate bond is very slow in certain cases.
Lewis acids since they are electron deficient in nature. Example 4. (a) What is the Lewis acid and base in the
However, cations such as Na+, K+, Ca2+, etc., (inert gas following reaction?
configuration) have a very little tendency to accept 2NH3(aq) + Ag +(aq) ~ [Ag(NH3ht(aq)
electrons, while the cations like H+, Ag+, Fe3+, Cu2+, etc., have
greater tendency to accept electrons and, therefore, act as (b) What allows ethoxyethane to behave as a Lewis base?
Lewis acids. (c) Whether aluminium trichloride is a Lewis acid or a base or
both?
Ag+ +2:NH3 ~ [H3N -4Ag f-NH31+
Solution:
Fe2+ +6CN- ~ [Fe(CN)614 - (a) The silver ion accepts the lone pairs from
(iv) Molecules having a multiple bond between ammonia. Therefore, Ag+ is a Lewis acid and ammonia a
atoms of dissimilar electronegativity : Typical examples Lewis base.
of molecules belonging to this class of Lewis acids are CO2, (b) The ether has two lone pairs on the oxygen like
S02 and S03' Under the influence of attacking Lewis base, water.
one n-electron pair will be shifted towards the more negative (c) AICl3 acts both as a Lewis a{:id and base, i.e.,
atom. aluminium atom is the Lewis acid and chlorine the Lewis
base. Due to this reason it forms dimer, A12Cl6.
OH
Example 5. (a) How do you account for the formation of
t;J C=O+OH-~--O-~=O or HC03 S20j- from soj- and 5 in terms of Lewis acid theory?
(b) Whether the following reaction is Lewis acid-base reaction
(v) Elements with an electron sextet: Oxygen and or not?
sulphur atoms contain six electrons in their valency shell and
can accept a lone pair of electrons and act as Lewis acids.
The following species can act as Lewis bases : Solution:
(i) Neutral species having. at least one lone pair of (a) A sulphur atom is electron deficient and can thus be
electrons: For example, ammoni.a, amines, alcohols, etc., regarded as an acid. SO~- acts as a base.
act as Lewis bases as they contain a pair of electrons.
Acids and Bases 163
..
:0:
2-
:0:
2- and reducing agent as bases.. Some examples of acid-base
reactions in terms of this concept are given below :
.. I I Acid Base' Salt J~tification
..
:8
Acid
+ :8
I
0:
••
---)10> :8.. 8-0:
I
.. Cl z + 2K ----7 2KCI K loses an electron while
o gains an electron.
:0: ..
:0: 50 3 + Cab ----7 Ca504 CaO yields i f and S~
accepts 0 2- •
(b) The reaction is not a Lewis acid-base reaction as it does As z5s +3(NH4hS ----7 2(NH4hAsS4 (NH.qh5 loses 52- ions
not form a coordinate bond. while ASz5s gains 52-
3-1 THE LUX-FLOOD CONCEPT Fe(CN)z +4KCN ----7

ions.
K 4Fe(CN)6 Fe(CNh combines with
The concept proposed by Lux (1939) and extended by Flood CN- ions given by KCN.
(1947) to explain acid-base reactions in terms of the oxide
It is the most general concept out of the concepts of
ion. According to this concept, a base is any substance acid-base so far given. The concept is undoubtedly too broad
which gives up oxide ions and an acid is any substance
that nearly all the chemical reactions fall into acid-base
which gains oxide ions.
category.
so~- ~ S03 + 0 2
-
Base Acid 3~~4 HARD AND SOFT ACIDS AND BASES
CaO ~ Ca2+ + 0 2- All the Lewis acids and bases are classified as hard and soft
Base Acid
acids and bases. It was proposed by Pearson in 1963 in
Si02 + 02- ~ SiO~- order to explain the stabiUty of the complexes formed by the
Acid Base
combination of a Lewis acid and a Lewis base.
Thus, acids are the oxide ion acceptors, while bases are Soft bases have donor atoms which are easily polarised
the oxide ion donors. and have low electronegativity. The hard bases have
The following reactions, thus, involve CaO, PbO as bases properties opposite to those of the soft bases, i.e., hard bases
and SiOz, S03 as acidic oxides which react together to form have donor atom with low polarizabilities and higl
salts respectively. electronegativity. Within a group in the periodic table;
Cao + Si02 ----7 CaSi03 softness increases with increasing size of the donor atom.
Base Acid Salt Hard bases: H20, OH-, F, CH3CCXT, PO~-, SO~-,
PbO + S03 ----7 PbS04 CC CO~-, CI04' , N03' ROH, RO-, R20, NH3, RN2, N 2I-4.
Base Acid Salt
Soft bases: R2S, RSH, RS-, r, SCN-, S20~- , R#, R3As,
Substances are termed amphoteric if they show a tendency
(RO)#, CN-, RNC, CO, C 214, C 6Hti, H-, K.
of losing as well as accepting an oxide ion.
ZnO + 02- ~ Zn~- ; Zno ~ Zn 2+ + 02-
Border line: C~5NH2' CsHsN, Br-, NO sot N3' z,
Acid Base Soft acids are those which possess acceptor atoms, large
Al203 + 02- ~ 2AlO z ; Al20 3 ~ 2Al3+ + 30 2- in size, of low positive charge, have high polarizability and
low electronegativity and do not have noble gas
The Lux-Flood concept can be extended to include transfer configuration. Hard acids are those in which acceptor atoms
of any anion, for example, halide, sulphide, etc. have small size, high electronegativity, low polarizability and
3NaF + AIF3 High temp. ) 3Na + + AIF~- possess noble gas configuration.
Base Acid •
H ard aCIds: +.+I N a +I K+,Be2+I C a2+, Sr2+I Mn2+I Al3+I
HILI
3+
G a, In3+I
La3+I
C0 3+,Cr3+, Fe 3+lT·4+
l ,etc.
USANOVICH CONCEPT •
Soft aCids: Cu,+ Ag +,.Au+, Te, + H g, + Pd2+"" Cd2+ P t2+,
2
Hg +, GaCl3, 1+, Br+, 12, Brz, etc.
This concept is an extension of Lewis concept. According to
this concept, an acid is any chemical species which reacts Border hne:• Fe2+, C~2+
L1, N·1 +, CU
2 2+, Zn2+" 2+ '5n 2+ ,
Pb',
3
with bases, gives up cations or accepts anions or electrons Sb +, SOz, etc.
and a base is any chemical species which reacts with acids, The bonding between hard acids and hard bases are
gives up anions or accepts cations or donates electrons. predominantly ionic whereas the soft-soft interactions give
Besides, Arrhenius, Bronsted-Lowry or Lewis acids and largely covalent compounds. Hard acids have vacant orbitals
bases, this concept includes all the oxidising agents as acids and can accept a-electrons while hard bases with filled outer
valence shell orbitals, can donate the a-pair of electrons. For The two factors which influence acid strength work
weak acids and weak bases, n-bonding seems to be impor- against each other in these hydrides. The effect of atomic
tant. The compounds between hard acids and hard bases size outweighs the electronegativity effect. A proton is more
and between soft acids and soft bases are stable. easily removed from a hydride in which the central atom is
larger than from one in which the central atom is small. The
3.gl
":~
SOME GENERAL TRENDS IN ACIDIC charge density on the conjugate base is in the order:
AND BASIC PROPERTIES (On the basis of 0 2- > 52-> 5e2- > Te2~
Arrhenius and Bronsted-Lowry concepts) and F > Cl- > Br- > 1-
In order to analyse the relationship between molecular Greater charge density on the conjugate base will result
structure, the acids are divided into two types: in greater protol1 attraction.
(i) Covalent hydrides: In these the proton is directly The acidic nature of the hydrides of VIlA group elements
attached with the central atom of the molecule. Examples are: is also explained by the fact that bond energies decrease.
H X (X = F, Cl, Br, l), H 20, CH 4, H 25, etc. These are also called
H-F > H-c-CI > H-Br > H-I
hydracids or: hydroacids.
135 kcal mol-1 103kca] mol-1 88 kcal mol-1 71 kcal mol-1
(ii) Oxy-acids: In these the protorl'i$ attached to an
oxygen atom, the later being bonded to the central atom. Due to large electronegativity, hydrogen bonding exists in
the hydrides of oxygen and fluorine which also decreases
.
Examples are: H 2503, HN03, H 2SO4, HCl04, etc.
their acid strength .
ri~ (i) Covalent hydrides :' In the hydrides of the elements having nearly the same
Two factors influence the acid strength of the hydride of electronegativity, the acidic nature increases as the size of
an element : The electronegativity of the element and the the central element increases. C, 5 and I possess same electro-
atomic size of the element. The first of these factors is best negativity, the acidic nature follows the following order:
understood by comparing the hydrides of the elements of a CH4 < H25 < HI
period of the periodic table. The second is important when as the size increases from carbon to iodine.
group comparisons of the periodic table are made.
(a) Hydrides of the elements of a period: The acid ~ Oi) Oxy-acids :
strengths of the hydrides of the elements of a period increase
In oxy-acids, the proton is attached to oxygen atom which
from left to right in the same order as electronegativity
is linked to the central atom. .
increases. Highly electronegative element withdraws ele-
ctrons from the hydrogen easily and facilitate the release of a b
H-O-Z
hydrogen as proton. The electronegativities of the following
second and third period elements fall in the order: The main factors which affect the strength of an oxy-acid
N < 0 < F and P < 5 < Cl are: (a) the size of the central atom, (b) the electronegativity
The acid strength of the hydrides increases in the sarrie of the central atom and (c) the number of other electronegative
order: atoms attached to the central atom.
NH3 < H 20 < HF and PH3 < H 25 < HCl Smaller the size and' greater the elec::tronegativity of Z
The inc-p;:!se in acidic nature is also due to the fact that mal<e the oxy-acid stronger. These factors will shift the
electron pair between Z and 0 towards Z and this displace-
the stability of their conjugate bases increases in tlle order:
ment will in turn cause a shifting of electron pair between
NH2 < OH- < F
oxygen and hydrogen towards oxygen. Thus, O-H bond
The increase in acidic properties is supported by is weakened and proton is easily released. In the series,
successive increase in the dissociation constant.
HOI < HOBr < HOCl
NH3 (=10-35) < H 20(=10-14) < HF(=1O- 4)
The electronegativity increases and size decreases: of
(b) Hydrides of the elements of a group: The acidity
the central element. 5ame trend is observed in the oxy
of the hydrides of the elements of a group increases with
-acids of different elements in the same oxidation state
increasing size of the central atom. For example in the
HCI04 > HBr0 4 > HI04·
hydrides of VIA or XVI group and VIlA or XVII group, the
Greater the number of negative atoms present in the oxy-
acidic nature)ncreases as the atomic number of the central
acid make the acid stronger. In general, the strengths of acids
element increases.
that have general formula,
H 20 < H 25 < H 25e < H 2Te (HO)mZOIl
and HF < HCl < HBr < HI
can be related to the value of n.
Acids and Bases 165
If n 0, the acid is very weak, HOC!, (HOhB, (HO)4Si.

If n I, the acid is weak, HOClO, HONO; (HO)zSO, Basic Less basic v
Neutral
(HOhPO·
If n 2, the acid is strong, HOCI02, HON02, (HO)zS02' (c) The larger the size of the atom holding the unshared
If n 3, the acid is very strong, HOCI03, HOl03. electrons, the lesser is the availability of the electrons, i.e., the
The negative atoms draw electrons away from the Z-atom basic strength of halide ions follow the following order:
and make it more positive. The Z-atom, therefore, becomes P- > Cl- > Br- > 1-
more effective in withdrawing electron density away from Smaller Larger
size size
the oxygen atom that is bonded to hydrogen. In tUrn, the
electrons of 8-0 bond are drawn more strongly away Similarly,
from the H-atom. The net effect makes it easier for the (d) The basic nature of a substance decreases with the
proton release and increases the acid strength. increase of the electronegativity of the atom holding the lone
This effect is illustrated by the following series of acids: pair of electrons, i.e., the tendency to donate the electron pair
+1 . +3 +5 . +7 .. to proton decreases with increase of electronegativity.
HOCl < HOCIO < HOC 10 2 < HOC 103
+4 +6 : NH 3 > H 2 0: >Hf.:
H 2S03 < H 2S04
+3 +5 (e) The presence of a positive charge on the atom holding
HN0 2 « HN03 the lone pair decreases the base strength while a negative
Note: In the above examples, it is evident that strength of the charge increases the base strength.
acid increases as the oxidation number of the central +
atom increases. However, this rule fails in oxy-acids of ..
:OH>H-O-H> H30: ..
phosphorus, (f) Base strength increases with decrease in oxidation state
of the central atom.
as all are weak acids, i.e" about the equal strength. Thus,
NH3 > N2~
prediction on the basis of oxidation number is incorrect. Oxid. Number -3 -2
Formal charge on the central atom gives more reliable
prediction. The strength of the acid increases as the Amphoterism
formal charge on the central atom increases.
Substances which behave as bases towards strong acids
Formal charge = Group number - number of bonds
and acids towards strong bases are called amphoteric and
number of unshared electrons.
the phenomenon as amphoterism. Some metal oxides and
HOCI < HOCIO < HOClOz < HOCI03 hydroxides are amphoteric. Por example, Zno and Zn(OH)z,
Formal charge on CI 0 +1 +2 +3 Al20:3 and AI(OHh, SnO and Sn(OH)z, PbO and Pb(OH)z,
Cr203 and Cr(OHh are amphoteric in nature.
ZnO + 2HCl ---j ZnClz + HzO
H
I
OH
I
...
ZnO + 2NaOH---j NazZnOz + H 20
HO-P --+0 HO P --+ 0
I .I Sn(OH)z + 2HCl ---j SnClz +- 2H20
OH OH Sn(OH)z +2NaOH ---j NazSnOz + 2H20
Formal charge on P +1 +1 +1 The salts of ,.5n2+, Pb z+, AI3+ and Cr3+ dissolve in
As the formal charge is same, all the above oxy-acids
excess of NaOH solution due to formation of hydroxide first.
of phosphorus are nearly of equal· strength.
ZnClz + 2NaOH ---j Zn(OH)z + 2NaCI
Strength of Bases Zn(OH}z + 2NaOH ---j Na2ZnOZ + 2H20
(a) Among alkali and alkaline earth metals oxides and

Example 6. Explain on the basis of SHAB principle,
hydroxides, the basic nature increases as the size of the (a) Ag(CN)'Z is stable while AgCli is .unstable.
central atom increases, i.e., electropositive nature increases. (b) The alkaline earth metals are found in nature as carbonates
CsOH > RbOH > KOH > NaOH > LiOH and sulphates whereas mercury and silver are found as sulphides.
Ba(OH}z > Sr(OH)z > Ca(OH}z >. Mg(OHh > .Be(OH)2 Solution:
(b) Among the hydrides of the same group, the basic (a) Ag + is a soft acid, CN- is a soft base while cr is a
nature decreases with increase in the size of central atom as hard base. Therefore, Ag(CN)2 (soft acid + soft base) is a stable
the tendency to accept proton decreases due to decrease in complex while AgCli (soft acid + hard base) is an unstable
electron density (or ability to donate the electron pair complex.
decreases).
(b) The ions ci+, Mg2+, Ba2+, etc., are hard acids while Solution:
SO~- and CO~- ions are also hard bases. Since compounds (a) Br- ion contains lone pair of electrons which it can
of hard acids and hard bases are stable, alkaline earth metals donate. Hence, it acts as a Lewis base. Br- can accept proton
are found in nature as sulphates and carbonates. However, and hence, it acts as a Bronsted base.
Hg2+ and Ag+ ions are soft acids. They combine with s0ft (b) NH3 acts as a Lewis base as the nitrogen possesses
bases such as S2- to form stable compounds. a lone pair of electrons which it can donate (HiN ~
BP3)' It can combine with H+ to form ammonium,
Example 7. ExPtain the following : NH! ion. Hence, it is a Bronsted base ..
(a) Br- ion is a Lewis as well as Bronsted base. (c) BP3 acts as a Lewis acid as it is an electron pair
(b) NH3 is a Lewis as well as Bronsted base. acceptor (H:?N: + BP3 ~ H3N ~ BP3). BP3 does not
(c) BF3 is a Lewis acid but not a Brollsted acid. possess.the tendency to lose a proton, hence it is not
a Bronsted acid.
C1 SUMMARY',ANIO IMPORTANT POINTS TO REMEMBER g

1. The word acid IS a: L~tin word-acidus meaning sour. 7. Chemical species that differ in composition only by proton
2. Liebig, in 1830, defint:;d acid as a compoWld which contains are called a conjugate pair.
one or more hydrogen atoms replaceable partially or Acid ~ H+ + Base
completely by a metal or a positive radical to produce a
salt. Every acid has its, conjugate base. If acid is strong, its con-
3. According to Arrhenius concept, all substances which give jugate base is strong and vice-versa. An acid base reaction
H+ ions when dissolved in water are called acids while those involves two conjugate pairs, i.e., when acid reacts with a
which ionise in water to furnish OH- ions are called bases. base another acid and base are formed.
The reaction between an acid and a base is termed neutrali- Acid J + Basen ~ Acidu + Basel
sation, i.e., neutralisation involves the reaction between H+
HCl + HzO ~ H30+ + Cl-
and OH- ions to form water.
Acid Base Acid Base
Limitations NH3 + H 20 =-== NH4+ + OH-

Basel Addu Acid) Baseu
(0 It is applicable to aqueous solutions only, i.e., water is
necessary to explain the acidic or basic properties of H 20 can act either as an acid or a base (amphiprotic).
the substances. 8. HC03, HSO~ HZP04r HPO~-, H2P03 and H~ are
(ii) It fails to explain acidic properties of non-protic amphiprotic in nature.
compoWlds such as ~ PzOs, etc. 9. Solvents which neither donate nor accept protons, e.g.,
(iii) It fails to explain the basic nature of compoWlds like benzene, carbon tetrachloride, carbon disulphide, etc., are
NHJ, Na ZC03, etc. . called aprotic solvents.
(iv) It fails to explain the acidic nature of salts like AICl3 10. The strength of an acid depends upon its tendency to lose
in aqueous solution. its proton and the strength of the base depends upon its
tendency to gain the proton.
4. Modified Arrhenius concept rectifies most of the limitations.
Water is a weak electrolyte and neutral in nature, i.e., [H30+] HA + H:P ~ H30+ + K; B + H 20 ~ H+B + OH-
[OH-]. [H3 0 +][K]
The substances wpi.:h increase the concentration of H30+ Ka [HA]
ions in water act as acids while those which increase the
Larger the value of Ka indicates Larger the value of Kb indicates
concentration of OH- ions act as bases. SOzis thus an acid that the acid is stronger in nature. that the base is stronger in nature.
and NH3 is a base.
The strength of an acid also depends on the solvent. The
water acids H004, HCI, H ZS04 and HN03 which have nearly
S02 + H 20 ~ H 2S03 ~ H30+ + HSO"3
same strength in water, will be in the order of :
NH3+H20~~OH ~ ~+ +OH-
HCI04 > H ZS04 > HCI > HN~
5. The strength of an acid or a base in Arrhenius concept is
in acetic acid. HCI acts as a stronger acid in NH 3, weak acid
based on the extent of ionisation, i.e., on the equilibrium
in acetic acid, neutral in benzene and weak base in fIF.
constant of an acid, Ka, and on the equilibrium constant of
a base, Kb• In order to avoid writing negative powers, Ka or Kb are
generally converted into pKa (-IOgIO Ka) or pKb (-logIO Kb)
6. According to Bronsted-Lowry concept, a substance is known
respectively. Smaller the value of pKa indicates the stronger
as an acid if it can donate a proton and as a base if it can
add.
accept a proton. Acids are proton donors (protogenic) and
bases are proton acceptors (protophilic). 11. Any species, that is an acid by Arrhenius concept remains
an acid in the Bronsted-Lowry concept. The same is true for
Acids and Bases 167
bases. Certain species which do not contain OH- group Hard acids are those in which atoms have small size, high
which are not regarded as bases by Arrhenius concept such electronegativity, low polarizability and possess noble gas
as HCO"3, H2P04', etc., are regarded as bases by Bronsted- configuration. The examples are : H+, U+, Na+, ea2+, Mn2+,
Lowry concept. Al3+ and Ti4+, etc.
12. According to Lewis concept, a base is a substance which can The bonding between hard acids and hard bases are
furnish a pair of electrons to form a coordinate bond whereas predominantly ionic whereas the soft-soft interactions
an acid is a substance which can accept a pair of eleC'trons. give largely covalent compounds. All these compounds are
Lewis acid is an electron acceptor, i.e., electrophile while a stable.
Lewis base is an electron donor or nucleophile. Lewis acid 16. Trends in acidic and basic properties:
is electron deficient while Lewis base is electron rich species Acids are divided into two types:
(lone pair of electrons). (0 Covalent hydrides: In these, proton i:; directly attached
The following species can act as Lewis acids ; to the central atom of the molecule.
(0 Molecules in which central atom has incomplete octet (ii) Oxy-adds: In these, proton is attached to an oxygen
such as : BF3, AICI3, GaCI3, etc. atom, the later being bonded to the central atom.
(ii) Molecules in which central atom has empty d-orbitals 1. Covalent hydrides: Two factors influence the acid
such as ; SiX4, SnCI4, PFs, SF 4, PX3, etc. strength, the electronegativity and the size of the central
(iii) Simple cations such as : H+, Ag+, Fe3+, Cu2+, etc., have
atom.
a tendency to accept electrons. (a) The acid strength of the hydrides of the elements of
a period increases from left to right as the electro-
(iv) Molecules having a multiple bond between atoms of
negativity increases. Highly electronegative element
dissimilar electronegativity such as ; CO2, SOz, S03,
withdraws the electrons from the hydrogen easily
etc.
and facilitate the release of hydrogen as proton.
(v) Elements with an electron sextet such as oxygen and·
sulphur atoms. NH; < H 20 < HF and PH3 < H 2S < HCl
The following species can act as Lewis bases : Acidic nature increases.
.. ..
(1) Neutral species having at least one lone pair of
.. (b) The acid strength of the hydrides of the elt::Hl":"lts of
a group increases wiJ;h increasing size of the central
..
electrons such as: NH 3 , R-NH2' R-O-H, etc.
atom. ..
(ii) Negatively charged. species or simple anions such as ;
CC CN-, OH-, etc. H 20 < H 2S < H;5e < H2Te
(iii) Multiple bonded compounds such as : CO, NO, C 2f4 HF < HCl < HBr < HI
C2Hz, etc. Acid strength increases as the size increases.
H may be noted that all Bronsted bases are also Lewis bases 2. Oxy-acids: The main factors which affect the acid
but all Lewis acids are not Bronsted acids. strength ·of an oxy-acid are :
13. According to Lux-Flood concept, a base is any substance (a) The size of central atom,
which gives up oxide ions and an acid is any substance which (b) Theelectronegativity,
gains oxide ions. Thus, acids are the oxide acceptors, while
(c) The number of other electronegative atoms attached
bases are oxide ion donors.
to the central atom.
sof- ~ S03 + 0 2- Si02 + SiO~- Smaller the size and greater the electronegativity of
Base Acid Acid Base central atom make the oxy-acid stronger. These
factors shift the electron pair of the bond of oxygen
14. According to Usanovich concept, an acid is any chemical
towards central atom and this displacement will in
species which reacts with bases, gives up cations or accepts
turn cause a shifting of electron pair between oxygen
anions or electrons while a base is any chemical species
and hydrogen towards oxygen. Thus, O-H bond is
which reacts with acids, gives up anions or accepts cations
weakened and proton is easily released.
or donates electrons. This concept is an extension of Lewis
concept. This concept regards all oxidising agents as acids HOI < HOBr < HOCl Acid strength increases
and reducing agents as bases. HI04 < HBr04 < HCI04 Acid strength increases
is. All the Lewis acids and bases are classified as hard Greater the number of negative atoms present in the
and soft acids and bases. It was proposed by Pearson in 1963. oxy-acid make the acid stronger. In general, the
Soft bases have donor atoms which are easily polarised and strengths of the acids that have general formula,
have low electronegativity such as : RSH, C R#, CN-, etc. (HO)m ZOn
Hard bases have donor atoms which have high electron-
can be related to the value of n.
egativity and low polarizabilities such as : H 20, OH-, F-,
CC coj-, NH3, etc. If n = 0 , the acid is very weak Example HOCI
Soft acids are those which have acceptor atoms, large in size, If n 1, the acid is weak Example HOClO
low electronegativity, low positive charge and do not have If "l 2 , the acid is strong Example HOCl02
noble gas configuration. These possess high polarizability. If n = 3 , the acid is very strong Example HOCl03
The examples are: Ag+, Au+, Cd2+, Sn2+, Hi+ and I+, etc.
[Formal charge on the central atom gives more reliable Be(OHh < Mg(Ol.fh < Ca(OHh < Sr(OHh < Ba(OH)z
prediction: about the strength of acid. The strength increases strength increases
as the formal charge on the central atom mcreases. In the
(b) Among the hydrides of the same group, the basic nature
case of oxy-acids of phosphorus, the acid strength of the
following oxy-acids is nearly same as formal charge is +1 decreases.
in them: ,NH3 > PH3 > !\SH3 > SbH 3 > BiH 3,
Basic Less basic Net.'itral
(c) The presence of a positive charge on the atom holding
,Strength of Bases
the lone pair decreases the' base strength while the
(a) Among alkali and alkaline earth metals the basic nature, negative charge increases the base strength.
of oxides and hydroxides increases as the size of the
.. +
cation increases, i.e., electropositive nature increases. :9.H > H-g-H > H30:
LiOH< NaOH < KOH < RbOH < CsOH strength
increases
~-,~~ .'~'''' PRACTICE PROBLEMS ~ •• '.'~

- ~ - - .
• Subjective Type Questions (vii) pot + H 20 ~ HPO~- + OH-

(viii) H 2Fe(CO)4 + CH30H ~ [HFe(CO)4f +CHgOH2'
1. In the following equations, label each species as an acid or
(ix) HS04 + OH- ~ SO~- + H20
a base.', Show the conjugate acid-base pairs.
(a) HCOi{aq)+HF(aq) H 2C0 3 (aq)+F-(aq)
7. Write down the conjugate acid and base of :
(i) NH3 (ii)HCOi (iii) H804'
(b) HC03(aq)+OH-(aq)-;-:-'CO~-(aq)+ H 20(l)
(iv) H 20 (v) CH 3COOH (vi) H 2NCH 2COOH
2. In the following reactions, identify the Lewis acid and the
Lewis base.
(a) Ag + + 2NH3 Ag(NH3); '8. In the reactions, which reactant is the Lewis acid and which
(b) B(OHh + H 20 ,B(OH)4" + H+ is the Lewis base?
H (i) NH3 + BF3~ H3N: BF:3
I
F:3B:0-CH3 (ii) BeF.i + 2F- ~ BeFi-
(iii) 5+ S20~-
(d) d- + C02 r==::! CO~-
3. Identify each of the following as an acid or a base in terms
(iv) (CH 3)gN + S03~ (CH 3hN: SOg
of the Arrhenius concept. (v) + 6CN- ~ [Fe(CN)61 4-
(a) BaO (b) H 2S (c) CH~2 (d) 802 .{\d) CO 2 + OH- ~ HCO:3
4. Give the conjugate acids of: 9. W~~d each of the following species iJ;l solution tend to
, (i) HCO g (ii) HS04' (iii) [Fe(H20)s(0H)f+ b,iQCluce a basic, a neutral or an acidic solution?
(iv) OH- (v) soj- (vi)' N2H4 .(~j' C2H 30- (b) Na+ (d SO~- (d) F-
(vii) Br~ (viii)CH 3NH 2 (ix) PHg
!Hint : In each case the conjugate acid is formed by addition of ',(¢) NH t (f) AIC1 3 '
a proton.] <{Hint : A conjugate of a weak acid produces an alkaline solution
whereas a conjugate of a weak base produces an acidic
5. Give the conjugate base of : solution. The aqueous solution' of a species whose
(i) OH- (ii) NH3 (iii) H 20 , conjugate is strong, is neutral.] ,
(iv)' HgO+ (v) HCOi (vi) CHgCOOH
10. ~'{c;hof the following pairs is the strongest acid? Give
(vii) C 2H sOH (viii) H S ( i x ) HN03
"'li¢,ason for your choice :
[Hint : In each case, the conjugate base is formed by loss of a
proton,] , {a) [Fe(H 20)61 3+ or [Fe (H20)612+
6. Label the conjugate acids and bases in these reactions : (b) [Al(H 20)61 3+ or [G'1 (H20) 61 3+
(i) + H30+ ~ HS- + H~ (c) Si(OH)4 or Ge(0H)4
(ii) T:lJ2H4 + H 20 ~ N2Hs + OH- (d) HCI03 or
(iii) NH2' + H 20 ~ NH3 + OH- (e) H 2Cr04 or
(iv) CHgCOOH + H20 ~ CH3COO- + HgO+ (f) H 3P04 or
(v) [A1(H20)6]3+ + H 20 ~ [A1(H20)sOH]2+ + HgO+ 11. Answer the following :
(i) What is the nature of the solution which turns blue
(vi) CO~- + H 20 ~ HC03' + OH-
litmus to red?
Acids and Bases 169
(ii) What is the nature of the solution which turns red (iv) Water behaves as an acid and also like a base on the
litmus to blue? basis of protonic concept.
(iii) Conjugate acid-base pair differ by .......... . [Hint : With strong acid, water behaves as a base as it
accepts proton.
(iv) Arrhenius theol}' of acids-bases is not applicable to
HCl + H20 ~ H30+ + Cl-
With strong base, water behaves as an acid as it
(v)AICl3 is a Lewis acid because it is .......... .
donates proton.
(vi)NB3 is a Lewis base because it is .......... . NHi + H 20 ~ 'NH3 + Off' J
(vii)The ligands in the complex compound are ........... .
(v) Neither pure H 2SO4 nor pure HCl04 conducts electric
(viii)A substance gives .H30+ ions in aqueous solution. current but a lluxture of the two does. , .
What is that substance? [Hint : Both the pure acids ~re unionised. However, when
(ix) The conjugate base of a strong acid is .......... . mixed'the stronger acid, HCI04, donates a proton
(x) In a reaction H+ ions combine with OH- ions to form , to H 2SO4 and ions are formed. ~
water. What is the type of reaction? HCl04 + H2SO4 ~, .H3S04'+ Cl04- ]

12. Arrange the following in the order of their : (vi) AgIz complex is more stable than AgF2'
[Hilit : Ag+ ion is a soft acid. Its interaction with l' ion, a
(a) increasing acid strength HF, HCl, HBr and HI soft base, yields a stable complex' whereas its
(b) increasing acid strength HCl04, HCI03,HCl02, HCIO interaction with F- ion, hard base yields an
[I.I.T. 1986] unstable complex,)
(c) increasing basic nature H 20, OH-, CH30H, CH30- , (vii) CsF reacts with Lileven though both are ionic.
[I.I.T. 1992] [Hint : The reaction is an interesting example of
(d) increasing acid character CO 2, NzOs, Si02, S03 preferential combination of soft-soft and hard-hard
[I.I.T. 19881 species.
(e) increasing basiC strength ClO-, Cl02, CI03, CI04" CsF + Lil ~ CsI -+ LiF
Soft-hard Hard-soft. Soft-soft Hard-hard 1
(f) increasing acid strength [Na(HzO)n]+, [Ca(H 20)n]2+,
(viii) 503 has acidic behaviour.
[Al{HzO)6]3+, '[Fe(H20)6]3+
[Hint : Sulphur atom is attached with three very highly
(g) increasing basic strength F, OH-, CH3, NH z ·electronegative oxygen atoms. As a result, elec-
(h) increaSing acid strength CH 4, NB3, H 20 and HF tronsare drawn towards oxygen atoms and
(i) increasing basic strength H30+, H20,OH- 5-atom remains' with low electron density and
thus, has the tendency to accept electrons. So, it
(j) increasing basic strength CH30H, CH3NBZ, CHgF
acts as a Lewis acid.)
13. Predict the direction of the following reactions in .aqueous
solution: (ix) H 3P04 is tribasic but HgP03 is dibasic in aqueous
solution.
(a) HNOz + CN- ~ HCN + NO z [Hint : In H3P04, three hydrogen atoins are bonded to
(b) F- + H 20 ~ HF + OH- phosphorus atom through oxygen atoms and these
(c) Na+ + H 20 ~ NaOH + H+ three hydrogen' atoms are dissociated into H+ ion.
. Hence, H3P04 is tribasic. In H 3P03,' twe hydrogen
14. Define and give one example each of the following terns:
atoms' are bonded to phosphorus atom through
(a) Bronsted-Lowry acid (b) Bronsted-Lowry base oxygen atoms. So, H;>P03 is dibasic.]
(c) Lewis acid (d) Lewis base
(x) Dilute sulphuric acid is said to be stronger than
(e) . Amphoteric compounq (f) Neutralisation'
(g) Hard acid (h) SOft base concentrated sulphuric acid.
[Hint: Strength of the add depends on the number of H+
15. Explain giving reasons : ions present in the solution. Degree of dissociation,
(i) CC4 does not ad as a Lewis acid while' SiCl4 and i.e., the tendency to liberate H+ ions increases with
SnC4 do so. dilution, Thus, dil. H 2SO4 is stronger than cone.
[Hint : Carbon does not have d-orbitals to accommodate H 2S04 ,]
the accepted electron pair while Si and Sn possess
d-orbitals and thus, accept electron pair electrons.
SnCl4 +2:9:- ~[SnCld-]
u,wis add,
(ii) BF3 acts as a Lewis acid whereas NF3 does not.

Match the following :
[Hint : BF3 is an electron defident compound. It can (a) BF3 (i) Cationic Bronsted base
accept an electron pair. N in NF3has completed (b) NH; (ii) Cl-
octet and d-orbitals are not present. It cannot (c) H 2O (iii) H 3POZ '
accept an electron pair.] (d) [Al(H 2O)sOH]z+ (iv) Ag+
(iii) HCl04 is stronger acid than H 2SO4 , (e) Monobasic acid (v) Bronsted acid
[Hint : The number of terminal oxygen atoms in HCl04 (f) Soft acid (vi) H++OH-~H20
are three while in H 2SO 4 are two. Chlorine is more (g) Hard base (vii) Lewis acid
electronegative than S.]
(h) Neutralisation (viii) Amphiprotic
Answers : Subjective Type Questions 8. Lewis acid Lewis base

1. (a) Hi=03 and HC03 are a conjugate acid-base pair. NH3 Lone pair donated by NH3 and
HF and Ii are a conjugate acid-base pair. accepted by BF3.
(b) HCO; and CO~- are a conjugate acid-base pair. (jj) BeF2 Ii Lone pair donated by F- and
H 20 and OR"' are a conjugate acid-base pair. 'accepted by BeFz.
2. (a,) Ag+ Lewis acid Ag+ +2: NH3 ~[Ag(:NH3)Zt (iii) 5 SO~- Lone pair donated by SO~- and
accepted by S.
NH3 Lewis base
(iv) 503 (CH 3hN Lone pair donated by (C~)N and
(b) B(0H)3 Lewis acid
accepted by 503.
OH H OH CN" Lone pair donated by CN" and
I . 00 I
accepted by Fi+ .
HO-B + :O:H~ HO-B:OH +H+
I I (vi) CO 2 OH- Lone pair donated by mr and
OH OH accepted by CO:a.
HP Lewis base 9. CZH30-, SO~- and F - These are conjugate of weak acids,
F H FH (a) (d (d) hence their aqueous solutions are
I I I I
alkaline.
(c) BFg Lewis acid F-B + : O-CHg ~ F-B: 0-CH3
I 00 I 00
(b) Na+ It is a conjugate of a strong alkali, hence
F F the aqueous solution is neutral.
CHPH Lewis base z- (e) NHt - It is a conjugate of a weak base, hence
o :0: its aqueous solution is acidic.
[:§:f ~~
00 1\ (£) AlCl3 -[AI(H20)d+ is a conjugate of a weak
(d) CO2 Lewis acid + :0- C
I, I base, hence its aqueous solution is
o :0: acidic.
Oz- Lewis base [Al(H20)613+ + H 20 ~ [Al(H20)s(OH)]2+ + HgO+
g
3. (a) BaO is a basei BaO + H20 - - 7 Bi+ + 20R"' 10. (a) [Fe(HzO)61 + Small radii, and higher charge increases acid
(b) H2S is an acid; HzS + H 20 - - 7 H30+ + HS- strength.
(c) CH~2 is a base; CH~2 + H20 - - 7 CH3NH! + OR"' (b) [AI(H20)i+ Smaller size of Al3+ than Ga3+.
(d) SOz is an acid; SOz + 2HzO - - 7 H30+ + HS03 (c) Si(0H)4 Smaller size of Si than Ge.
4. (i) H ZC03, (ii) H 2SO4, (iii) [Fe(HzO)613+, (iv) H 20, (v) HSO;, (d) HCl04 More electronegative oxygen atoms with CI than in
(vi) N2Ht, (vii) HBr, (viii) CH~t (ix) pm. HClOg or formal charge is more on Cl in HCI04 than in
5. (i) 02-, (li) NHi, (iii) OH-, (iv) H 20, (v) CO~-, (vi) CH3COO-, (vii) HCl03·
C2H s(T, (viii) ,(ix) NOi. (e) HMn04 Higher oxidation number of Mn.
(f) H 2SO 4 Higher electronegativity of S.
6. Conjugate pairs Conjugate pairs 11. (i) Acidic, (ii) Alkaline, (iii) one proton, (iv) non-aqueous
Acid Base Acid Base solutions, (v) an electron pair acceptor, (vi) an electron pair donor,
(i) HS- S2- H30 + H 2O (vii) Lewis bases, (viii) A Bronsted acid, (ix) Weak base, (x)
(ij) NzH5 N zH 4 H 2O OH- Neutralisation.
(iii) NHg NHi H 2O OR"' 12. (a) HF < HCl < HBr < HI
CH3 COO- H30 + (b) HClO < HCIO z < HCI0 3 < HCl0 4
(iv) CH 3 COOH H2O
(c) H 20 < CH30H < OH- < CH:;O-
(v) [AI(H20)613+ [AI( H zO)s(OH)]2+ H3 0 + H2O
(d) SiOz < CO 2 < NzOs < 503
(vi) HC03 CO~- H2O OH-
(e) CIO:! < ClO; < CIOi < CIO-
(vii) HPO~- POt- H2O OR"' (f) [Na(H20)nl+ < [Ca(H20)n]2+ < [Al(H20)6J3+ < [Fe(H20)613+
(viii) H zFe(CO)4 [HFe(CO)4r CH30H~ CHgOH (g) F- < OH- < NHi' < CH;
(ix) HS0 4 SO~- H2O OR"' (h) CH4 < NH3 < H20 < HF
7. Species Conjugate acid Conjugate base (j) H30+ < H 2 0 < OH-
(0 NHg NH4 NHi (j) CH3F < CH30H < CH:;NH z
(ii) HCO:; H 2COg CO~- 13. (a) The reaction moves from left to right as HN02 is stfonger
(iii) HS0 4 H 2S0 4 SO~- than HCN, i.e., it is a better proton donor.
(iv) H 20 HgO+ OR"' (b) HF is a strong acid than HzO, The reaction moves from right
(v) CH 3 COOH CHgCOOH~ CHgCOO- to left.
(vi) H2NCHzCOOH
.
H 3NCHzCOOH H 2NCHzCOO-
(c) The reaction moves from right to left as Na+ is a very weak
acid while NaOH is a strong alkali.
(vii) HS- 52-
Oz- Answers : Matching Type Questions
(a-vii); (b-v); (c-viii); (d-i); (e-iii); (f-iv); (g-ii)i {h-vil.
Acids and Bases 171
tttUS1MTIONS OF OBJECTIVE QUESTIONS

1. Boric acid is a weak Lewis acid. When it is dissolved in 7. Consider the following Lewis add-base reaction,
water, the aqueous solution contains ions : SnCl4 + 2Cr ---7 SnCI~-
(a) H 3B03 :;:::::::!! HzBO; + H+ Acid
Hybridization of Sn in SnC4 and SnC~- are respectively:
(b) H 3B03 + HzO :;:::::::!! B(OHY;;; + H+
(a) sp3, sp3d2 (b) dsp2 to sp3d z
. (c) H 3B03 .:;:::::::!! HBO~- + m+ (c) sp3, sp3d3 (d) sp3 to isp3
(d) H 3B03 :;:::::::!! BOr + 3H+ Ans. (a)
Ans. (b) 8. Which of the following statements is incorrect?
(Hint : B(OH)3' i.e., H 3B03 in aqueous medium coordinates with (a) Liquid ammonia like water is an amphiprotic.
a molecule of water to form a hydrated species,
(b) In the equation, Ag+ + 2CN- ------,t [Ag(CN)£, Ag + ion
H
H
>O---cT B(OHh. B3+ ion pulls the cr-electron charge acts as a Lewis add.
of the coordinated O-atom towards itself. The coordinated (c) 1- ion is a Lewis as well as Bronsted base.
oxygen, in tum, pulls the cr-electron charge of the O-H (d) BF3 is a Lewis as well as Bronsted acid.
bond of the attached water molecule towards itself. This Ans. (d)
facilitates the removal of proton ion from the O-H bond.] (Hint : (a) NB3 + NH3 ~ NH4 + NH2
2. Which is the correct trend of the acid strength? Acid Base Acid Base
(a) HCI04 > HCl03 > HCIOz (b) Ag + acts as a Lewis add as it accepts lone pairs of
(b) H 3P04 > H3P03 > H 3PO Z electrons from CN- ions.
(c) HF > HCl > HBr (d r ion contains lone pair of electrons which it can
(d) HCl > HF > HzS donate, hence it can act as a Lewis base. r can accept
Ans. (a, d) proton, hence it acts as a Bronsted base.
(Hint: (a) The number of electronegative atoms with central (d) BF3 acts as a Lewis add as it is an electron pair
atom increases. acceptor but it has no tendency to lose a proton, hence
(b) All the three have nearly same acid strength. it is not a Bronsted acid.]
(c) Acid strength increases in the hydrides in a group, if 9. Given,
size of the central atom increases. Acid pKa
(d) HO is stronger than HF and HF is stronger than HzS.] (A)CH3C0 2H (i) 0.7
~. In 13, Lewis base is : (B) CCl 3CO zH (ii) 0.2
(a) 12 (b) I~ (C) CICHzCOzH (iii) 4.8
(d 12 (d) 1- (D) F3CCO zH (iv) 2.9
Ans. (d) The correct code is:
!Hint: 12 + [' ---cT I3 ] A B C D
Acid Base
(a) (iii) (D (iv) (ii)
4. AlC13 acts as an add according to the concept of : (b) (ii) (iv) (D (iii)
(a) Bronsted-Lowry (b) Arrhenius (c) (iii) (ii) (i) (iv)
(c) Lewis (d) all of these (d) (i) (iii) (ii) (iv)
Ans. (c) Ans. (a)
(Hint : AI in AlCl3 is electron deficient. It can accept an electron (Hint : Smaller the value of the pK. indicates the stronger acid.]
pair.]
10. Which of the following represent conjugate acid-base pairs?
5. The conjugate base of NH3 is :
(a) HzO, H30+ (b) OW, HN03
(a) NH4 (b) NH2
(c) HZS04t SO~- (d) HCZH30z, C2H 30 Z
(c) NH2- (d) NH20H
Ans. (a, d)
Ans. (b) (Hint : The conjugate acid-base pairs differ by H+.
!Hint : NB3 :;:::::::!! NH'2 + H+j
6.
Acid Base
1 mole of H 3P03 is neutralised by.......... mole/s of NaOH:
H20 H3O+). (HC2H 30 2 C2 H
( Base Acid' Add Base]
P2')
(a) 6 (b) 3 (c) 2 (d) 1
Ans. (c)
(Hint : H3P03 is a dibasic acid. H 3P03 :;:::::::!! 2H+ + HPO~- ]
172
-..•!'---
...
I OBJECTIVE QUESTIONS
Note: Choose the correct answer out of given alternatives in each question..
. 1. Acids are the substances that yield H+ ions in aqueous (a) NHt EJ ·(b) CO~- EJ
solutions while .bases yield OH- ions. In a neutral solution: (c) H 2SO 4 EJ (d) HS- EJ
(a) There are rio 1-1+ ions. EJ 15. Which of the followillg is a soft acid according to Pearson's
(b) There are no OH- ions EJ concept?
(d There are neither H+ nor OH- ions EJ (a) Ag+ EJ (b) Sr2+ EJ
(d) H+ and OH- ions are present in very small but equalin (c) A13+ EJ (d) K+ EJ
number EJ 2
16. The conjugate acid of HP0 - is : .
4
2. Which of the following is a weakest base ? 2
EJ
~;~ ~~~H ~ .~~~ ~:~~~;~ ~ ~:; ~bi?4 ~ ~:; ::~~:- EJ
3. Which of the following represents acid-base pair for. the 17. Which of the following is a Lewis base ?
equilibrium reaction, (a) H 20 EJ (b) HCI EJ
HCl +. H 20 ::.i== H30+ + Cl- ? (c) NHt EJ (d) CH 4 EJ
(a) HCI; H 20 0 (b) HCl, H30+ EJ. 18. In the reaction,
(d HCli cr' EJ (d) cr, H 20 EJ Bel3 + PH3 ~ Cl3B f- PH3, LeWIS base is :
4. The conjugate acid OfS20~- is : (a) BCl3 EJ (b) PI-I3 EJ
(a)· HS 20ii EJ (.b) HS04 EJ (c) Cl3B-PH3 EJ (d) none of these EJ
(c) H 2SO4 EJ (d) H 2S20 3 EJ 19. In the reaction,
5. The conjugate base of H 2P04is : [C.E.T. (Kamataka) 2008] HC 20 4 + pot ::0:::=. HPO~- + czoI-
(a) H 3P04 EJ (b) HPO~- EJ
which are the two Bronsted bases ?
(c) pot EJ ·(d) H 3P03 EJ
(a) HC Z0 4, pot EJ (b) HPO~-, c 20l- EJ
6 .. Which of the following is a Lewis acid ?
(c) pot, C20~- EJ (d) HC 20 4, HPO~- EJ
(a) NH3 EJ (b) H 2S04 EJ
+ 20. The conjugate acid of NHi is :
(d H30 EJ (d) AICl 3 EJ
(a) NH3 .EJ (b) NH20H EJ
7. BF3 is taken as an example of Lewis acid because it behaves:
(a) electrophile EJ (b) nucleophile EJ (d NHt EJ (d) N2H4 EJ
(d neutral molecule EJ (d) free radical' EJ 21. The strongest Bronsted base in the following anion is :
8. The strongest acid of the follOwing is : fa) ClO- EJ (b) ClO2: EJ
(a) HCl EJ (b) H 2SO 4 EJ (c) Cl0 3 EJ (d) Cl0 4 EJ
(d HCl0 4 EJ (d) H 3P04 EJ 22. The strongest Lewis base among the following is :
9. Which of the following is the Bronsted acid ? (a) OH- EJ (b) NH 2" EJ
(a) Cl- EJ (b) HC03 EJ (d CHi EJ (d) P- EJ
(c) .HCOO- EJ (d) CH3COO- EJ 23. Which of the following is a Lewis acid ?
10. The. reaction of water with ammonia is given by the (a) PCls EJ (b) NCl 3 EJ
following equation, (c) NF3 EJ (d) AICl 3 EJ
H20 + NH3 ::;::= NHt + OH- 24. The following equilibrium is established when HCI is
in this reaction water behaves as :
. dissolved the acetic acid,
(a) neutral EJ (b) base EJ
HCl + CH3COOH ::;::= Cl- + CH3COOH!
(c) acid EJ . (d) both acid and base EJ
the set that characterises the conjugate acid-base pairs is :
11. The compound that is not a Lewis acid is :
(a) BF3 EJ (b) BaCl 2 EJ (a) (HCI, CH3COOH) and (CC CH3COOH z) EJ
'(c) AICl 3 EJ (d) SnCl 4 EJ z)
(b) (HCl, CH3COOH and (CH 3COOH, Cn EJ
12. Weakest acid of the following is : z,
(c) (CH3COOH HC!) and (Cr, CH3COOH) EJ
(a) CI03(OH) D (b) CI02(OH) EJ z,
(d) (HCl, cn and (CH3COOH CH3 COOH) EJ
(c) SO(OH}z EJ (d) S02(OH)2 EJ 25. What is the decreasing order of strength of bases,
13. Ionic theory of acids and bases was proposed by : OH-, NHi, H-C==C and CH3-CH2: ?
(a) Lowry EJ (b) Bronsted EJ (a) CH 3-CH2: > NHi > H-C=C > OH- EJ
(c) Lewis EJ (d) Arrhenius EJ (b) H-C=C > > NHi > OH- EJ
14. WhiCh of the following can act as both a Bronsted acid and (d OH- > NH2: > H-C==C > CH3-CH2: EJ
a Bronsted base ? (d) NH2: > > OW > CH3-CH2: EJ
Acids and Bases 173
26. Which is the weakest base among the following ? 39. For. HCl + CH3COOH system, acetic acid serves as :
(a) Cl- D (b) r D (a) protophilic solvent D. (b) protbgEmic solvent D
(d Br- D (d) F- D (c) aprotic solvent D (d) none of these D
27. Among the trihaHdes of nitrogen, which one is the. least 40. Ampholyte is :
basic? (a) H 20 D (b) Zn(OJIh D
(a) NI3 D (b) NBr3 D (c) H 2NCH 2COOH D. (d) all of these D
(c) NC1 3 D (d) NF3 D 41. A reaction between AlCl3 and NH3 is called:
28. In which of the following cases the acid strength is highest? (a) addition D (b) substitution D
(a) pKa 5 D (b) pKb = 10 D (c) neutralisation D (d) hydrolysis D
(c) Ka 10-6 D (d) Kb == 10-11 D 42. Which of the following gases on dissolution in water make
29. Dissociation of H 3P03 occurs in ..... stages. the solution acidic ?
(a) 1 D (b) 2 D (A) CO, (B) COz, (C) S03 arid (D) PH3
(c) 3 D (d) 4 D (a) (A) and (B) D (b) (B) and (C) D
30. The strength of the acid depends on the: (c) (C) and (D) D (d) (B) and (D) D
(a) number of hydrogen atoms present in the molecule D 43. Acid strength of the weak acids HAv HA z and RA3 can be
(b) density D written as,
(d oxygen content D HAl < HAz and HA3 < HAl
(d) concentration of hydrogen ions furnished by ionisation . the correct order of strength of the conjugate bases would
D be:
31. The dissociation conStants of acids HA, HB, HC and HD (a) Ai > Ai > A2 D (b) Ai = A2 < Ai D
are 3 x 10-5, 5 x 10-9, 1 x lO-z and 7 x 10-5 respectively. The . (c) Ai = Ai < Ai D (d) none of these D
weakest acid is : 44. Pair of amphiprotic species is : [Roorkee 1991]
(a) HD D (b) HA D (a) H ZC03 and HC03 D (b) H ZC03 and H 20 D
(c) HB D (d) HC D (c) CO~- and H30+ D (d) HC03 and HzO D
32. On the basis of ..... acid-base concept, the redox reactions 45. For the reaction,
are also considered as acid-base reaction. NHt + NH3 + HS-,
(a) Arrhenius D (b) Lewis D NH3 and Sz- are a group of :
(c) Usanovich D (d) Bronsted-Lowry D (a) bases D
33. The concept that acid is proton donor and base is proton (b) acids D
acceptor was given by : (d conjugate pair of acid and. base D
(a) Arrhenius D (b) Bronsted-Lowry D (d) none of the above D
(c) Lewis D (d) Faraday D 46. HN03 and HF both are acids. But when HN0 3 dissolves in
34. According to Lewis concept, the acid is : HF, it behaves as :
(a) proton acceptor D (b) electron-pair donor D (a) an acid 0 (b) a base D
(c) electron pair acceptor D (d) proton donor D (c) a Zwitter ion 0 (d) amphiprotic solvent D
35. According to the Lewis acid-base concept: 47. Which of the following is not a Lewis acid?
(a) molecule in which all atoms have their octets is an acid [P.E.T. (M.P.) 2002]
D (a) CO 0 (b) SiCl 4 D
(b) negatively charged ions are acids D (c) 503 D (d) Znz+ D
(c) all positively charged ions are not acids D 48. Species acting both as Bronsted acid and base is :
(d) molecule in which a central atom has available d-orbital [A.l.E.E.E. 2002]
to accommodate electron pair is an acid D (a) HS04 o (b) Na2C03 o
36. Which of the following is a Lewis base ? (c) NH3 o (d) OH- o
(a) CH3NH2 D (b) H30+ D 49. In the equation: 12 + r~· Ii, which is the Lewis base?
(c) AICl 3 0 (d) BF3 D [P.M.T. (Raj.) 20021
37. According to Lowry-Bronsted concept, the relative strength (a) 12 o (b) 1- o
of the bases CH3COO-,OH- and Cl- follows the order: (d 13 o (d) None of these o
(a) CH3COO- > OH- > cr D 50. Which represent only umphiprotic species ?
(b) OH- > CH3COO- > cr D (a) HjO, HPOt HC0 3 D
(c) CH3COO- > Cl- > OH- D (b) H 20, HPO;-, H2P0 2 o
(d) OH- > cr > CH3COO- D (d HS0 4, H ZP0 4, H 2POi o
38. Which of the following could act as a Lewis acid but not (d) All of these o
Bronsted acid ? 51. Which does not react with NaOH ?
(a) HCl D (a) NaH2P02 0 (b) NazHP03 o
(c) H503 D (c) NazHPOz D . (d) NaHC0 3 D
52. [Cu(HzOh(OHW + [Al(HzO)613+ ~ [CU(H ZO)4]Z+ (a) (iii) < (0 < (iv) < (ii) 0
(b) (iv) < (ij) < (iii) < (i) 0
At Az A3 (c) (ii) < (iii) < (i) < (iv) 0
(d) (i) < (iii) < (ii) < (iv) 0
+ [Al(H2O)s(OH)f+ 64. H3P03 has ..... non-ionisable P-H bond or bonds.
A4
[J.E.E. (Orissa) 2008)
(a) At is an acid and Az is a base 0 (a) none o (b) 1 o
(b) At is a base and Az is an acid 0 (c) 2 [] (d) 3 o
(c) A3 is conjugate acid of At and A4 is conjugate base of 65. Which is tribasic acid ? [B.C.E.C.E. 2008)
Az 0 (a) H3P02 0 (b) H 3P0 4 o
(d) A3 is conjugate base of At and ~ is conjugate acid of (c) H 4PZ0 7 0 (d) H 3P03 D
0 66. Identify Bronsted-Lowry acids in the reaction given :
Az
53. Water is a : [K.C.E.T. 2002] [AI(H 20)6]3+ + HC03' ~ [Al(H 20)s(OH-)]2+ + H 2C03
(a) protophobic solvent 0 (b) protophilic solvent 0 (A) (B) . (C) (0)
(c) amphiprotic solvent 0 (d) aprotic solvent 0 The correct answer is : [E.A.M.C.E.T. (Med.) 2008]
54. Ammonium ion is : [K.C.E.T. 2002] (a) (A), (e) 0 (b) (8), (0) 0
(a) a conjugate acid 0 (c) (A), (D) 0 (d) (B), (0 0
(b) a conjugate base 0 67. Which is· correct trend of the acid strength ?
(c) neither an acid nor a base 0 (a) H 25 > H20> HF o
(d) both an acid and a base 0 (b) HCI04 > HCl03 > HCl02 o
55. H:iP03 phosphorus acid is : [P.M.T. (Kerala) 2003] (c) H 3P04 > HsP03 > H3P02 o
(a) diprotic acid 0 (b) triprotic acid 0 (d) HN02 > HN03 > H zN 20 2 o
(c) monoprotic acid D (d) insoluble in water 0 68. The order of Lewis acid strength is :
56. Arrange NHt, H 20, H;O, HF and OH- in increasing order (a) BBr3> BCl3 > BF3 0 (b) BCl3 > BBr3 > BF3 0
of acidic nature : [B.V. (Pune) 2003] (c) BF3 > BCl3 > BBr3 0 (d) BCl3 > BrF3 > BBr3 0
(a) H30+ < NH! < HF < OH- < H.P 0 69. The increasing order of acidity of HzOz, H 20 and COz is :
(b) NHt < HF < H30+ < H 20 < OH- 0 (a) H20z> H 20> CO2 0 (b) H 20 Z > C02> H20 0
(c) OH- < HzO < NHt < HF < H30+ 0 (c) H 20> H202 > CO2 0 (d) CO2 > HzOz > H20 0
(d) H30+ > HF > HzO > NHt > OH- 0 '70. The true statement for the acids of phosphorus, HsP02,
57. Which among the following is amphoteric oxide ? H3P03 and H3P04 is :
[A.I.E.E.E. 2003] (a) all of them are reducing agents 0
(a) Zno 0 (b) Na20 0 (b) all of them are tribasic acids 0
(c) S02 0 (d) BZ0 3 0 (c) the geometry of phosphorus is tetrahedral in all the
58. Which of the given hydride of the nitrogen is acidic in three 0
nature? [P.M.E.T.2003] (d) the order of acidity is H 3P04 > H3P03 > H 3P02 0
(a) NH3 0 (b) N3H 0 71. Of the following acids, the one which has the capability to
(c) N zH 4 0 (d) All of these 0 form complex compounds and also possesses oxidising and
59. A group of acidic oxide is : [P.E.T. (M.P.) 2003] reducing properties is : [J.E.E. (W.B.) 2009]
.(a) cr03t Mnz07 0 (b) ZnO, Al20 3 0 (a) HN03 0 (b) HN02 0
(c) CaO, Zno 0 (d) NazO, Al20 3 0 (c) HCOOH 0 (d) HCN 0
60. The conjugate acid of 50~- will be : . 72. Three reactions involving H 2P04 are given below :
[M.G.I.M.S. (Wardha) 2003] (i) H 3P04 + H 20 ~ H30+ + H 2P04
(a) H 2SO4 0 (b) H50 4 0 (ii) H2P04 + H 20 ~ HPO~- + H30+
(c) 50~- 0 (d) 5 2- 0 (iii) H 2P04 + mr ~ H 3P04 + 0 2-
61. H 3B03 is: [I.LT. (5) 2003] In which of the above does H 2P04 act as an acid ?
(a) Monobasic and weak Lewis acid 0 [A.I.E.E.E. 2010]
(b) Monobasic and weak Bronsted acid 0 (a) (i) only 0 (b) (ii) only 0
(c) Monobasic acid and strong Lewis acid 0 (c) (i) and (ij) only 0 (d) (iii) only 0
(d) Tribasic and weak Bronsted acid 0 73. Pair of amphoteric species is :
62. For H 3P03 and H3P04 the correct choice is : [U.T. (5) 2003] (a) H2C03 and H 20 0 (b) HC03 and H 20 []
(a) H 3P03 is dibasic and reducing 0
(b) H 3P03 is dibasic and non-reducing 0
(c) H2C03 and HC03' 0 (d) CO~- and H30+ o
(c) H 3P04 is tribasic and reducing 0 74. Hg is found in nature as Hg5 because : .
(d) H 3P03 is tribasic and non-reducing 0 (a) Hg2+ is soft acid and 52- soft base o
(b) Lattice energy of HgS is high []
63. Four sI?ecies are listed below :
(i) HC03 (ii) H30+ (iii) HS04 (iv) HS03F (c) Hg and 5 are close in periodic table o
which of the following is the correct sequence of their acid (d) Ionisation energy of Hg is very high o
strength? [A.I.E.E.E. 2008]
Acids and Bases 175
1. (d) 2. (b) 3. (c) 4. (a) 5. (b) 6. (d) 7. (a) 8. (c) 9. (b) 10. (d
11. (b) 12. (c) 13. (d) 14. (d) 15. (a) 16. (a) 17. (a) 18. (b) 19. (c) 20. (a)
21. (a) 22. (d 23. (d) 24. (d) 25. (a) 26. (b) 27. (d) 28. (d) 29. (b) 30. (d)
31. (c) 32. (c) 33. (b) 34. (d 35. (d) 36. (a) 37. (b) 38. (d) 39. (a) 40. (c)
41. (c) 42. (b) 43. (a) 44. (d) 45. (a) 46. (b) 47. (a) 48. (a) 49. (b) 50. (c)
51. (a) 52. (b, c) 53. (c) 54. (a) 55. (a) 56. (c) 57. (a) 58. (b) 59. (a) 60. (b)
61. (a) 62. (a) 63. (d) 64. (b) 65. (b) 66. (c) . 67. (b) 68• (a) 69. (d) 70. (c)
71. (b) 72. (b) 73. (b) 74. (a)
-~ Objective Questions for liT ASPIRANTS -~

1. In the reaction, AlCl3 + Cl- = AlGi, AlCl 3 can be classified 6. BF3 is a:
as: (a) Bronsted acid 0 (b) Bronsted base 0
(a) an acid o (b) a base o (c) Lewis acid 0 (d) Lewis base 0
(c) a salt o (d) none of these o 7. Which is correct trend of the acid strength?
2. Identify the species that is amphiprotic: (a) HCl04 > HCI03 > HClOz 0
(a) HI 0 (b) H ZP0 4 o (b) HsP04> H3P03> H 3PO Z 0
(c) NH4 0 (d) C05- o (c) HCl > HBr > HI 0
[Hint : H2POi + H20 ~ H3P04 + OH-; (d) All are true 0
H2POi + H20 ~ HPO~- + H30+.J 8. Which of the following cannot act as a Bronsted base?
3. Consider the following Lewis acid-base reaction, (a) HC03" 0 (b) CO~- 0
AICl3 + Cl- ~ AICl 4 (c) NHi 0 (d) NHt 0
Hybridization of Al in AICl3 and AIC14 are respectively: 9. Which one of the following is most basic?
(a) sp3, dspz 0 (b) spz, dspz 0 (a) CI- 0 (b) F- 0
(c) dsp2, sp3d 0 (d) sp2, sp3 0 (c) 1- 0 (d) Br- 0
4. In a mixture of concentrated H 2SO4 and HN03, inter- [Hint: The conjugate base of a weak acid is a strong base.}
mediate formed is: 10. Which of the following statements is true?
(a) H2SO4 o (b) SO;- o (a) HsP03 is a stronger acid than H2S03 0
(c) H zN03" o (d) HzNOj o (b) An aqueous solution of HF is a stronger acid than HCl
[Hint : HP04 + HN03 ~ H2NOj + HS04:1 o
5. HN03 can accept proton and thus, acts as Bronsted-Lowry (c) HCI04 is a weaker acid than HCl03 o
base in: (d) HN03 is a stronger acid than HNOz o
(a) H ZS04 o (b) HF o
(c) both o (d) none of these o
[Hint : HF + HN~ H2NOj + n
1. (a) 2. (b) 3. (d) 4. (d) 5. (c) 6. (c) 7. (a) 8. (d) 9. (b) 10. (d)
176 G.R.E. Inorganic Chemistry for Competitions
Matrix Matching Questions for liT A§pirant§

1. Match List-l with List-II: (d) Cl04. is weakest (s) Strongest Bronsted acid
List-I List-II conjugate base of
(e) CH 4 (0 Weakest Bronsted acid
(a) HF (p) Strongest acid
4.· Match List-I with List-II:
(b) HCI (q) React with glass
(c) RBr (r) Monobasic List-I List-II
(d) HI (s) Strongest reducing agent (a) Molecules with empty (p) Lewis base
2. Match the solvents in List-l with their classifications in d-orbital with the'
List-II: central atom
List-I List-II (b) Molecules with incomplete (q) Electron pair acceptor
octet
(a) Benzene (p) Protogenic
(c) Multiple .bonded (r) Lewis acid
(b) Water (q) Protophilic
compounds like CO, NO
(c) Liquid NH3 (r) Amphiprotic
(d) CS2(l) (s) Aprotonic (d) R-NH2' R-~-H (s) Electron pair donor
3. Match List-I with List-II: 5. Match List-I with List-II:
(a) OH- (p) Conjugate acid of 0 2- (a) Oxide ion donor (p) Add-base equilibrium
(b) HCl04 (q) Conjugate acid of H 20 (b) CaO Ca2+ + 0 2- (q) Acid (lux-flood)
(d H30+ (r) Conjugate base of H 20 (c) 503 (r) Hard base
(d) C01- (s) Base (lux-flood)
1. (a-q) (b-r) (c-r) . (d-p, r, s) 4. (a-q, r) ar:q, r) (c-p, s) (d-p, s)

2. (a-s) (b-p, q, r) (c-q) (d-s) 5. (a-s) (b-p) . (c-q, r) (d-r, s)
3. (a-p, r) (b-s) (c-q) (d-s) (e-t)

The following questions consist of an Assertion (A) and 3. (A) If a base is strong, its conjugate acid is weak.
Reason (R). Use the following key to choose the correct answer: (R) HA is a conjugate acid of the base A-.
(a) If both (A) and (R) are correct and (R) is the correct 4. (A) H 2PO'3 is amphiprotic ..
explanation of (A). (R) H 2P0'3 can act as an acid by losing a proton as well as a
(b) If both (A) and (R) are correct but (R) is not the correct base by accepting a proton.
explanation of (A).
s. (A) pH of 10-9 N HCl is 9.
(c) If (A) is correct but (R) is incorrect.
(R) pH is defined as the negative logarithm of [H+].
(d) If both (A) and (R) are incorrect.
6. (A) CaO donates oxide, hence it is a base and CO 2 accepts
(e) If (A) is incorrect but (R) is correct.
an oxide, hence it is an acid. This is in accordance with
1. (A) HCI04 is stronger acid than HCl03•
Lux-Flood concept.
(R) Oxidation state of Cl is + 8 in HCl04 and in HCI03 is (R) Cu+, Ag+, Au+, etc., are soft acids while U+, Na+, Ca+,
+5. etc., are hard acids.
2. (A) BF3 is a Lewis acid as well as Bronsted-Lowry acid. Molecular mass
7. (A) Equivalent mass of a base;;; - - - - - - -
(R) Any species which can accept a lone pair of electrons is
Acidity
a Lewis acid and the species that can lose a proton is
(R) Acidity is the number of replaceable hydrogen atoms
Bronsted-Lowry acid. in one molecule of the base. IA.I.E.RE. 20081
1. (c) 2. (e) 3. (b) 4. (a) 5. (e) 6. (b) 7. (c)

Acids and Bases 177
Tile answer to eadl of the following questions is a single 3. The total number of amphoteric oxides and hydroxides
digit integer, rallging from 0 to 9. among the following is:
1. The total number of diprotic acids among the following is: Na20 CaO Al(OHh Cr(OHh
H 3P04 H2SO4 H3P03 H 2C03 SnO Zno Ca(OHh Fe(OHh
H2S207 H3B03 H3P0 2 H 2Cr04 4. Oxy acids in gene;al can be formulated as XOn(OH)m' What
HzS0 3 is the value of 'm' in H 3P03?
2. The total number of triprotic acids among the following is: 5. The total number of Lewis acids among the following is :
H3P041 H3PO~ H 3POZI H3B03, H4P207 BF31 H 20, NH31 AlC131 Ag +, PCl3, R-NH z
1. (6) Six out of the given adds are diprotic. 4. (2) H3P03 is diprotic. It has tWo --OH groups. It is represented
H2Sz~,Hz5O:l, H 2SO4, H3P03, H 2C03, H 2Cr04 as HPO(OH)2'
2. (1) Only H3P04 5. (4) BF3, AICI3, Ag+, PC13 are Lewis adds.
3. (4) SnO, ZnO, Al(OHh and Cr(OH)3 are amphoteric in natun'
CHAPTER 4
General Principles of
Extraction of Metals
4.1 OCCURRENCE OF ELEMENTS

Contents: All materials found in the earth are composed of chemical elements. At present
117* elements are known but all of them do not occur in nature. Out of the 92
4.1 Occurrence of Elements
elements from hydrogen to· uranium all with the exception of few such as
4.2 Occurrence of Metals
technetium, promethium, astatine, francium, etc., are found in earth. The
4.3 Metallurgy
elements above uranium are man-made which have been synthesised by
4.4 Concentration or Dressing of the Ore
artificial means. These elements are called transuranic elements and are
4.5 Extraction or Isolation of Crude Metals radioactive in nature.
4.6 Thermodynamic Principles of Out of naturally occurring elements, only ten elements make up about 99%
Metallurgy
mass of the earth's crust, oceans and atmosphere. The first ten most abundant
4.7 Applications of Eillngham Diagram in
elements in nature (earth's crust, oceans and atmosphere) are:
Pyrometallurgy
4.8 Third Operation-Refining or 1. Oxygen 2. Silicon 3. Aluminium 4. Iron 5. Calcium
Purification (49.5%) (25.7%) (7.5%) (4.7%) (3.4%)
4.9 Furnaces 6. Sodium 7. Potassium 8. Magnesium 9. Hydrogen 10. Titanium
4.10 Refractory Materials (2.6%) (2.4%) 0.9%) (0.87%) (0.58%)
Thus, a few elements are very abundant, but most of the elements are
very scarce. [Some of the common elements such as copper, zinc, tin and
lead are not abundant but are found in nature in rich deposits from which
these can be easily extracted.]
If the e:ntire universe is considered, then 90% of the matter is hydrogen.
Helium is the second most abundant element amounting to 9% and the
remaining elements make up only 1% of the universe with oxygen, neon,
carbon and nitrogen next in order of decreasing abundance.
The natural mode of occurrence of an element is largely dependent upon
its chemical nature. The elements occur in nature sometimes free (or native)
but mostly in the combined state.
(i) Native state: The elements which are least reactive and have little
Fig. 4.1 Element in native state : or no affinity for oxygen, moisture and other chemical reagents occur in a
Gold is so unreactive that it occurs in free or native state, i.e., in uncombined state, e.g., gold (Fig. 4.1), silver and
the Earth as the metal itself. The vein
of gold are shown in this rock
platinum metals are found in native state. Liquid droplets of mercury are
*Recently, elements with atomic numbers 113, 115 and 118 have been reported.
General Principles of Extraction of Metals 179
found associated with cinnabar (HgS). Nitrogen, oxygen and Carbonate Sidetite FeC03
noble gases are found in free state in the atmosphere. Carbon Lead Carbonate Cerussite PbC0 3
in the form of diamond, graphite and coal is found in a free Sulphate Anglesite PbS0 4
Sulphide Galena PbS
state in earth's crust. Deposits of sulphur are also found
MagneSium Sulphate Epsom salt MgS0 4, 7H20
deep underground in uncombined state. Chloride KCI,MgCI 2,6H20
Carnallite
(ii) Combined state: Elements which are chemically Carbonate Magnesite MgC0 3
reactive, i.e., are readily affected by oxygen, moisture, CO2, Manganese Oxide Pyrolusite MnOz
etc., of the atmosphere occur in a combined state in the form Mercury Sulphide Cinnabar HgS
of simple or complex compounds. These compounds are Silver Sulphide Argentite or Ag 2S
called minerals. In the combined state, elements are Silver glance
generally pr-esent as oxides, carbonates, sulphides, silicates, Chloride Horn silver AgCI
Zinc Sulphide Zinc blende ZnS
Oxide Zindte ZnO
Carbonate Calamine ZnC03
Sodium Carbonate Trona Na ZC0 3 ,2NaHC03 ,3HzO
Natron Na ZC0 3,H zO
Sulphate Glauber's salt Na ZS04,10H 2O
Chloride Common salt NaCl
Potassium Nitrate Indian nitre KN03
Chloride Carnallite KCI, MgClr 6H zO
Sylvine KCI
Silicon Oxide Sand, quartz Si0 2
or flint
Silicates Constituent of
igneous rocks
Fig. 4.2 Element in combined state : which consists
Ruby, an ore of aluminium, is aluminium oxide, AI 20 s, of silicates of
containing a small percentage of chromium oxide, Cr20S Mg, AI, K or Fe
Phosphorus Phosphate Phosp);(orite Ca3(P04)2
halides, sulphates, etc. A few common elements along with
Fluorapatite 3Ca3(P04h,CaF2
their nature of occurrence have been listed in the follOWing
Fluorine Fluoride Fluorspar
table.
Cryolite Na3AIF6
SOME COMMON ELEMENTS WI'rH "rHEIR Bromine Bromide Bromocarnallite KBr' MgBrz' 6H2O
Sea water contains
NATURE OF OCCURRENCE
bromides of Na,
Nature of Name of K, Mg and Ca
Composition of
Element Iodine Iodate Caliche NaI03
occurrence minerals minerals
Iodide Kelp-ashes of
Aluminium Oxide Bauxite A1203,2H20 sea'weeds
Corundum Al 203 contain iodides
Diaspore A1203'HzO
Fluoride Cryolite Na3AIF6 Earth is the storehouse of a large number of elements, The
Silicate China day AI203,2SiOz-2H20 distribution of these elements is not uniform. The elements
Mica K20,3Alz03,6Si02' 2H 2O are distributed in three main parts of the earth known as
Feldspar KAlSi 30 8 atmosphere, hydrosphere and lithosphere.
Calcium Carbonate Limestone CaC0 3 (A) Atmosphere: It is a blanket of gases which i~
or calcite surrounding the lithosphere and hydrosphere parts of the
Dolomite CaCO y MgC0 3
earth, It has no well defined upper limits and gradually
Fluoride Fluorspar CaF2
Sulphate Gypsum CaS04,2H 2O
merges with the outer space, Of the total mass of atmosphere,
Copper Carbonate Malachite CUC03,CU(OH)2 about 99% is within a height of 30 krn trom the earth's
Azurite 2CuC03 ,Cu(OH)2 surface, The major gases in the atmosphere are nitrogen (78%)
Sulphide Copper pyrites CuFeSz and oxygen (21 %) by volume. Remaining 1% account for
Chalcocite or CUzS other gases such as argon, neon, krypton, xenon, heliurri,
Copper glance carbon dioxide, etc.
Iron Sulphide Iron pyrites FeS2 (8) Hydrosphere: The liquid phase of the earth is called
Oxide Haematite Fe203 the hydrosphere. It covers about 80% of the earth's surface
Magnetite Fe304
and constitutes lakes, streams, rivers and oceans. There are
Limonite Fe20s,3H20
a large number of elements in the form of their dissolved 0 65.0 Mg 0.5

salts present in sea water. C 18.0 K 0.34
Although, sea water contains elements like Na, Mg, Ca, H 10.0 S 0.26
K, Sr, Ba, CI, Br, S, Li, AI, Rb, etc., only four elements Na, Mg, N 3.0 Na 0.14
Cl and Br are commercially obtained from sea water. Sulphur,
Ca 2.4 Cl 0,15
tin, gold, natural gas and petroleum are also being obtained
P 1.0 • Fe 0.005
from sea sources. Iodine, agar-agar, laminarin are the
products which are recovered from seaweeds. Efforts are on BeSides these, the. following elements are present in very
to extract some of the rare metals from the rock-like objects small amounts:
called nodules found on the sea floor. Cu, Zn, Co, Mn, Mo, I and F.
(C) Lithosphere: It is the outermost solid part of the Many elements get accumulated in living organisms. Some
earth and consists of different types of rocks. Almost all the examples are : (i) iodine in seaweeds (ti) vanadium in
naturally occurring elements are found in the lithosphere. It cucumbers (iii) potassiUltt in plants. The reason for such
consists of different types of rocks in which various elements accumulation is not yet known. Living organisms also
are present in the form of minerals. The distribution of main contain different elements in different parts. For example:
(i) Carbon, hydrogen, nitrogen and oxygen are the
r----Calcium 3.6
;---Sodium 2.8 major constituents of biomolecules which are
;---Potassium 2.6 present in the bodies of animals and plants.
.A./--Magnesium 2.1 (ti) Iron is present in haemoglobin-a red pigment of
Titanium 0.4 blood cells.
Silicon Manganese 0.1
27.7 Hydrogen 0.1' (iii) Magnesitim is a constituent of chlorophyll-a green
Phosphorus 0.1 pigment of plants responsible for photosynthesis.
Others < 0.5 (iv) Zinc is present in the eyes of certain animals.
Oxygen (v) Manganese, iron and copper are present in
46.6 chloroplasts.
(vi) Calcium and phosphorus are present in the teeth and
bones of animals.
It is important to note that very little is known as to why
a particular element is present in a specific region of the
Fig. 4.3 Percentage distribution of different living organism. However, it is. known that deficiency of a
elements in lithosphere particular element in the living organism brings many
elements in terms of their relative abundance in the litho- disorders. For exa·mple, deficiency of iron causes anaemia
sphere is shown inFig. 4.3. It is observed that, while that of iodine causes goitre. Similarly, the deficiency
(i) Oxygen and silicon constitute about 73% by mass of
of nitrogen, phosphorus and· potassium in plants retards
the earth's crust. their growth.
(ti) First five elements comprise almost 92% by mass of
the earth's crust.
4111 OCCURRENCE OF METALS
(iii) Aluminium is the most abundant normal or
C,,", (Minerals and Ores)
representative element. The earth's crust is the biggest source of metals. Metals occur
(iv) Iron is the most ,abundant transition metal. in nature sometimes free but mostly in a combined state.
(v) First ten make up over 995% and first twenty make The rocks in which metals occur in the native state or
up 99.97% by mass of the earth's crust. combined state (in the form of compounds) are called
minerals. Every mineral has a definite composition. It may
t1~~ Elements in Living Organisms be a single compound or a complex mixture, usually
Animals and plants organisms consist of complex associated with a number of impurities. The minerals from
substances composed of both metallic and non-metallic which the metals can be conv,eniently and economically
elements. When the analysis of ash of animal tissues is extracted are known as ores.
carried out, it is observed that about 30 elements are present All the ores are minerals but all minerals cannot
in the animal tissues. Abundance of selected elements in the be ores. For example, iron is found in the eo.rth's crust as
hu~an body (mass %) is given ahead: oxides, sulphides and carbonate.
Haematite Fe203 (iii) Halide ores: Metallic halides are very few in nature.
Magnetite Fe304 Chlorides are most common. Fot example,
Iron pyrites FeS2 Metal Name of the ore Composition
Copper pyrites CuFeS2 Na Common salt NaCl
Siderite" FeC03 KandMg Carnallite KG MgCl2, 6H20
Out of the above minerals iron is extracted from oxides. Ag Hom silver AgCI
Thus, oxides of iron, i.e., haematite, magnetite, etc., are the (Iv) Oxldised ores: In these ores, metals are pres~nt as
ores of iron. The minerals of copper are: their oxides or oxysalts such as carbonates, sulphates,
Cuprite CuzO phosphates, silicates, etc.
Copper glance CU2S IInportant ores of this group are :
Copper pyrites CuFeS2 Metal Name of the ore Composition
Malachite CuC03, Cu(OH}z AI Bauxite A1203,2H20
Azurite 2CuC03· Cu(OH}z Sn Tin stone Sn02
Copper is conveniently and economically extracted (cassiterite)
from copper pyrites. Thus, copper pyrites is the ore of Mn Pyrolusite
copper. Similarly, aluminium has several minerals Cr Chromite FeO, Cr20 3
such as: Zn Zincite Zno
Ti llmenite FeO, Ti0 2
Bauxite Al20 3 · 2H 20 Fe Haematite FeZ03
Cryolite Na3AIF6 Magnetite Fe304
China clay A1203,2SiOz' 2H zO Ca Limestone CaC03
,Feldspar KAlSi30S Mg Magnesite MgC03
Mica KzO.3Alz0 3 • 6Si02, 2H20 Zn Calamine Znco3
Ba Barytes", BaS04
However, the mineral bauxite is used for the extraction of Ca Gypsum "' CaS04, 2H20
aluminium. Thus, bauxite is an ore of aluminium. Li Lepidolite (Li,Na,KhAI2(S04h(F,OHh
It is evident from the above examples that a metal may Triphylite (Li,NabP04' (Fe,Mnh(P04h
occur in a number of minerals but every mineral is not
4_
Be Beryl' 3BeO, AI 20 3, 6Si0 2
suitable for the extraction of the metaL This is because the
mineral may contain low concentration of metal or may METALLURGY
contain a large concentration of impurities which 'may not
The whole process of obtaining a pure metal from one of
be easy to remove or process of extraction may not be feasible
its ores is known as metallurgy. .
or commercially viable.
In order to extract the metals from ores, several physical
Ores may be divided into four groups:
and chemical methods are used. The method used in a
(i) Native, ores: These ores contain metals in a free
particular case depends upon the nature of the ore, the
state, e.g., silver, gold, platinum, mercury, copper, etc.
properties of the metal and the local conditions. Thus, it is
These are found usually associated with rock or
not possible to have a universal method for the extraction of
alluvial materials like clay, sand, etc. Sometimes
all the metals from their ores. However, the metallurgy of a
lumps of pure metals are also found. These are
metal involves three main operations:
termed nuggets. Iron is found in free state as
(i) Concentration or dressing of the ore,
meteorites which also have 20 to 30% nickeL
(ii) Isolation of the metal in crude state from the
, (Ii) SulphurisecJ and arsenical ores : These ores
concentrated ore.
consist of sulphides and arsenides in simple and
(iii) Purification or refining of the crude metaL
complex forms of metals. Important ores of this group
are: CONCENTRATION OR DRESSING
Metal Name of the ore Composition OF THE ORE
Pb Galena PbS
Zn Zincblende ZnS The ores usuauy are obtained after mining in the form of big
Hg Cinnabar HgS lumps. These are broken into small pieces with the help of
Ag Argentite or Ag 2S crushers or grinders. This process is called crushing. These
silver glance pieces are then converted into a fine powder with the help
Ni Kupfer nickel NiAs of either a ball mill or stamp mill. This process is termed
Cu Copper pyrite CuFeSz pulverisation.
The ores usually contain soil, sand, stones and other The powdered ore is suspended in a stream of water. The
useless silicates. These undesired impurities present in ores heavier ore particles collect behind the riffles and the gan-
are called gangue (pronounced gang") or matrix. The
II gue particles are carried away with the stream of water.
removal of these impurities from the ores is known as Hydraulic classifier is shown in Fig. 4.5. Powdered ore is
concentration or dressing or benefaction of the ore. To dropped from the top of classifier and a strong stream of
separate the useful minerals from the gangue, both physical water is introduced from the bottom. The lighter gangue
I and chemical methods are used depending on the ore. It can particles are carried away by the water while the heavier ore
be done in a number of ways depending upon the nature of particles settle down. Generally, oxide and carbonate ores
the impurities. are concentrated by this method. For example, tin ore
(cassiterite) and iron ore (haematite) are concentrated by
Ii (A) Gravity Separation gravity method.
This separation is based on the difference in the specific
~ (8) Electromagnetic Separation
gravities of the gangue particles and the ore particles. The
powdered ore is agitated with water or washed with a When one component, either the ore or impurity, is
running stream of water. The heavy ore particles settle down magnetic in nature, this method can be used for separation.
while the lighter particles of sand, clay, etc., are washed A magnetic separator consisting a belt moving on two rollers
away. For this either Wilfley table or hydraulic classifier is is used, one of which is a strong magnet. The powdered ore
used. WOOey table is a wooden table having a slanting floor is dropped on the belt from one end (non-magnetic) and at
on which long wooden strips called riffles are fixed (Fig. 4.4). the other end (magnetic) the magnetic particles are attracted
and fall nearer the roller while non-magnetic particles fall
away from the roller. Ferro-magnetic ores are concentrated
Water by this method. For example, wolframite (FeW04)-a
magnetic ore, is separated from the non-magnetic ore,
cassiterite (SnOz) by this method. "
Electromagnets
Fig. 4.4 The Wilfley table ..;::::z-._======-_--.:~;;?· ."

•• f:~.·
Pov.!ClerliKl ore Moving belt
J •
-.
.:- .: :V.
'. : •• Gangue
-...
Q
Q 0
...
Q
Magnetic ore" _.7~~·,'

~ ....".,"..:....
-:.\,\\.".
Fig. 4.6 Electromagnetic separation
.!!J (C) Froth Floatation Process

Froth floatation is a physical method of separating mineral
from the gangue that depends on differences in their
wettabilities by a liquid.solution. This method is used for the
concentration of sulphide ores. The method is based on the
preferential wetting properties with the frothing agent and
water. The powdered ore is added to water containing pine
oil (frothing agent) and sodium ethyl xanthate (collecting
agent). Cresols and aniline are also added. They act as froth
stabilizers. A vigorous stream of air is now passed through,
which thoroughly agitates the mixture and disposes the oil
Concentrated ore into colloid sized particles. As a result of this, the sulphide
Fig. 4.5 Gravity process
particles of the ore stick to the oil droplets and rise to the
1200"C'
surface in the form of froth supported by air bubbles. Water Al203' xH 20 ) Al203 + xH 20
wets the gangue particles which sink to the bottom. With this
[The above process is known as Baeyer's process.]
method, it is possible to concentrate tlie dense ores such as
(ii) Leaching of silver and gold: Gold and silver are
galena and zinc blende.
extracted from their native ores or silver from argentite ore
Foam carrying (Ag 2S) by leaching. This is also known as Mac':'Arthur Forest
ore particles
Water cyanide process.
dn,,----~J-. --
In this process, the finely powdered argentite ore or the
o native silver particles, or the native gold particles are treated
InlHI with a dilute solution (0.5%) of sodium or potassium cyanide
«
Ore + Water while a current of air is continuously circulated. As a result
+ S~~t~h"
+Pine oil
ll,lllt'lr
Imm;~I~U~-~--I-I--I-------- Wot
.,
silver and gold dissolve by forming respective complex
cyanides. The impurities remain unaffected. These are
filtered off.
Gangue Concentrated
ore 4Ag+SNaCN+02 +2H 20 ~
Fig. 4.7 Froth floatation process 2Na[Ag(CNhl + 4NaOH
Sodium dicyanoargentate (I)
Sometimes depressants are used to prevent certain type (Soluble)
of particles from forming the froth with the bubbles. In the Ag2S + 4NaCN ~ 2Na[Ag(CNhl + Na2S
concentration of galena ore, sodium cyanide is added as a
Na2S is largely oxidised to Na2S04'
depressant for zinc sulphide (ZnS). NaCN forms a layer of
zinc complex, Na2Zn(CN)4 on the surface of ZnS and thereby 4Na2S + 2H20 + 502 ~ 2Na2S04 + 2NaOH + 2S
prevents it from the formation of froth while PbS forms a froth. 4Au + SNaCN + O 2 + 2H20 ~
Thus, PbS is separated from ZnS. 2Na[Au(CNhl +4NaOH
Sodium. dicyanoaurate (I)
;~ (D) Leaching )Soluble}
Ag or Au is recovered from the solution by the addition of
It is a chemical separation. It involves the treatment of
electropositive metal like zinc. ,
the ore with a suitable reagent as to make it soluble while
impurities remain insoluble. The insoluble impurities are 2Na[Ag(CNhl + Zn ~ Na2[Zn(CN)41 + 2Ag
separated by filteration.The impurities, in this case, include 2Na[Au(CNhl + Zn ~ Na2[Zn(CN)41 + 2Au
not only gangue but also chemical entities which are not Sodium tetracyanozincate (ID
solubilized during leaching operation. The following (Soluble)
examples illustrate the procedure.
(i) Leaching of alumina from bauxite ore : Bauxite ore
EXTRAC1"ION OR ISOLATION OF
contains ferric oxide, titanium oxide and silica as impurities. CRUDE .METALS (OxidationIRed~ction)
When the powdered ore is digested with an aqueous solution Metals are usually extracted by reduction. Thus, the concen-
(45%) of sodium hydroxide at about 200°C under pressure' trated ore is converted into a form which is suitable for
(35-36 bar), the alumina dissolves forming sodium aluminate reduction. Oxides are easier to reduce, therefore, the extraction
while ferric oxide (Fe203), Ti02 and silica remain as insoluble of metals involves the following tWo major steps:
part. (1) Conversion of the ore into metallic oxide
Ah03·2H20 + 2NaOH + H20~ 2Na[AI(OH)41 (2) Reduction of the metallic oxide to the free metal.
Sodium aluminate
, (Soluble) 1. Conversion of the ore into metallic oxide
The solution of sodium aluminate is filtered. It may also The ores of the metals are usually in the form of hydrated
contain some sodium silicate and free sodium hydroxide. The oxides, carbonates, sulphides, etc. Depending upon the
filtrate is neutralised by passing CO2 gas, the hydrated Al20 3 nature of the ores, two methods are used for conversion into
gets precipitated. At this point, the solution is seeded with oxides.
freshly precipitated aluminium hydroxide which induces the Note : The ores which are already in anhydrous form-for
precipita tion. example, rutile (Ti0:0-are not subjected to these
2Na[Al(OH)41 + 2C02 ~ A1203' XH20 + 2NaHC03 methods. After concentration, these are directly reduced.
The sodium silicate remains in the solution and hydrated (A) Calcination: This method is commonly used to
alumina is filtered, dried and heated to about 1200°C to get convert hydrated oxides or hydroxides and carbonates into
pure alumina. respective oxides. It involves heating of the ore below its
fusion temperature in absence of air. This step is generally Most of the FeS is converted into FeO which combines with
performed in a reverberatory furnace. The concentrated ore silica to form iron silicate (FeSi03)-a siag (fusible in nature).
is put on the hearth of the furnace and heated by flames Copper is obtained in the form of copper 11Ultte which
deflected from the roof. During· calcination the following contains CU2S and small amount of FeS.
changes may occur. The material becomes porous which can be made easily
Moisture is driven out. Water is removed from hydrated workable in the subsequent step.
oxides or hydroxides. Organic matter is expelled. In some cases chlorinating roasting is done as metal is
obtained by redUction of halide (usually chloride). For
A1203. 2H 20 Heat) A1203+2H20
Bauxite Alumina example, silver ores are heated with sodium chloride.
Heat AgzS + 2NaCl ~ AgCI + NazS
Fe203 ·3H20 ~ Fe203 +3H 20
Limonite Ferric oxide Note: (i) Calcination and roasting may be carried out in the
Carbonates lose carbon dioxide and are converted into same reverberatory furnace. During calcination, air
corresponding oxides. holes are partiany or completely closed while in
roasting, the air holes are open. .
CaC03 Heat) CaO + CO2 (ii) When roasting is done at moderate temperature,
Limestone Cakium oxide the sulphide ore is partially oxidised into oxide
CaC03 . MgC03 . Heat) CaO+ MgO + C02 and partially into sulphate. For example, in the
Dolomite Magnesium roasting of galena and zinc blende.
. oxide
2PbS + 302 ---7 2PbO + 2502
CUC03 ·Cu(OHh Heat) 2CuO +H20 + C02 PbS + 202 ---7 PbS04
Malachite Cupric oxide
2ZnS + 302 ---7 2Zn0 + 2S02
ZnC03 Heat) ZnO· + CO2 Zns + 202 . ---7 ZnS04
Calamine Zinc oxide
The material becomes porous which can be easily reduced ~ 2. Reduction of the metallic oxide
in the subsequent step. to the free metal
(8) Roasting: It is a process in which the ore is heated
in presence of air. During this operation, the temperature is The crude metal is obtained when the roasted or calcined
. kept below the meltirig point of the ore. The sulphide ores ore is put to reduction by using a suitable reducing agent.
are generally subjected to roasting. The roasting is generally The selection of a suitable reducing agent depends upon the
done in a reverberatory furnace or in a small blast furnace. reactivity of the metal. Some of the methods commonly used
As a result of roasting, the following changes occur. to get the free metal from the roasted or calcined ore are briefly
described here.
(0 Moisture is driven out.
(ii) Organic matter is burnt.
(A) Smelting
(iii) The non-metallic impurities such as sulphur,
phosphorus, arsenic are converted into respective volatile This involves reduction of ore to the molten metal at a high
oxides which get removed. temperature. For the extraction of less electropositive metals
S8 + 802 ~ 8502 (Sulphur dioxide) such as Pb, Zn,Fe, Sn, etc., powerful reducing agents such
P4 + 502 ~ P40 10 (Phosphorus pentoxide) as C, Hz, CO, water gas, Na, K, Mg, AI may be used. Some
examples are given below:
4As + 302 ~ 2As20 3 (Arsenious oxide)
PbO+C~Pb+CO
Sulphide ores are converted into metallic oxides.
2ZnS + 302 ~ 2ZnO + 2S02 W03 + 3H2 ~ W + 3H20
Zinc oxide CuO + CO ~ Cu + COz
2PbS+ 302 ~ 2PbO·+ 2S0z Cr20 3 + 2AI ~ 2Cr + AI20 3
. Lead oxide
The process of extracting the metal by heating the metal
2CuzS+30z~ 2Cu20 +2S0 Z
Cuprous oxide oxide with a suitable reducing agent is called PYro-
The sulphm dioxide thus evolved is utilised for the metallurgy.
manufacture of H ZS04• Out of the various reducing agents~ carbon, carbon
In the extraction of copper, the ore is copper pyrites monoxide and aluminium are generally used.
(CuFeSz) which consists of FeS also. The· ore is mixed with (i) Carbon reduction process: It is generally called
silica before roasting. During heating, initially a mixture of smelting. The oxides of less electropositive metals are
CuzS and FeS is .formed. reduced by strongly heating them with coal or coke. Carbon
combines with the oxygen of the metal oxide to form carbon
2CuFeS2 ~ CU2S + 2FeS + S
monoxide which can also act as a reducing agent.
S+O:z ~S02
General Principles of Extraction of Metals
MxOy + yC ~ xM + yeo 3Mn304 + 8Al ~ 9Mn + 4Al20 3

PbO+C~Pb+CO
Large amount of heat energy is released during reduction,
PbO + co ~ Pb + CO2 which fuses both the alumina and the metal.
Similarly, Fe203 + 3C ~ 2Fe + 3CO
Fe203 + 3C0'~ 2Fe. + 3C02 !!§l (8) Self Reduction Process
The ores, even after concentration, contain some gangue. This process is also called autoreduction process or air
To remove. gangue, certain substances are mixed with reduction process. The sulphide ores of less electropositive
concentrated ore which combine with the gangue to form a metals like Hg, Pb, Cu, etc., are heated in air as to convert
fusible material which is not soluble in molten metal. The part of the ore into oxide or sulphate which then reacts with
substances used are called fluxes and the fusible material the remaining sulphide ore to give the metal and sulphur
formed during reduction process is called slag. Slag is dioxide. No external reducing agent is used in this process.
usually lighter and floats on the surface of the molten metal.
.. 2 ~ 2HgO + 2S02} Extraction of Hg,
2HgS + 30
Concentrated ore + gangue + reducing agent + flux 2HgO + HgS ~ 3Hg + 50 2 from cinnabar ore
J.. heated
Metal + slag + gases 2CU2S+302 ~2CU20+2502} ExtractionofCu
Fluxes are classified .as (i) Acidic flux and (ii) Basic flux. CU2S + 2CU20~ 6Cu + 502 from copper glance
An acidic flux (e.g., silica, borax, etc.,) is the chemical
. 2PbS+302'~ 2PbO+2S02} Extraction of lead
substance which removes the basic impurities. 2PbO + PbS ~ 3Pb + 50 2 from galena ore
Si02+ CaO ~ CaSi03 .
Acidic flux Basic impurity Slag
(Gangue) . ~jlJ (e) Electrolytic Reduction
The basic flux (e.g., limestone, magnesite, ferric oxide, etc.,) The oxides of the highly electropositive metals like Na, K,
is the chemical substance which removes the acidic Mg, Ca, AI, etc., cannot be reduced easily with carbon at
impurities. moderate temperatures. For reduction, a very high
MgC03 + 'Si02 ~MgSi03 + CO2 temperature is required at which the metal may combine with
Basic flux Acidic impurity Slag carbon to form a carbide. These metals are thus extracted by
(Gangue)
the electrolysis of their oxides, hydroxides or chlorides in
(ii) Reduction by aluminium (Goldschmidt alumino-
fused state. Sometimes, a small amount of some other salt is
thermic process): This process is employed in the case of
those metals which have very high melting points and are.
to be extracted from their oxides. Their reduction with carbon
Mixture of aluminium
Magnesiu'm fuse
powder and oxide ore
Molten
sodium
"c'---;-- Ring-shaped
steel cathode
Bed of Sand
Fig. 4.8 An apparatus for therrnite reaction
Molten NaCI
is not satisfactory. A mixture of concentrated oxide ore and and CaCI2
aluminium powder, q)mmonly called as thermite, is taken Fig. 4.9 Production of sodium meta.l from fused mixture of NaCI
in a steel crucible placed in a bed of sand. The reaction is and CaCI 2 by Electrolytic reduction by the Down's process
started by the use of an ignition mixture containing mag-
nesium powder and barium peroxide. added to lower the fusion temperature or to increase the
conductivity or both. The metal is liberated at the cathode.
Cr203 + 2Al ~ 2Cr + Al20 3 Sodium is obtained by the electrolysis of fused mixture of
NaCl and CaCl2 (Down's process) or by electrolysis of fused Ellingham Diagram

sodium hydroxide (Castner's process).
Ellingham diagram consists of graphs which represent
NaCI the variation of standard free energy with temperature of the
formation of oxides of various elements, i.e., plots of AfGo V5
llFused T. Similar plots can also be plotted for sulphides and halides.
Cathode ~ Na + + cr ---t Anode These were first plotted by H.J.T. Ellingham. These diagrams
Na+ + e---t Na cr e CI help us in predicting the feasibility of thermal reduction of
an ore.
2CI---t Cl2
Consider the formation of a metal oxide (MxO).
Aluminium is obtained by the electrolysis of alumina
mixed with cryolite. 2xM(s) + 02(g) ---7 2MxO(s)
In this reaction, there is decrease in the value of t1S 0 as
4~1 THERMODYNAMIC PRINCIPLES MxO is solid and Oz is a gas, i.e., ~S is negative. Thus, if
OF METALLURGY temperature is increased, T~SO becomes more negative.
As in the equation,
The basic concepts of thermodynamics are quite helpful in
selecting which element will be the most suitable reducing ~GO ~Ho T~So
agent for a particular oxide during a metallurgical operation. T~So is subtracted, therefore, ~Go becomes less negatiy~,.
It can also predict the optimum temperature at which the i.e., ~G' is likely to increase with rise in temperature
reduction can occur smoothly. and this trend is confirmed from the curves of metal oxides
For any reaction or process, Gibb's Helmholtz free in Fig. 4.10. The following observations are made from the
energy change (~G) is given by the equation, curves.
~G till - T~S ... (i) (i) The slope of the curves of the formation of metal
where till is the enthalpy change and ~S is the entropy oxides is +ve because ~GO becomes less negative or
change and T is the absolute temperature at which the increases with the rise in temperature.
reaction is carried out. For the feasibilitY' 'of any reaction at (ll) Each curve is a straight line except when some
any temperature the value of ~G must be negative at that change takes place in phase (5 ~ 1or 1---7 g). The
temperature. The free energy change is also related to the temperature at which such a change occurs is
equilibrium constant 'K' of the reaction at temperature J::by indicated by an increase in the slope on the +ve side.
the following equation, For example, in the Zn-Zno curve, the melting of
~G - RT In K ... (in
zinc is indicated by an abrupt increase in the +ve
slope at temperature 692 K.
A negative ~G implies a +ve K in the above equation. This
can happen only if the reaction proceeds towards the +200
products. The following conclusions can be drawn :
(D Greater the negative value of free energy change (~C;), 0
more spontaneous is the reaction.
CONOrrlONS FOR ~G TO BE NEGATIVE -200

Oi
AH TAS Favourable conditions N
0
ve (Exothermic) +ve Any temperature '0 -400
- ve (Exothermic) - ve AH> TAS L0
(Temp. should be low) ..,E
.><:
-600 Alz 0 3
+ ve (Endothermic) +ve TIlS > AH CO
(Temp. should be high)
.so
C, -800
<l
(ll) If two reactions are put together in a system and the
net ~G of both the reactions is -ve, the overall reaction -1000
will occur, i.e., a reaction with ~G positive can be
made to occur if it is coupled with another reaction
having a large negative ~G so that the net ~G of both 500 1000 1500 2000 2500
the reactions is negative. Temperature in K -
Such coupling reactions can be easily understood through Fig. 4.10 Ellingham diagrams for oxides of some elements
Ellingham diagram.
(iii) In the case of less reactive metals like silver and nearly the same with rise in temperature, i.e., liGo is indepen-
mercury, liGo becomes positive at high tempera- dent of temperature.
tures. It indicates that both silver oxide (AgzO) and In the s~ond reaction (formation of CO), there is increase
mercury oxide (HgO) are unstable and decompose at in entropy (liSO is positive) and therefore, ~Go becomes more
high temperature. negative with increase in temperature.
However, in thi,rd reaction, there is decrease in entropy
2Ag2 0 Heat) 4Ag + Oz (liSa is negative) and therefore, liGO becomes less negative
2HgO Heat) 2Hg + Oz with increase in temperature.
(iv) In the curve of CO,liGo decreases as liSa increases. ~
This is indicated by ,the downward trend. ~ -200

(v) Any metal oxide with lower value of liGo is more
o
15
stable than a metal oxide with higher liCO. This
t 1s
I
/
I
implies that the metal oxide placed higher in the I E -800 ,,
/
diagram can be reduced by the metal involved in the ~ I,,

formation of the oxide placed lower in the diagra.m.
.5 -1000 ,
~ -1200
/
/
For example, Cr203 can be reduced by AI metal but 983/
/
AI20 3 cannot be reduced by Cr. 500 1000 1500 2000 2500

Cr203 + 2AI----7 AI20 3 + 2Cr Temperature in K -
Thus, the relative tendency of the various metals to Fig. 4.11 Ellingham diagram for the reducing nature of carbon
act as reducing agents is:
Ca > Mg > AI > Cr > Zn > Fe > Ni The above observations can be seen in Fig. 4.11. The three
curves have been found to intersect at 983 K. It implies that
Limitations of Ellingham Diagram above this temperature, the reaction (ii) is most suitable. It
means that carbon can reduce any metal oxide at very high
Ellingham diagram simply tells whether the reduction of temperatures and is then itself oxidised to CO. However, the
a particular oxide with a specific reducing agent is possible reduction with carbon at high temperatures is not preferred
or not. However, it does not tell anything about the kinetics in all cases due to the following reasons:
of the reduction process, i.e., whether the reduction is fast or
(a) It involves high cost.
slow.
(b) Some metals react with carbon at high temperatures
The interpretation of liGo is based on the equilibrium
and form carbides.
constant, 'K'.
(c) There are many practical difficulties in the main-
liGo = - RT In K tenance of high temperature.
Thus, it is presumed that the reactants and products are From the plot for the reaction of carbon monoxide with
in equilibrium: oxygen, it is evident that carbon monoxide acts as a better
MxO + A~xM+AO reducing agent than carbon at temperatures below 983 K.
But, this is not always true because the reactant/product Theory of Reduction of
may be solid.
Metal Oxide with Carbon
Reducing Nature of Carbon During reduction the metal oxide decomposes,
Carbon in theiorm of coke, charcoal or carbon monoxide MxO(s) ----7 xM(s or 1) + 1/2 Oz(g) ... (i)
is used as a reducing agent in pyrometallurgical operations. and the carbon (reducing agent) takes away the oxygen, i.e.,
Such a reduction process used in the extraction of a metal is it undergoes oxidation.
termed smelting. C(s) + 1/202(g) --4CO(g) ... (ii)
When carbon is to act as a reducing agent, the following tlGO(c, CO)
three reactions are possible:
... (iii)
C(s) + 02(g) --4 COz(g) ... (i) 1/2 .1G'(C, C02)
2C(s) + Oz(g) --4 2CO(g) ... (ii) or CO(g) + 1/2 Oz(g) --4C02(g) ... (iv)
2CO(s) + Oz(g) --4 2COz(g) ... (iii) .1GO(C, coz)
In the first reaction (formation of CO2) there is hardly any The role of the reducing agent is to provide a large
change in entropy, i.e., liSa '" 0 and therefore, liGO remains negative ~Go to make the sum of the lirGo of the above
two reactions, (i.e., reduction of metal oxide and oxidation formation oiCO from carbon and formation of C02 from
of carbon or carbon monoxide) negative. CO. The curves cross each other at 1073 K.
Reversing the equation (i) Above 1073 K, ~G" for the formation of Fe203 is less
xM(s or l) + 1/202(g) ~MxO(s) ... (v) negative than ilGq for the formation of carbon monoxide from
AGO(M, MxO) carbon. Thus, above 1073 K, carbon (coke) can reduce Fe203,
i.e., ~rG() for the reaction,
Subtracting equation (v) from equations (ii), (iii) and (iv)
> 1073 K
respectively, we have, Fe203(s) + 3C{s) ) 2Fe(s) + 3CO(g)
MxO(s}+ C(s) ~ xM(sor 1) + CO(g) ... (vi) is negative.
MxO(s) + 1/2 C(s) ~ xM(s or l) + 1/2C02(g) ... (vii) Below 1073 K, ilGO for formation of CO from carbon is less
negative than ~G" for the formation of Fe203. ~rGo for the
MxO(s) + CO(s) ~ xM(s or l) + CO2(g) ... (viii)
reduction of Fe203 with carbon will be positive and hence,
The equations (vi), (vii) and (viii) describe the reduction reduction- is not possible. However, it is observed from the
of the metal oxide, MxO. The~rG() values of these equations diagram that ~Goof formation of CO2 from CO is more
can be obtained from Ellingham diagram (Fig. 4.10). If ~rG() negative than ilGO of formation of Fe203' This means that
values are negative, the reduction is feasible otherwise not. Fe203 can be reduced by CO below 1073 K, i.e., ilrG" for the
Greater the difference, easier is the reduction. reaction,
Without making any calculations for ~rG(), the prediction > 1073 K
about the feasibility of a reduction process can be made by Fe203(S) + 3CO{s) . ) 2Fe(s) + 3C02(g)
looking at the Ellingham diagram. Metal oxide placed is negative.
higher in the diagram can be reduced by the element Thus, in the blast furnace, reduction of Fe203 occurs in
(metal) involved in the formation of the oxide placed lower different temperature ranges either below 1073 K by carbon
in the diagram. monoxide or above 1073 K by carbon (coke).
It is important to riote that if a particular reduction process
does not take place at a lower temperature, it may take place (8) Theory of reduction of CU20
at a higher temperature. Ellingham diagram also helps.in (i.e., Extraction of copper from cuprous oxide)
selecting such a temperature. The temperature is indicated In the Ellingham diagram (Fig. 4.13), it is observed that
by the intersection of ,the two curves. For example, the CU20 curve lies almost at the top while the lines showing
temperature at the intersection point 'A' in Fig 4.10 of two the formation of CO2 from C and CO and the formation of
curves for Al----7 Al20 3 and Mg~ MgOis approximately CO from carbon lie much below it. So it is quite easy to
1665 K. Below this temperature Mg reduces Al20 3 into Al reduce CU20 to the metal by heating with coke at temperatures
but above 1665 K, Al can reduce MgO into Mg. after 500-600 K.
4(1 APPLICATIONS OF ELLINGHAM ~
!2.l
DIAGRAM IN PYROMETALLURGY 0'"
The utility of Ellingham diagram in pyrometallurgy can be 'l5 -400
illustrated by discussing the extraction of iron, copper and
zinc from their respective oxides. l~ '"')
-800
.l<:
~E -1000
(A) Theory of reduction of Haematite (!'l
<:J -1200
In the Ellingham diagram (Fig. 4.12), there are three curves
which illustrate the formation of ferric oxide from iron, 500 1000 1500 2000 2500
Temperature in K -
Fig. 4.13 Ellingham diagram for copper and carbon oxides
However, most of the ores of copper are sulphides and

contain iron sulphide also. Thus, the ores are first roasted in
such a way so that iron is removed and copper sulphide is
converted into cuprous oxide.
2CU2S + 302 ----7 2CU20 + 2502
500 1000 1500 2000 2500
Temperature in K -
The oxide can then be easily reduced to metallic copper
by using coke.
Fig. 4.12 Ellingham diagram for the reduction of haematite CU20 + C ----7 2Cu + CO
However, this method is not used in actual practice for The non-volatile impurities are left-behind in the retort.
the extraction of copper. This is used for the purification of Zn,Cd, Hg, etc.
(c) Pyrometallurgical oxidation process: This process
(C) Theory of reduction of ZnO is used when the impurities have a greater affinity for oxygen
Ellingham diagram (Fig. 4.14) reveals that the curves than the metal itself. This method is usually employed for
involving the formation of ZnO and carbon monoxide cross refining the metals like Fe, Cu, Ag, etc, The oxidation is done
each other at about 1270 K. by various ways.
(i) Cupellation: The impure metal is heated in a cupel
or oval shaped crucible made of bone ash or cement and a
blast of air is passed over the molten mass. The impurities
get oxidisedand removed with the blast of air. For example
the impurity of lead present in silver is removed by
l~ I
I
I
I
cupellation process. .
2 I
I
(ii) Bessemerisation: The impure metal is heated in a
.!: -1000 ,
I
furnace and a blast of compressed air is blown through the
~ -1200
I
,
I
molten mass. The impurities get oxidised. For example, the
'1270\ molten pig iron is taken in a bessemer converter and
500 1000 1500 2000 2500 compressed air is passed which oxidises the impurities.
Temperature in K - - 2Mn + 02 ~ 2MnO
Fig.4.14 Ellinghamdiagram for formation of ZnO and CO
Si+02 ~ Si02
There is a sudden increase in the value of ilCO for the 2C+02'~ 2CO
formation of ZnO above 1180 K. This is due to the fact that MnO + Si02 ~ MnSi03
zinc begins to boil at this temperature. Above 1270 K, ilrGQ Slag
of the following equation, (iii) Poling: The impure metal containing oxides as
> 1270K impurity can be purified by this method. The molten impure
ZnO(s) + C(s) ) Zn(g) + CO(g)
metal is stirred with green poles of wood. The green poles of
is considerable negative and thus, reduction of Zno with
wood release the hydrocarbon gases which reduce the oxide
coke occurs easily.
impurities. This method is espedally used in the purification
4.1 THIRD OPERATION-REFINING of copper (old method).
(d) Electrolytic refining of metals: Many of the metals
- OR PURIFICATION
such as copper, silver, gold, aluminium, lead, etc.,. are
The metals obtained by the application of above reduction purified by this method. This is perhaps the most important
methods from the concentrated ores are usually impure. method. The impure metal is made anode while a thin sheet
These impure metals may be associated with small amounts ot pure metal acts as a cathode. The electrolytic solution
of (a) unchanged ore, (b) other metals produced by the consists of generally an aqueous solution of a salt or a
simultaneous .reduction of their compounds originally complex of the metal. On passing the current, the pure metal
present in the ore, (c) non-metals like silicon, carbon, is deposited on the cathode and equivalent amount of the
phosphorus, etc., (d) residual slag, flux, etc. The impure metal metal gets dissolved from the anode. Thus,' the metal is
is thus' subjected to some purifying processes known as transferred from anode' to cathode through solution. The
refuting in order to remove the undesired impurities. The soluble impurities passinto the solution while the insoluble
following refuting processes may be applied depending one, especially less electropositive impurities collect below
upon the nature of the metal under treatment and the nature the anode as anodic mud or anode sludge. Some examples
of the impurities. are given below:
(a) Liquation process: This process is based on the
(i) Purification of copper
difference in fusibility of the metal and impurities. When the
impurities are less fusible than the metal itself, this process Impure metal-:Anode;
is employed. The impure metal is placed on the sloping Thin sheets of copper~~ ...
hearth of a furnace and gently heated. The metal melts and Electrolyte-An aqueous solution of copper sulphate
flows down leaving behind the impurities on tlite hearth. This containing H 2SO4 ,
method is used to purify the metals like Bi, Sn, Pb, Hg, etc. A current of 1.3 volt is used. Anodic mud contains
(b) Distillation: This process is used for those metals Ag, Au, Pt, Pd, etc., and impurities like Fe, Zn, Ni,
which are easily volatile. The impure metal is heated in a etc., pass into the solution. 99.9% pure copper is
retort and its vapours are separately condensed in a receiver. obtained.
190 G.R B. Inorganic Chemistry for Competitions
Heating
Impure metal + h-------tMetal iodide ---'--7) Meta1+ 12
Tungsten
! (Vapours) filament (Pure) I
523 K
Ti(s) + 2I2(g) ---7) Til4(g)
Impure
This method is quite expensive.

Anode mud - __--:ail (iii) Zone refining or Fractional crystallisation: Elements
such as Si, Ge; Ga, etc., which are used as semiconductors
are refined by this method. Highly pure metals are obtained.
Electrolyte The method is based on the difference in solubility of impuri-
ties in molten and solid state of the metal. A movable heater
Fig. 4.15 Purification of copper by electrolysi$ is fitted around a rod of the impure metal. The heater is
slowly moved across the rod. The metal melts at the point of
(ill Purification of silver heating and as the heater moves on from one end of the rod
Impure metal-Anode; to the other end, the pure metal crystallises while the
A thin sheet of pure silver-Cathode. impurities pass on the adjacent melted zone.
Electrolyte-An aqueous solution of AgN03 Molten zone
containing
containing HN03. impurity
(ill) Purification of lead
Impure metal-Anode;
A sheet of pure lead-Cathode.
Electrolyte-A solution of lead silico fluoride PbSiF6
contai~g 8-10% of H2SiF6'
(e) Special methods: Sometime some special methods
are used for refinirig or purification of metals, some of which Moving circular
are given below: heater
(i) Mond's process: Nickel is purified by this method. Fig. 4.16
Impure nickel is treated with carbon monoxide at 60-80°C
Different metallurgical processes can be broadly divided
when volatile compound, nickel carbonyl, is formed. Nickel
into three main types.
carbonyl decomposes at 180°C to form pure nickel and
1. Pyrometallurgy : Extraction is done using heat energy:
carbon monoxide which can again be used.
The metals like Cu, Fe, Zn, Pb, Sn, Ni, Cr, Hg, etc., which are
180°C
Impure nickel + CO -----7 Ni(CO)4 ----7 Ni + 4CO found in nature in the form of oxides, carbonates, sulphides
• Gaseous compound I. are extracted by this process.
2. HydrometaIlurgy: Extraction of metals involving
(ii) Van Arkel process: This method is generally applied aqueous solution is known as hydrometallurgy. Silver, gold,
for obtaining tiltrapure metals. The impure metal is converted etc., are extracted by this process.
into a volatile compound while the impurities are not 3. ElectrometaIlurgy: Extraction of highly reactive
affected. The volatile compound is then decomposed metals such as Na, K, Ca, Mg, AI, etc., by carrying electrolysis
electrically to get the pure metal. of one of the suitable compound in fused or molten state.
Ti, Zr, Hf, Si, etc., have been refined by this method.
SUMMARY OF THE EXTRACTION OF METALS
Metal Main Occurrence Main Method· of Extraction

Sodium Common Salt, NaCl Electrolysis of fused NaCI with CaCl2
Magnesium Carnallite, KCl-MgCI2'6H20; Magnesite, MgC03 Electrolysis of fused MgCh with KCI
Calcium Limestone, CaC03; Gypsum, CaSO(2H 20 Electrolysis of fused CaCh and CaF2
Aluminium Bauxite, Al20:3-2H20 Electrolysis of Al20:3 in molten Na3AlF6 (cryolite)
Copper Copper pyrites, CuFeS2 Partial oxidation of sulphide ore
Cuprite, CU20 (2CU20 + CU2S ---7 6Cu + SOz)
Silver Argentite, .Ag2S Hydrometallurgy
Native silver Ag2S + 4NaCN ---7 2NaAg(CN)2 + Na2S
2NaAg(CNh + Zn ---7 Na2Zn(CN)4 + 2Ag
Zinc Zine blende, znS Reduction of ZnO with ~arbon or electrolysis of ZnS04
Calamine, Znc03 Zno + C---7 Zn + CO
Lead Galena, PbS Reduction of PbO with carbon
PbO + C ---7 Pb +CO
Tin Cassiterite, Sn02 Reduction of Sn02with carbo...
Sn02 + 2C ---7 Sn + 2CC'
Iron Haematite, Fez03 Reduction of oxide wit}:tcarbon monoxide
Magnetite, Fe304 Fe20:3 + 3CO ---7 2Fe -f 3C02
Chromium Chromite, FeO-Cr20:3 Reduction of Cr203 with 'Al
Cr2O:3 + 2AI ---7 2Cr + A12O:3
Nickel Millerite, NiS Reduction of NiO with CO
NiO + SCO ---7 Ni(CO).i + CO2; Ni(CO)4 ---7 Ni + 4CO
Mercury Cinnabar, HgS Direct reduction of HgSby heat alone
HgS + Oz ---7 Hg + S02
FURNACES from the roof of the furnace to the charge undergoing reaction.
Thus, this furnace can :be used for reduction as well as for
Furnace isa device in which high temperature is produced
oxidation purposes.
either by burning a fuel or by using electricity. Several types
The furnace consists of three main parts namely fire place,
of furnaces are used in the extraction of metals. The
hearth and chimney. The fire place is built at one end of the
important ones are described below:
furnace at slightly lower level than that of the hearth.Theroof
is made slanting and connects with the chimney on the other
l1!! (i) Reverberatory Furnace
end. The hot gases from the fire place are reflected by the
This is the kind of a furnace in which fuel does not come concave ceilingoverthe hearth. The furnace is surrounded
in direct contact with the charge. The flames are deflected . on all sides by walls of fire bricks_ Air supply can be
controlled by vents and direct blast.
The furnace is used for smelting (reduction) and roasting
of the ores. The reduction is done by the use of some suitable
reducing agent. The furnace is used (a) for reducing the
roasted tin stone (Sn02) to molten tin metal by the use of coke,
(b) for roasting the galena ore (PbS) as to convert it into PbO
and PbS04 by the use of air, (c) for roasting of copper pyrites
(CuFeS2) as to convert it into CU20 and FeO by means of air.
(ii) Blast Furnace

Iron ore is converted to iron in a special type furnace,
called blast. furnace (fig. 4.18)_ It is a huge chimney like
structure which can be between 25 and 60 metres in height
Fig. 4.17 Reverberatory furnace and 5 to 10 metres in diameter: It is constructed of steel plates
and the inner regions lined with fire-bricks. It has a double around. In an electric muffle furnace the closed chamber is
cup and cone arrangement at the top for the introduction of surrounded by heating electric coils. Such a furnace is used
charge. Preheated air at a temperature of about 600°C is for the extraction of zinc, for annealing of gold and silver
injected into the furnace through a number of pipes called assaying.
tuyeres in the bottom of the furnace. It is provided with two
tap holes plugged with clay; molten metal is tapped from the (iv) Electric Furnaces
lower one and molten slag from the other. The temperature In these furnaces, electrical energy is converted into heat
range in the furnace is from 1600°C at the bottom and energy. Such furnaces are largely used where cheap power
200-300°C at the top. Carbon and carbon monoxide reduce is available and very high temperatures are required and
the metallic oxides to the free metals. also for carrying electrolytic reduction. The electric furnaces
Charge are generally of three types :
Cup and cone
arrangement (a) Induction furnace,
(b) Arc furnaces and
(c) Resistance furnace.
(a) Induction furnace: In this furnace the charge lying
on the furnace bed or in a crucible constitute the secondary
coil of an induction unit and the induced currents produced
Refractory
bricks
by making and breaking the primary circuit, heat up the
materiaL
(b) Arc furnaces: Heat is generated by arcs and a
temperature over 3000°C may be obtained. Carbon electrodes
are used to carry the current and an arc is struck between
them and the charge. Arc furnaces are of two types:
(i) Direct heat and
(ii) Indirect heat.
In the direct heat arc furnaces, arc is used to heat up a
gas in which the arc is burning and in indirect heat arc
furnace, the arc burns above the charge, i.e., the arc radiates
heat towards the charge.
Molten Molten
Metal Slag (c) Resistance furnace : Heat is generated by the
resistance in the electric circuit. In some cases the material
forming the charge may act as the resistance and in other
Fig.' 4.18 Blast furnace cases, the body of furnace is made up of resistance material
and this material cause heating. In some cases, rods of poorly
Blast furnace is frequently used for the extraction of iron conducting materials are embedded into the charge which
and copper from their ores. Slag formation plays an become intensely hot on passage of the current.
important role in the blast furnace as it covers the melted
metal and thus protects the metal from being reoxidised. REFRACTORY MATERIALS
The materials which can withstand very high temperatures
(iii) Muffle Furnace
without melting or becoming soft are known as refractory
This furnace is' used materials. These are not affected by slags formed during the
when high' temperature is -_~::::::S-~ \ \ extraction of metals. These are used in the form of bricks for
required and th~ fuel and Flames and hot gases the internal linings of furnaces. Refractory materials used are
its products of combustion of three types:
Muffle
are not to be desired to (i) Acid refractories: Silica, quartz, siliciQUS sand
come into contact with the stones, etc., are the exatnpt'es.
material to be heated. The (ii) Basic refractories: lime, dolomite, magnesite, etc.,
muffle-is a chamber made are the examples.
of refractory material. The (iii) Neutral refractories: Graphite, chromite, bone ash,
muffle is surrounded' by etc., are the examples.
hot flames and hot gases all Fig. 4.19 Muffle furnace Silica (92% Si02, 2.7% A120 3) and quartz can tolerate
temperatures upto about 1750°C, bauxite upto 1800°C, 2200°C, Some carbides such as silicon carbide is used as
alumina upto 2000°C and magnesite, chromite, etc., upto refractory for special purposes.
MINERAL RESOURCES OF INDIA

Mineral resources of a country determine the economic for the development of aluminium industry in India.
position of the country. The country which is rich in mineral 4. Copper: The known copper ore deposits in India are
resources is definitely a prosperous country. India has large meagre. Almost all the present production of copper ore
mineral resources but not too large in view of the country's comes from Singhbhum and Hazaribagh districts of
huge size and population. India has abundant reserves of . Jharkhand and Khetri of Rajasthan,
coal, mica ore, manganese ore, iron ore, aluminium ore, 5. Gold: India has very meagre gold reserves. The only
titanium ore, etc., but particularly poor in non-ferrous metals. gold mine is at Kolar in Karnataka state. If is one of the
A short description of the important metals found in India deepest mines of the world.
is given here.
6. Chromium: Chromite (FeO Cr203) is the chief ore of
1. Iron: India contains some of the world's largest chromium. It is mainly found in Orissa, Jharkhand,
reserves of iron ore, mainly. haematite and magnetite. Mysore and Maharashtra.
India holds the sixth position regarding the production
7. Barium: Barytes is the main ore of barium. !tis mainly
of iron ore in the world. Large deposits have been
found in Andhra Pradesh, Rajasthan and Tamil Nadu.
reported in Bihar, Jharkhand, Orissa, Madhya Pradesh,
Kamataka, Andhra Pradesh and Goa. The states of 8. Lead and Zinc: India has no important deposits of
Orissa and Jharkhand [Singhbhum Oharkhand); lead and zinc ores. Recently lead and zinc ores have been
Keonjhar, Sonai and Mayurbhanj (Orissa)] produce over found at Zawar mines near Udaipur and at Hazaribagh
75% of the total iron ore produced in India. The Oharkhand). Zawar deposits contain 8-10% Zn and 5%
important steel plants are located at Bhilai, Durgapur, lead.
Rourkela, Jamshedpur, Bhadravati and Bumpur. 9. Calcium: The sulphate ore of calcium (gypsum) is
2. Manganese : India possesses large reserves of mainly found in Rajasthan. Limestone and marble
manganese ore mainly pyrolusite (Mn02)' India holds (calcium carbonate) are found in large amounts in
the fourth position in the production of manganese ore almost all the states of India.
in the world. Orissa is the leading producer followed 10. Titanium: The principal ore of titanium is ilmenite. It
by Kamataka, Madhya Pradesh and Maharashtra. is mainly found in the eastern and western coasts of
3. Aluminium : India is rich in bauxite reserVes. India.
Workable deposits are found in Jharkhand, Madhya 11. Thorium: Beach sands of Kerala and Tamil Nadu
Pradesh, Tamil Nadu, Maharashtra, Kamataka, Orissa contain a useful mineral monazite which is used for the
and Gujarat. The availability of cheap power is a must extraction of thorium and rare-earths.
Problem 1. What are four most abundant elements in Problem 3. Why do metal sulphides occur mainly in rocks
earth's crust? Arrange them in decreasing abundance. and metal halides in lakes and seas?
Solution: Solution:
Oxygen, silicon, aluminium and iron are the most Metal sulphides are insoluble in water while metal
abundant elements in the earth's crust. The abundance order chlorides are soluble in water. Thus, chlorides get dissolved
is: in rain water and washed away to lakes and seas.
0> Si > Al > Fe Problem 4. What is the role of depressant in froth floatation
Problem 2. In general which metal do you expect to occur in process?
the native state in nature? Give examples. Solution:
Solution: The depressants help in the separation of two sulphide
The metals which are below hydrogen in the electro- ores. For example, in case of an ore containing PbS (Galena)
chemical series, i.e., which are less electropositive metals can and ZnS (Zinc blend e), the depressant is NaCN. It prevents
occur in native state in nature. These metals are not readily znS from coming to the froth but allows PbS to corne with
attacked by oxygen, moisture, carbon dioxide, etc. Examples froth in the froth floatation process. ZnS forms a soluble
are: Ag, Au, Pt, Pd, etc. complex with NaCN.
(c) It removes CO2 from a carbonate ore.

ZnS+4NaCN ---7 Na2Zn(CN)4 +Na2S
Sodium tetracyanozincate (II) CaC03 ---7 CaO + CO2
Problem 5. What is the significance of leaching m the CuC03· Cu(OH)z ---7 2CuO + CO2 + H 20
extraction of aluminium? This process is generally done in a reverberatory furnace.
Solution: This process makes the ore porous.
The bauxite ore is always associated with silica, iron Roasting is a process in which the ore (usually the
oxide and titanium oxide as impurities. These impurities are sulphide ore) is heated strongly in the presence of excess
removed by the process of leaching. The powdered bauxite of air. The heating should be done at a temperature below
ore is heated with 45% solution of NaOH at 473-523 K the melting point of the ore. The ore is heated alone or
Alumina and silica dissolve while Fe203 and Ti02 remain mixed with some other materials. The process does the
insoluble. These are filtered off and solution is neutralised following things.
with CO2 and freshly precipitated Al(OHh is added when (a) It dries the ore.
hydrated alumina separates out. The sodium silicate remains (b) The volatile impurities like CO2, 502 organic matter,
in solution. Hydrated alumina is separated and dried. This moisture are all driven out.
gives pure alumina on heating strongly. (c) The ore is converted into oxide.
. 473-523 K 2ZnS + 302 ---7 2ZnO + 2502
Al203 ·2H20+2NaOH+H20 )2Na[Al(OH)41
Bauxite Sod. aluminate 2HgS + 302 ---7 2HgO + 2S02
Si02 + 2NaOH ---7 Na2Si03 Sometimes sulphide ore is converted into sulphate.
Sod. silicate
PbS + 202 ---7 PbS04
2Na[Al(0H)41 + 2C02---7 Al20 3·2H20 + 2NaHC03 + H 20
(d) The sulphide ore is converted into chloride.
1473 K .
Al20 3·2H20 ) Al20 3 + 2H20 Ag2S + 2NaCl ---7 2AgCI + Na2S
Problem 6. Which of the ores can be concentrated by . Problem 8. Why is the reduction of a metal oxide easier if
magnetic separation? the metal formed is in liquid state at the temperature of
Solution: reduction?
The ores in which one of the components either the actual Solution: .
ore or the impurity is magnetic in nature can be concentrated The entropy of a substance is higher in liquid state than
by magnetic separation. For example, ores of iron such as in solid state. In the reduction of a metal oxide, the entropy
haematite, magnetite, siderite, etc., can be concentrated by change (AS) will be +ve if the metal formed is in liquid state.
magnetic separation. Thus, the value of AGO becomes negative and reduction
Problem 7. Differentiate between occurs easily.
(i) Minerals and ores . Problem 9. Out of C and CO which is a better reducing agent
(ii) Roasting and calcination. at 673K?
Solution: Solution:
(0 The natural 'substances in which metals occur in the When carbon acts as a reducing agent, it is either converted
earth are called minerals. The mineral has a definite into CO or C02 or both.
composition. It may be a single compound or a complex
. 2C + O 2 ---7 2CO
mixture. It is usually associated with a number of impurities.
The minerals from which the metals can be conveniently C + 02 ---7 C02
and economically extracted are known as ores.
CO is oxidised to C02 when it is used as a reducing agent.
Thus, all ores are minerals but all minerals are not ores.
For example, iron is found in the nature as oxides, 2CO + 02 ---7 2C02
carbonate and sulphides. Out of these minerals, the oxides
From the Ellingham diagram, it is clear that at the
of iron such as haemafite, magnetite, etc., are used for
temperature 673 K, the ACO of the.formation of C02 from CO
extraction. Therefore, oxides of iron are the ores of iron.
is more negative than the formation of CO or CO2 from
(ii) Calcination is a process in which the ore is heated
carbon. Hence, at temperature 673 K, CO is a better reducing
below its fusion temperature in absence of air. The process
agent than C.
does the following things:
(a) It removes the volatile impurities like COg S02 organic o.Problem 10. Out of C and CO, which is a better reducing
matter, moisture from the ore. agent for 2nD?
(b) It removes water from hydrated oxide ore. Solution:
From the Ellingham diagram, it is clear that the free
AlzO:r 2H20 ---7 Al20 3 + 2H20
energy of formation of CO from C is lower at temperatures
. 2Fe203·3H:{) ~ 2Fe203 + 3H20 above 1120 K while that of CO 2 from carbon is lower above
1323 K than free energy of formation of ZnO. However, the Thus, thermodynamic factor helps in choosing a
free energy of formation of CO2 from CO is always suitable reducing agent for the reduction of a particular metal
higher than that of ZnO. Hence, C is a better reducing agent oxide.
ofZnO. • Problem 12. (i) Suggest a condition under which magne-
Problem 11. The choice of a reducing agent in a particular sium could reduce alumina.
case depends on thermodynamic factor. How far do you agree with (ii) Predict condition under which At might be expected to
this statement? Support your opinion with two examples. reduce MgO.
Solution: Solution:
From the Ellingham diagram, it is evident that any metal (i) l'lG of formation of Al20 Sat temperatures below 1665 K
oxide with lower l'lG' is more stable than the metal oxide with is less negative than l'lG of formation of MgO.Thus, below
higher l'lGo, ThisAmplies that the metal oxidE' F!uced lower 1665 K magnesium can reduce Al20 S to AI.
in the diagram cannot be reduced by the metal involved in (ii) The temperature of intersection of the Al ~ Al20 S
the formation of the oxide placed higher in the diagram. and Mg ~ MgO curves in the Ellingham diagram is 1665
However, reverse can readily take place. Thus, AhOs cannot K. Above this temperature, l'lG of formation of Al20 Sis more
be reduced by Cr. However, chromium oxide can be reduced
negative than l'lG of formation of MgO. Thus, above 1665 K
by AI.
aluminium can reduce MgO into Mg.
At temperature 1773 K, the change in free energy for the
formation of Al20s and Cr20S is given below: Problem 13. Copper can be extracted by hydrometallurgy but
not zinc. Explain.
2Al + ~ 02 ~ AI20 S; . l'lG = -900 kJ morl '" (i)
Solution:
· 3 1 Copper is comparatively less active metal as its reduction
2Cr + 2: O2 ~ Cr20S; l'lG = -SOO kJ mol- .,. (ii)
The reaction for the reduction of Al20S with Cr may be potential, i.e., Eo(Cu2+ICu) is high (+ 0.34 V). It can be
obtained by subtracting eq. (i) from eq. (ii). displaced from solutions of Cu2+ ions by more active metals
Al20S + 2Cr ~ Cr20S + 2Al; l'lG = 400 kJ mol-1 which have fO values lower than copper. For example, EO of
This reaction is thermodynamically not feasible since l'lG zinc (Zn2+ IZn) is -0.76 V and thus, zinc can displace copper
has +ve value. from solutions of Cu2+ ions.
The reaction for the reduction of Cr20S with Al may be In contrast to displace zinc from solutions of Zn2+ ions a
obtained by subtracting eq. (ii) from eq. (i). more reactive metal than it is required. But, the more activp.
Cr20S + 2Al ~ Al20 S + 2Cr; l'lG = -400 kJ mol-1 metals readily react with water forming their corresponding
This reaction is feasible since l'lG has negative value. ions and evolve hydrogen gas. Thus, it is difficult to displace
Similarly, both Al and Zn can reduce FeO to Fe but Fe cannot zinc from solutions of Zn2+ ions. Hence, copper can be
reduce Al20 s or ZnO. extracted by hydrometallurgy but not zinc.
'i SUMMARY AND IMPORTANT POINTS TO REMEMBER n

1. The most abundant element in the earth's crust is oxygen. (b) Sulphurised or arsenical ores : The examples are:
Next to oxygen is the element silicon. Galena (PbS); Zinc blende (ZnS); Cinnabar (HgS);
2. The most abundant metal in the earth's crust is aluminium. Argentite (Ag2S); Copper pyrite (CuFeS:2); Kupfer nickel
3. The most abundant transition metal in the earth's crust is (NiAs).
iron. (c) Oxidised ores : Metals are present as oxides or
4. About 88 elements are naturally occurring while the oxysalts. The examples are : Haematite (Fe2O'3); Bauxite
remaining have been synthesized. The earth's crust is the (AI2O'3·2H2O'); Tinstone (Sn02); Rutile (riO'2); ancite
biggest source of metals. Metals occur in nature sometimes (ZnO'); Limestone (CaC~); Dolomite (CaCO'3· MgCO'3 );
free (native state) but mostly in the combined state.The Malachite [CuCO'3 · Cu(O'Hhl; Calamine (ZnCO'3); Chile
natural substances in which the metals or their compounds saltpetre (NaNO' 3); Gypsum (Ca50 4, 21120'); Barytes
occur in the earth are called minerals. The minerals from (Ba504); Beryl (3BeO'· Al20:,· 6SiO'2).
which the metal can be conveniently and economically (d) Halide ores: Examples are : Comlllon salt (NaCI);
extracted are called ores. Ores may be divided into four Carnallite (KCI·MgCI2·6H2O'), Fluorspar (CaF2)'
groups: 5. .The .whole process of obtaining a pure metal from one o{
(a) Native ores: Metals present in free state associated its ores is known as metallurgy. Metallurgy of a metal
1i\Tith rock or alluvial materials such as gold, platinum, involves three main operations: •
silver, etc. Sometimes lumps of pure metals are found. (a) Concentration or dressing of the ore (b) Isolation of crude
These are termed nuggets. metals (c) Purification or refining.
6; The undesired impurities such as sand, clay, rocks, etc., (i) Smelting : The process of extracting a metal by.
associated with the ore .are called gangue or matrix. The heating the metal oxide with a suitable reducing
removal of these impurities from the ores is known as agent such as C, Hz, CO, water gas, Na, K, Mg, Al,
concentration or dressing of ores. The concentration is done etc., at high temperature is called smelting. The
in a number of ways depending upon the nature of process, in general, is termed pyrometallurgy.
impurities. It is applicable especially for the extraction of less
(a) The process of removing the lighter particles of sand, electropositive metals such as Fe, Zn, Pb, Sn, etc.,
clay, etc., by washing with water either using Wilfley carbon, carbon monoxide and aluminium are
table or Hydraulic classifier is called levigation or generally used as reducing agents.
gravity separation. The term smelting is applied when coke or carbon
The oxide ores of iron (haematite) and tin (cassiterite is used as a reducing agent. The ore is mixed with
or tinstone) and native ores of Ag, Au, etc., are concen- a suitable quantity of. coke or charcoal (acts as a
trated by this process. reducing agent) and heated to a high temperature
(b) Electromagnetic separation methLd .is applied when above its melting point. An additional reagent is
either the ore or the impurities are magnetic in nature. usually added to the concentrated ore to remove if
Chromite ore (magnetic) is separated from non- still impurities are present. This additional reagent
magnetic silicious impurities. Wolframite (FeW04), a is called flux. Flux combines with impurities and
magnetic ore is separated from non-magnetic Qre, forms a fusible slag. The selection of flux depends
cassiterite (Sn02), by this method. on the nature of impurities. If impurities are acidic,
(c) Froth floatation process is used for the concentration of basic flux such as CaO is used while acidic flux such
sulphide ores. This process is based on the preferential as silica is used. if the impurities are basic. The
wetting of ore particles by oil (pine oil) and gangue process is carried out in a blast furnace.
particles by water. Zinc blende, copper pyrites, galena, (ii) Goldschmidt aluminothermic process-Reduction
etc., are concentrated by this process. by aluminium: This process is used in the case
(d) Leaching involves the treatment of the ore with' a of those metals which have very high melting
suitable reagent to make it soluble wpile impurities points and are to be extracted from their oxides. A
remain insoluble. The ore or the metal is recovered from mixture of metal oxide and aluminium powder,
the solution by a suitable chemical method. COrru:i1only called' as thermite, is' taken in a steel
For example, bauxite is digested with aqueous solution crucible placed in a bed of sand. The reaction is
of NaOH, when Al20 3 dissolves forming sodium meta started by the use of an ignition mixture containing
aluminate (NaAl02) while impurities such as Fez03' magnesium powder and barium peroxide.
TiOz and silica remain insoluble. Pure alumina is (iii) Auto or Self reduction process: .The sulphide ores
recovered from the filtrate. of less electropositive metals like Hg, Pb, Cu, etc.,
Native ores of Ag and Au are treated with aqueous are heated in air as to convert part of the ore into
dilute solution of NaCN in presence of oxygen. The Ag oxide or sulphate which then reacts with the
and. Au particles get dissolved forming. complex remaining sulphide ore to give the metal and S02.
cyanides. Ag or Au is recovered from the solution by No external reducing agent is used in this process.
addition of electropositive metal, Zn. (iv) Electrolytic reduction : The highly electro-
7. Extraction of crude metals: Metals are usually extracted positive metals such as alkali metals, alkaline earth
by reduction. Thus, the concentrated ore is converted into a metals, AI, etc., are extracted by the electrolysis of
form which is suitable for reduction. Oxides are easier to hydroxides, chlorides or oxides in the fused state.
reduce. Therefore, the extraction involves the following two Sometimes, a small amount of some other salt is
steps: added to decreases the fusion temperature or to
(a) Conversion of the ore into metallic oxide. increase the. conductivity or both. The metal is
(b) Reduction of metallic oxide. liberated at the cathode.
(a) Two methods are used for conversion into oxides. (v) Hydrometallurgy: Certain metals such as silver
0) Calcination involves heating of the ore below its and gold are extracted by dissolving the
fusion temperature in absence of air. This step concentrated ore in some suitable reagent and then
expels organic matter and moisture from the ores. recovering the metal from the solution by
Carbonates may be decomposed. treatment with some more electropositive metal.
(ii) Roasting involves heating. of the ore either alone 8. Thermodynamic principles : The. basic concepts of
or with some other material in presence of oxygen thermodynamics are quite helpful in selecting a suitable
(air) below its fusion temperature. This process is reducing agent for a particular oxide. In the oxidation
generally done in a reverberatory furnace. Non- reduction reaction, the Gibbs free energy change should be
metallic impurities are removed as their volatile negative at an appropriate temperature.
oxides. The ores such as sulphides are simulta- ilGO ilW - Tt.S
neously converted into corresponding oxides either
partially or completely. The concept is graphically displayed in plots of ilGo vs T
(b) Reduction of the oxide to the free metal is done by a (Ellingham diagram). Any metal oxide with lower value of
suitable reducing agent. The following methods can be ilGo is more stable than metal oxide with higher t.Go. This
applied. implies that metal oxide placed higher in the diagram can
be reduced by the metal involved in the formation of the volatile nickel carbonyl is formed. The carbonyl is
oxide placed lower in the diagram. This concept is applied subjected to 450-470 K, when it decomposes giving pure
in the extraction of Fe, Zn and Cu. nickel.
9. The concept of electrode potential is useful in the isolation Impure + CO 330-350 K) NiC0 4 450-470 K) Ni +4CO
of the metals either by electrolysis· or by displacing one nickel Volatile
metal by other in the solution. The sum of the E" of two
redox couples should be positive so that Gibbs energy
change is negative. (i) Chromatographic methods: It is based on selective
6.GO == -nFEO distribution of various constituents of a mixture
between two phases, a stationary phase and a moving
The process of extraction of metals by electrolysis of their phase. The stationary phase can be either solid or tightly
fused salts is called electrometallurgy. In electrolysis, bound liqui(1 on a solid support. The moving phase may
electrons act as reducing agent at cathode. One example of be a liquid or a gas. Different types of chromatographic
the electrometallurgy is the extraction ·of aluminium metal methods have been developed. The most common are :
from bauxite ore.
10. Third operation : Purification or refining : The process of
(a) Column chromatography,
purifying impure metals is called refining. (b) Thin layer chromatography,
(a) Liquation process : The process is based on the (c) Paper chromatography,
difference in fusibility of the metal and impurities. When (d) Gas chromatography, etc.
the impurities are less fusible than the metal itself, this Column chromatography is the simplest method. This
process is used: The impure metal such as Bi, Sn, Pb, is based on adsorption phenomenon. The extent of
Hg, etc., is placed on the sloping hearth of a furnace and adsorption of various constituents present in the mixture
gently heated. The metal melts and flows down. liquid (moving phase) varies with a given adsorbent
(b) Distillation: The process is used for those metals which (stationary phase). The common adsorbents used are
are volatile. The impure metal is heated and the vapours alumina, silica gel, magnesium oxide, active animal
are separately condensed in a receiver. This is used for charcoal, etc.
the purification of Zn, Cd, Hg, etc. It involves the following steps:
(c) Cupellation: The impure metal is heated in cupel or
(a) Preparation of adsorption column
oval shaped crucible made of bone ash or cement and a
(b) Adsorption
blast of air is passed over the molten mass. The
impurities are oxidised and removed with the blast of (c) Elution of components and recovery.
air. Impurity of lead in silver is removed by this process. This method is useful for those elements which are
(d) Poling: .It is used for purification of those metals which available in small amounts and the impurities are not
contain their own oxides as impurity. The molten impure much different in chemical properties from the element
metal is stirred with green poles of wood. to be purified.
(e) Electrorefining: Metals like Cu, Ag, Au, Ni, Cr, Al, 11. The materials which can withstand very high temperatures
etc., are purified by this method. The impure metal is without melting or becoming soft are known as refractory
made the anode and a strip of pure metal is made as materials. These are used in the form of bricks for the internal
cathode while electrolytic solution consists of a solution linings of furnaces.5ilica, quartz, lime, graphite, bone ash,
of a suitable salt of the metal. etc.! are used as refractory materials.Refractory materials are
(f) Zone refining: When highly pure metals are required, of three types:
this method is applied for purification. The method is 0) Acid refractories: Silica, quartz, silicious sand stones,
based on the difference in solubility of impurities in etc., are the examples.
molten and solid state of the metal. This method is used (ii) Basic refractories: Lime, dolomite, magnesite, etc.,
in purification of germanium, gallium, silicon, etc., are the examples.
which are used as ·semiconductors. (iii) Natural refractories: Graphite, chromite, bone ash,
(g) Van Arkel process: This method is used for obtaining etc., are the examples.
ultrapure metals. The impure metal is converted into Silica (92% Si02, 2.7% Al2~) and quartz can tolerate
volatile compound which is then decomposed temperatures upto about 1750°C, bauxite upto 1800"C,
electrically to get pure metal. Ti, Zr, Hf, Si, etc., are alumina upto 20000C and magnesite, chromite, etc.,
refined by this method. upto 2200°C. Some carbides such as silicon carbide is
used as refractory for special purposes.
Impure + 12 -7 Metal iodide THeati:,g) Metal + 12 12. India has abundant reserves of coal; mica ore, manganese
metal t vapours ffi~~e~~ pure I ore, iron ore, aluminium ore, titanium ore, etc., but parti-
cularly poor in non-ferrous metals.
(h) Mond's process: Nickel is purified by this method. The
impure nickel is treated with CO at 330-350 K, when
r.··- PRACTICE PROBLEMS

• Subjective Type Questions (vii) Autoreduction
r· .. -
(viii) Electrolytic refining
(ix) Reverberatory furnace (x) Blast furnace
1. (a) Name one oxide ore of each of the following metals : (xi) Leaching (xii) Cupellation
(i) iron (ii) zinc (iii) aluminium 9. (a) Which of the following metals can be obtained by the
(b) Name the metal present in : electrolytic reduction of aqueous solution of their salts-
(i) chlorophyll (ii) haemoglobin Al, Na, Cu and Ag?
2. (a) What types of ores are roasted? (b) Which of the metals Na, Ag and Fe are extracted by,
(b) How is copper pyrite concentrated? (i) Complex formation
(c) How is bauxite generally concentrated? (ii) Reduction with carbon and
3. (a) Name the diagram which can be used to compare the (iii) Electrolysis of fused salt?
reducing nature of different elements. (c) Which ores are generally concentrated by froth floatation
(b) Indicate the temperature at which carbon Ccln be used as process?
reducing agent for FeO. (d) (0 Which of the following metals is lightest and which
(c) Which is a better reducing agent below 983 K Carbon one of them is least reactive?
or carbon monoxide? Cu, Ag, Al, Fe.
4. Name the following :
(ii) Which one out of the two may be found in native
(i) Two metals which never occur in native state. state?
(ii) Two metals which always occur both in native and in 10. Explain the following:
combined states.
(i) Zinc but not copper is used for the recovery of Ag from
(iii) Two metals which always occur naturally in an
the complex [Ag(CN)2f.
uncombined state.
[Hint : Zinc is more powerful reducing agent in comparison
(iv) Two metals which are manufactured by the electrolysis
to copper. Zinc is also cheaper than copper.]
of their fused salts.
(v) Two metals which are used for the reduction in (ii) Partial roasting of sulphide ore is done in the metallurgy
metallurgical process. of copper.
5. Name the metals with which the following ores/minerals [Hint : Partial roasting of sulphide ore forms some oxide.
are associated: This oxide then reduces the remaining sulphide ore
(i) Cryolite (ii) Dolomite (iii) Calamine into metal.
(iv) Haematite (v) Malachite (vi) Lepidolite 2CuS + 30,. ---4 2CuO + 2S02
(vii) Polyhalide (viii) Triphylite (ix) Borax (x) Chromite
2CuO + CUS 3Cu + ~ (Autoreduction)
6. What term is assigned to the following?
(iii) Why is chalcocite roasted and not calcined during
(0 Naturally occurring compounds from which metals are
recovery of copper?
extracted profitably.
(ii) Sulphide ores are generally heated in a stream of air. [Hint : Chalcocite is a sulphide ore. It is to be converted into
(iii) Metal is extracted from its ore by heating the ore with oxide and thus roasting and not calcination is done.]
a suitable reducing agent. (iv) Aluminium metal is frequently used as a reducing agent
(iv) Metal ions get discharged on an electrode. for the extraction of metals such as chromium,
(v) The materials which can withstand very high tempera- manganese, etc.
tures without melting and softening. [Hint : Aluminium has great affinity for oxygen. It acts as a
(vi) The substances used for the removal of gangue in the reducing agent when the metal having high melting
ores in the form of slags. point is to be extracted from its oxide.
(vii) The process in which aluminium is used as a reducing Cr203 + 2Al ---4 2Cr + A1203]
agent for the extraction of metal from its oxide.
(v) Magnesium oxide is used for the lining in steel making
7. Differentiate the following giving a suitable example :
furnace.
(i) Mineral and ore
(ii) Calcination and roasting [Hint; Magnesium oxide acts as a flux to remove impurities
(iii) Flux and slag of 5i, P and 5 through slag formation.
(iv) Smelting and roasting- MgO + 5i02 ---4 MgSi03
8. Write short notes on : 3MgO + P20S ---4 Mg3(PO.v2
(i) Froth floatation process (ii) Calcination
MgO + 502 ---4 Mg50:3
(iii) Roasting (iv) Smelting
(v) Hydrometallurgy (vi) Pyrometallurgy
11. How the following impurities can be removed? • Matching Type Questions
(a) An impurity of lead in silver.
(b) An impurity of cuprous oxide in copper. Match the following:
(c) Impurities of Fe, Cu, etc., in aluminium. [A] (a) Al (0 Cinnabar
12. Describe the thermodynamic principles of metallurgy. How (b) Cu (li) Calamine
Ellingham diagram is useful in predicting the feasibility of (c) Mg (iii) Cryolite
thermal reduction of a metal oxide. (d) Zn (iv) Malachite
13. Describe the principle of extraction of each of the following: (e) Hg (v) Carnallite
(a) Cu from CuFeSz (b) Zn from ZnO (c) Fe from Fe203 [B] (a) Zn (i) Self reduction
14. Explain the following ; (b) Ag (ii) Fused salt electrolysis
(a). Carbon reduction process is not applied for reducing (d Fe (iii) Carbon reduction
alumina. (d) Ca (iv) Amalgamation
(b) Aqueous solution of sodium chloride cannot be used for (e) Cu (v) CO reduction
the isolation of sodium by electrolysis. [C] (a) Calamine (i) PbS
(d Graphite is used as anode and not diamond. (b) Galena (ii) KCI'MgCl 2'6H 20
(c) Cassiterite (iii) AIP3'2H20
(d) Bauxite (iv) Sn02
(e) Carnallite (v) ZnC03
[D] (a) Sulphide ore (i) Silver
(b) Mond's process (ii) Iron
(c) Cupellation (iii) Carbonate ores
(d) Calcination (iv) Froth floatation process
(e) Pyrometallurgy (v) Nickel
Answers : Subjective Type Questions 6. (i) ores, (ii) roasting, (iii) smelting, (iv) electrolytic reduction,
1. (a) (i) Haematite (li) Zincite (iii) Bauxite (v) refractory materials, (vi) fluxes, (vii) thermite process.
(b) (i) Magnesium (ii) Iron 9. (a) Cu and Ag; (b) (i) Ag, (m Fe, (iii) Na; (c) Sulphide ores; (d)
2. (a) sulphide ores (b) froth floatation process (d leaching (i) lightest element AI, least reactive Ag, (li) Ag.
3. (a) Ellingham diagram (b) Above 1123 K(c) Carbon monoxide 11. (a) Cupellation, (b) Poling, (c) Electrolytic.
4. (i) Sodium and potassium; (li) Copper, silver; (iii) Au, Pt; Answers : Matching Type Questions
(iv) Sodium, aluminium; (v) Aluminium, magnesium, iron or (A) (a-iii); (b-iv); (c-v); (d-ii); (e-i)
sodium. (B) (a-lii); (b-iv); (c-v); (d-ii); (e-i)
5. (i) Na and AI; (iil Mg .and Ca; (lii) Zn; (iv) Fe; (v) CUi (vi) Li, AI, (C) (a-v); (b-i); (c-iv); (d-lii); (e-ii)
Na and K; (vli) K, Mg and Cal (viii) Li, Na, Fe and Mn; (ix) Na; (D) (a-iv); (b-v); (c-i); (d-lii); (e-ii)
(x) Cr, Fe.
fUlJS1RATfONS OF OBJECTIVE QUESTIONS

1. The main ore of lead is galena (PbS). Lead is extracted from List I List II
galena ore either by (A) or (R). A. Mond's process 1. Purification of copper
(A) PbS R::~d) PhO + 502 B. Van Arkel method 2. Purification of zinc
C. Cupellation 3. Purification of nickel
Heated
D. Distillation 4. Purification of titanium
Ph + CO2
with C
Codes:
(B) PbS R?as~ed)
malt
PhO + PhS (a) A-I, B-2, C-3, D-4 . (b) A-2, B-3, C-4, 0-1
IHeated (c) A-3, B-4, C-l, 0-2 (d) A-4,B-l, C":'2, 0-3
. with PbS. Ph + S02 Ans : (c)
5. Match List I with List II and select the correct answer using
Auto-reduction process is :
(a) A (b) B (d both (d) none the codes given b.elow :
Ans. (b) List I List II
2. Which of the following processes involves smelting? A. Cinnabar 1. Zinc
B. Cassiterite 2. Aluminium
(a) Znco3 ~ Zno + COz C. Bauxite 3. Tin
D. Calamine 4. Me:r;cury
(b) .2PbS + 302 ~ 2PbO + 2SO:i Codes:
(a) A - 4, B-3, C 2, D - 1
(c) Al2~·2H20~ Al203 + 2H20 (b) A-I, B-2, C - 3, D - 4
(d A 2, B-3, C - 4, D 1
(d) Fez~ + 3C ~ 2Fe + 3CO (d) A - 3, B - 4, C - 1, D 2
Ans. (d) Ans : (a)
3. Consider the following statements : 6. The method of zone refining of metals is based on the
Roasting is carried out to : principle of :
1. convert sulphide into oxide (a) greater mobility of the pure metal than that of impurity
2. melt the ore (b) greater solubility of the impurity in the molten state
3. remove moisture, water of hydration and expel organic than in the solid
matter (d higher melting point of the impurity than that of the
4. remove sulphur and arsenic in the form of volatile pure metal
oxides (d) all above are correct
Out of these statements : Ans ; (b)
(a) I, 3 and 4 are correct (b) I, 2 and 3 are correct
7. In the equation, 4M + 8CN- + 2H 20 + ~ ~
(d 2, 3 and 4 are correct (d) 1,2 and 4 are correct
4[M(CN)z] + 40H , the metal Mis:
Ans. (a)
(a) copper (b) iron
(d gold (d) zinc
the codes given ahead :
Ans ; (c)
_.... -
Set I : This set contains questions with one correct answer.
1. The most abundant metal in the earth crust is : 12. Autoreduction process is used in the extraction of :
[J.E.E. (W.B.) 2010] (a) Cu and Hg 0 (b) Zn and Hg 0
(a) Al o (b) Fe o (c) Cu and AI 0 (d) Fe and Ph 0
(c) Ca o (d) Na o 13. I.n thermiteprocess, the reducing agent is :
2. Which metal is generally found in native state? (a) C O · (b) Zn 0
(a) Cu 0 (b) Au 0 (c) Na 0 (d) Al 0
(c) Al 0 (d) Fe 0 14. Complex formation method is used for the extraction of :
3. A mineral is called ore if : (a) Zn 0 (b) Ag 0
. (a) the metal present in the mineral is costly 0 (c) Hg 0 (d) Cu 0
(b) a metal can be extracted from it 0 15. Carbon monoxide reduction process is used for the
(c) a metal can be extracted profitably from it 0 extraction of :
(d) a metal cannot be extracted, from it 0 (a) Cu o (b) Ag o
4. Select the correct statement.
(d Fe o (d~ Sn o
16. Gold is extracted by hydrometallurgical process based on
(a) Dolomite is the ore of zinc 0
its property: [CE.T. (Kamataka) 2005]
(b) Galena is the ore of mercury 0
(a) of being electropositive 0
(c) Pyrolusite is the ore of iron 0
(b) to form complexes which are water soluble 0
(d) Cassiterite is the ore of tin 0
(d of being less reactive 0
5. Which of the following pairs consists of minerals of the
(d) to form salts which are water soluble 0
same metal?
17. Argentite is a mineral of :
(a) Bauxite, limonite o (b) Haematite, Magnetite 0 (a) Au 0 (b) Pt 0
(c) Galena, Cerusite o (d) Both (b) and (c) 0 (c) Ag 0 (d) Cu 0
6. Froth floatation process is based on : [P.E.T. (Kerala) 2005] lB. Electrometallurgical process (electrolysis of fused salt) is
(a) specific gravity of the ore particles 0 employed to extract :
(b) magnetic properties of the ore particles 0 (a) lead o (b) silver o
(c) wetting properties of the ore particles 0 (d sodium o (d) none of these o
(d) electrical properties of the ore particles 0 19. When Zns and PhS minerals are present together, NaCN is
7. The function of flux during the smelting of the ore is : added to separate them in froth floatation process because:
(a) to make the ore porous 0 (a) Pb(CNh is precipitated while there is no effect on Zns
(b) t6 remove gangue 0 o
(c) to facilitate reduction 0 (b) ZnS forms soluble complex, Na2Zn(CN}4 o
(d) to facilitate oxidation 0 (dPhS forms soluble complex, Na2Pb(CN)4 o
B. Name the metal M which is extracted on the basis of (d) both (a) and (b) . o
following reactions : [Hint : Zns + 4NaCN ~ Na2Zn(CN)4 + Na2S]
4M + BNaCN + 2H20 + 02 ~ 4NaM(CNh + 4NaOH 20. To obtain chromium from chromic oxide (Cr203), the
2NaM(CNh + Zn ~ Na2Zn(CN)4 + 2M method used is :
(a) Au or Ag 0 (b) Hg 0 (a) carbon reduction o
(c)· Ni 0 (d) Fe 0 (b) carbon monoxide reduction o
9. Which of the following statements is true ? (c) aluminothermic o
(a) All ores are minerals o (d) electrolytic reduction o
(b) All minerals are ores o 21. Poling process is used :.
(c) A mineral cannot be an ore o (a) for the removal of CU2Q from eu o
(d) An ore cannot be a mineral 0
(b) for the removal. of Al 20 3 from AI o
10. The impurities present in the mineral are called :
(c) for the removal cif Fe2~ from Fe o
[J.E.E. (Orissa) 2010]
(d) in all the above o
(a) flux 0 (b) gangue 0 22. ACl 2 + BCl 2 ~ A04 + B.J,
(Excess)
(c) alloy 0 (d) slag 0
BO Heat )B+l/2 O 2
11. Electrolytic reduction process is used for the extraction of :
(A and B are metals.)
(a) alkali metals 0 (b) alkaline earth metals 0
The ore of B is :
(c) aluminium 0 (d) all of these 0
(a) cinnabar o (b) azurite o 36. The furnace lining in steel manufacture consists of :
(c) galena o (d) siderite o (i) CaO (ii) SiOz (iii) MgO (iv) CaC03
[Hint: SnC12 + Hg02 ~ Sn04 + Hg (a) (ii) and (iv) 0 (b) (i) and (iii) 0
HgO ~ Hg + 1/2 O2 J (c) (iii) and (iv) 0 (d) (ii), (iii) and (iv) 0
23. Essential constituent of amalgam is : 37. The furnace which gives the highest temperature is :
(a) an alkali metal 0 (b) silver 0 (a) blast furnace 0 (b) reverberatory furnace 0
(c) mercury 0 (d) iron 0 (c) electrical furnace 0 (d) muffle furnace 0
24. Heating of pyrites in presence of air to remove sulphur is 38. Which method of purification is represented by the
called as : [A,F,M.C. 2005] following equations? [C.li.E. (Kefala) 2004;
(a) roasting 0 (b) calcination 0 P:,E. (Orislla) 2010]
(c) smelting P (d) fluxing 0
Ti+2Iz 523K ) TiI 4 1700K )Ti+2I z
25. Calamine is :
(a) Zns0 4 o (b) Zno o (a) Cupellation 0 (b) Poling 0
(c) ZnS o (d) ZnC0 3 o (c) Van Arkel 0 (d) Zone refining 0
26. Radium is obtained from : 39. Van Arkel method of purification of metals involves
(a) pitchblende 0 (b) haematite 0 converting the metal to a :
(c) monazite 0 (d) none of these 0 (a) volatile stable compound 0
27. From gold amalgam, gold may be recovered by : (b) volatile unstable compound 0
(a) addition of Zn metal 0 (c) non-volatile stable compound 0
(b) electrolytic refining 0 (d) none of the above 0
(c) distillation 0 40. Zone refining is a method to obtain :
(d) dissolving Hg in HN03 0 (a) very high temperature 0
28. Froth floatation process is used for the : (b) ultrapure Al 0
(a) oxide ores 0 (b) sulphide ores 0 (c) ultrapure metals 0
(c) chloride ores 0 (d) all of these 0 (d) ultrapure oxides 0
29. Leaching is a process of : 41. MgO can be used as refractory material because :
(a) reduction 0 (b) concentration 0 (a) it is a good electrical insulator 0
(c) refining 0 (d) oxidation 0 (b) it has high melting point 0
30. Which one of the following is not a basic flux? (c) it is a good conductor of heat 0
(a) CaC03 0 (b) CaO 0 (d) all of these 0
(c) SiOz 0 (d) MgO 0 42. Leaching can be used for the extraction of which metals ?
31. Ore dressing for iron is done by : (i) Ph (ii) Al (iii) Ag (iv) Au
(a) froth floatation process 0 (a) (ii), (iii) and (iv) 0 (b) 0), (ii) and (iii) 0
(b) magnetic separation 0 (c) (ii) and (iv) 0 (d) (iii) and (iv) 0
(c) hand picking 0 43. Of the following metals the one which cannot be obtained
(d) all of the above 0 by electrolysiS of the aqueous solution of its salt is :
32. In the manufacture of iron from haematite, limestone is (a) Ag 0 (b) Mg 0
added to act as : (c) Cu 0 (d) Al 0
(a) flux 0 (b) slag 0 44. The electrolytic reduction technique is used in the extraction
(c) a reducing agent 0 (d) an oxidising agent 0 of:
33. Carnallite is a double salt of : [C,I\.C.E,(Dtbll},) ~OlOJ (a) highly electronegative elements o
(a) NaCl, NaNO;! 0 (b) KzO, Alz03 0 (b) transition metals o
(c) KCl, MgCh 0 (d) NaCl, MgCl2 0 (c) metalloids o
34. Which of the following reactions occur during calcination? (d) highly electropositive elements o
(0 CaC03 ~ CaO + COz 45. The acidic refractory material is :
(ii) 4FeSz + 110z ~ 2Fez~ + 8502 (a) CaO 0 (b)P20s o
(iii) 2Al(OHh ~ AlP3 + 3HP (c) SiOz 0 (d) MgO o
(iv) CUzS + 2CuO ~ 4Cu + SOz 46. The metal extracted from sea water is :
(a) (i) and (iii) 0 (b) (0 and (in 0 (a) Mg 0 (b) Al o
(c) (i) and (iv) 0 (d) (iii) and (iv) 0 (c) Ca 0 (d) Ba o
35. The main function of roasting is : 47. The metallurgical process in which a metal is obtained in a
(a) to remove the volatile impurities o fused state is called :
(b) oxidation o (a) smelting o (b) roasting o
(c) reduction o (c) calcination o (d) froth floatation o
(d) to make slag o
48. Asbestos is a silicate mineral of calcium and : (c) ll-Bf ID-O, IV-A o
(a) AI 0 (b) Mg 0 (d) 1-0, II-A, ID-C, IV-B o
(c) Ba 0 (d) K 0 58. Which of the following does not contain Mg?
49. Which method of purification is represented by the (a) Magnetite 0 (b) Magnesite o
following equation? (c) Asbestos 0 (d) Carnallite o
Ni+4CO~Ni(CO)4 180°C )Ni+4CO 59. AgzS + NaCN ~ [A]
[A] +Zn~ [B]
(a) Van Arkel 0 (b) Zone refining 0
[B] is a metal. Hence, [A] and[B] are:
(c) Mond 0 (d) Cupellation 0
(a) Na2[Zn(CN)4], Zn 0 (b) Na[Ag(CN)2], Ag 0
50. Which oil is used as frother in froth floatation process?
(c) Na2[Ag(CN)41, Ag 0 (d) Na3[Ag(CN)4], Ag 0
(a) Mustard oil 0 (b) Coconut oil 0
60. Which of the following metals is leached by cyanide
(c) Olive oil 0 (d) Pine oil 0
process? lA.I.B.B.E. 2002]
51. The incorrect statement is :
(a) Calamine and siderite are carbonates 0
(a) Ag o (b) Na o
(b) Argentite and cuprite are oxides 0
(c) Al o (d) Cu o
61. Pyrolusite is a/an: [D.P.M.T.2002J
(c) Zinc blende and iron pyrites are sulphides 0
(a) oxide ore 0 (b) sulphide ore • 0
(d) Malachite and azurite are ores of copper 0
(c) carbide ore 0 (d) not an ore 0
52. In the commercial electrochemical process for aluminium
62. Which one of the following ores is not concentrated by froth
extraction, the electrolyte used is :
floatation process? fe.Ii.T. (Tamil Nadu) 2001J
(a) AI(OH)3 in NaOH solution 0
(a) Copper pyrites 0 (b) Pentlandite 0
(b) An aqueous solution of AI2(S04)3 0
(c) Pyrolusite 0 (d) Zinc blende 0
(c) A molten mixture of Al20 3 and Na:¥\lF6 0
63. The common method of extraction of metal from oxide ores
(d) A molten mixture of AI20 3 and AI(OHh 0
is : [P.E.T. (M.P.) 2002)
53. When an aqueous solution of sodium chloride is
(a) reduction with carbon 0
electrolysed using platinum electrodes, the ions discharged
(b) reduction with hydrogen 0
at the electrodes are :
(c) reduction with aluminium 0
(a) sodium and hydrogen o (d) electrolytic method 0
(b) sodium and chloride o 64. Sulphide ores of metals are usually concentrated by froth
(c) hydrogen and chloride o floatation process. Which one of the following sulphide ores
(d) hydroxyl and chloride o offers an exception and is concentrated by chemical
54. Cassiterite is an ore of :
leaching? [C.B.S.E. 2007]
(a) Mn 0 (b) Ni 0
(a) Galena 0 (b) Copper pyrite 0
(c) Sb 0 (el) Sn 0
(c) Sphalerite 0 (d) Argentite 0
55. Cryolite is : tCP.M.T. 2000]
65. Among the metals Cr, Fe, Mn, Ti, Ba and Mg, the one that
(a) Na3AlF6 and is used in the electrolysis of alumina for
cannot be obtained by reduction of its metal oxide by
decreasing electrical conductivity' 0
aluminium is: [P.M.T. (Kelala) 2007]
(b) Na~6 and is used in the electrolysis of alumina for
(a) Cr 0 . (b) Fe 0
lowering the melting point of alumina 0 (c) Mn 0 (d) Ba 0
(c) Na3AlF6 and is used in the electrolytic purification of
Mg
(e) 0
alumina o 66. Native ·silver metal forms a water soluble complex with a
(d) Na3AlF6 and is used in the electrolysis of alumina 0
dilute aqueous solution of NaCN in the presence of:
56. The process of converting hydrated alumina into anhydrous
lU:r. 2008]
alumina is called : [Roork(!(! (8) 20(0)
(a) nitrogen 0 (b) oxygen 0
(a) roasting 0 (b) smelting 0
(c) carbon dioxide 0 (d) argon 0
(c) dressing 0 (d) calcination 0
[Hint : 4Ag + 8NaCN + 2H20 + ~ 4[NaAg(CN)2]
+ 4NaOH]
codes given below in the lists : rS.c.R.A. 20(1)
67. Which of the following factors is of no significance for
List I List II
roasting sulphide ores to the oxides and not subjecting the
I. cyanide process A. ultrapure Ge
sulphide ores to carbon reduction directly?[A.l.E. E..E, 20(8)
II. floatation process B. pine oil
(a) CO2 is more volatile than C~ 0
III. electrolytic reduction C. extraction of Al
(b) Metal sulphides are thermodynamically more stable
IV. zone refining O. extraction of Au
than CSz 0
Codes:
(c) CO2 is thermodynamically more stable than C~ 0
(a) I-C, II-A, ID-O, IV-B o (d) Metal sulphides are less stable than the corresponding
(b) 1-0, II-B, ID-C, IV-A o oxides 0
[Hint : The reduction process is on the theni'lodynamic stability (a) Zinc can be oxidised by CO D
of the products and not on their volatility.] (b) Zinc oxide can be reduced by C D
68. Composition of azurite mineral is: {J.E.E. (W.E.) 2008] , (c) Both statements (a) and (b) are true D
(a) CuC03· CuO D (b) Cu(HC03h' Cu(OHh D (d) Both statements (a) and (b) are false D
(c) 2CuC03· Cu(OHh D (d) CuC03· 2Cu(OHh D 74. The ore that is concentrated by froth floatation process is :
69. Which of the following metal is not manufactured by {C.E.T. (Karnataka) 20091
electrolysis? (P.M.T. (Kerala) 2008] (a) cinnabar' D (b) bauxite D
(a) Na D (b) Mg D (c) malachite D (d) zincite D
(c) Al D (d) Fe D 75. Hydro-metallurgical process of extraction of metals is based
(d) Li D on : {J.E'£' (Orissa) 2009]
70. The method not used in metallurgy to refine the' impure (a) complex formation D (b) hydrolysis D
metal is: [P.M.T. (Kerala) 20081 (c) dehydration D (d) dehydrogenation D
(a) Mond process D (b) Van Arkel process D 76. In alumino-thermic process, aluminium is used as :
(c) Amalgamation process D {J.E-E. (Orissa) 2009]
(d) Liquidation D (a) oxidising agent D
71. Extraction of zinc from zinc blende is achieved by: (b) reducing agent D
II.LT.2007J (c) dehydrating agent D
(a) electrolytic reduction D (d) complex formation agent D
(b) roasting followed by reduction Witncatb6h D .\ 77. According to Ellingham diagram, the oxidation reactioif of
(c) roasting followed by reduction with another metal D carbon and carbon monoxide may be used to reduce which
(d) roasting followed by self reduction D one of the following oxides at the lowest temperatures?
[Hint : 2ZnS + 302 ----t 2ZnO + 2502; fP.E.T. (KeraL1) 2010)
D (b) CU20 D
Zno + C > 1270 K) Zn + CO ] .
D (d) Zno D
72. IlGo vs T plot in Ellingham diagram slopes downward for
78. The chemical reaction that involves roasting process is :
the reaction: lK.C.E.T. 2006J
fEAM.CE.T. (E'ngg.) 20101
(a) Mg + ~ O 2 ----7 MgO D (b) 2Ag + ~ O2 ----7 Ag20 D (a) Fe203 + 3CO ----7 2Fe + 3C02 D
1 1 (b) 2AI + Fe203 ----7 2Fe + Al20 3 D
+ 2 O2 ----7 CO
(c) C D (d) CO + 2 O2 ----7 CO2 D
(c) 2Zn5 + 302 ----7 2ZnO + 3502 D
73. .Consider the following reactions at 10000(.
(d) FeO + 5i02 ----7 Fe5i03 D
. 1 1
(A) Zn(s) + 2 02(g) ----7 ZnO(s); IlGO = - 360 kJ mor
(B) C(s) + ~ 02(g) ----7 CO(g); IlGo = - 460 kJ morl
Choose the correct statement at 1000°C.
[M.E.E. (Kerala) 20061
Set II : This set contains questions with two or more correct answers.
79. Ca3 (P04h is : (a) Cu .1 D (b) Al D
(a) Thomas slag
(b) used in cement manufacturing
(c) used in manufacture of phosphorus fertilizer
D
D
D
Ij 85.
(c) Mg D (d) Ag
Which of the following ores is/are oxide ore(s) ?
i (a) Cassiterite D (b) Bauxite
D
D
(d) used as a refractory material D (c) Cryolite D (d) Haematite D
80. Metal(s) which does/do not form amalgam is/are: 86. Auto-reduction process is used for the extraction of :
(a) Fe D (b) Zn D UUtU.2OO71
(c) Ni D (d) Au D (a) C u ] (b) Hg D
81. Bauxite is purified by : (c) Pb 0 (d) Al D
(a) Hall's process D (b) Baeyer's process D 87. Which of the following are correctly matched?
(c) Serpeck's process D (d) Bett's process D (a) Malachite CuC03· Cu(OHh D
82. The processes which do use catalysts are: (b) Chalcopyrite CuFe~ D
(a) contact process D (b) therrnite process D (c) Copper glance CU25 D
(c) Ostwald's process D (d) Haber's process D (d) Azurite C U20 D
83. Metallurgy involves steps : 88. Which of the following are correct processes ?
(a) concentration of ore D (b) reduction of ore D (a) Fe + Al 20 3 ----7 7AI + Fe203 D
(c) purification D (d) alloy formation D (b) Zno + C ----7 Zn + CO D
84. Which of the following metals are extracted by electrolytic (c) Cr203 + 2AI ----7 2Cr + Al20 3 D
reduction ? (d) 2[Ag(CNhr + Zn ----7 2Ag + [Zn(CN)4f- D
1. (a) 2. (b) 3. (c) 4. (d) 5. (d) 6. (c) 7. (b) 8. (a) 9. (a) 10. (b)
11. (d) 12. (a) 13. (d) 14. (b) 15. (e) 16. (b) 17. (c) 18. (c) 19. (b) 20. (c)
21. (a) 22. (a) 23. (c) 24. (a) 25. (d) 26. (a) 27. (c) 28. (b) 29. (b) 30. (c)
31. (b) 32. (a) 33. (e) 34. (a) 35. (b) 36. (b) 37. (e) 38. (c) 39. (a) 40. (c)
41.. (d) 42. (a) 43. (b) 44. (d) 45. (c) 46. (a) 47, (a) 48. (b) 49. (c) 50. (d)
51. (b) 52. (e) 53. (c) 54. (d) 55. (b) 56. (d) 57. (b) 58. (a) 59. (b) 60. (a)
61. (a) 62. (c) 63. (a) 64. (d) 65. (e) 66. (b) 67. (a) 68. (e) 69. (d) 70. (c)
71. (b) 72. (e) 73. (br 14. (a) 75. (a) 76. (b) 77. (b) 78. (c) 79. (a, b, c) 80. (a, c)
81. (a, b, c) 82. (a, c, d) 83. (a, b, c) 84. (b, c) 85. (a,b,d) 86. (a,b,c) 87. (a,b,c) 88. (b,c,d)
·i.~· Objective Questions for liT ASPIRANTS ~.'I:

1. The ore having two metal atoms is: (b) Calamine and azurite are carbonates o
(a) haematite D (b) galena D (c) Zinc blende and pyrites are sulphides o
(c) magnetite D (d) copper pyrites D (d) Malachite and azurite are ores of copper o
2. The metal for which, its property of formation of volatile [Hint : Argentite is a sulphide ore.]
complex is taken into account for its extraction is: 6. Chromium is obtained by reducing purified chromite ore
(a) cobalt D (b) nickel D with:
(c) vanadium D (d) iron D (a) red hot coke [J (b) gaseous hydrogen 0
[Hint : Nickel forms Ni(CO)4 (volatile complex) with CO which
(c) aluminium powder D (d) carbon monoxide 0
decomposes to give nickeL]
7. Which one of the following reactions is an example for
3. Zone refining is based on the principle of: calcination process?
(a) fractional distillation D (a) 2Ag + 2HCl + [0] 2AgCl + H 20 0
(b) partition coefficient D (b) 2Zn + O 2 2ZnO 0
(c) fractional crystallisation D (c) 2ZnS + 302 2Zn0 + 2S02 0
(d) chromatographic separation D (d) MgC0 3 MgO + CO 2 0
4. When an impurity in metal has greater affinity for oxygen 8. The most electropositive metals are obtained from their ores
and is more easily oxidised than the metal itself, then the by:
metal is refined by: (a) high temperature reduction with carbon 0
(a) cupellation D (b) zone refining D (b) electrolysis of fused ionic ~alts 0
(c) poling D (d) electrolytic process D (c) self reduction 0
5. Among the following, the incorrect statement is: (d) thermal decomposition 0
(a) Argentite and cuprite are oxide ores D
1. (d) 2. (b) 3. (c) 4. (a) 5. (a) 6. (c) 7. (d) 8. (b)

1. Match the ores of List-I with their composition in List-II: (c) Cupellation (r) Manufacture of Na2C03
List-I List-II (d) Solvay process (s) Purification of titanium
(a) Malachite (p) Sulphide of copper 4. Match List-I with List-II:
(b) Azurite (q) Sulphide of iron List-I List-II
(c) Chalcopyrites (r) Oxide of copper (a) Magnesite (p) Ore of magnesium
(d) Cuprite (s) Ore containing carbonate (b) Dolomite (q) Ore of aluminium
of copper (c) Corundum (r) Oxide ore
2. Match the ores of List-I with their composition in List-II: (d) Bauxite (s) Carbonate ore
List-I List-II 5. Match List-I with List-II:
(a) Iron pyrites (p) FeS2 List-I List-II
(b) Fool's gold (q) Sulphide ore (Metal) (Procedure of extraction)
(c) Galena (r) Fe203 (a) Iron (p) Carbon reduction method
(d) Haematite (s) Concentrated by froth (b) Lead (q) Self reduction
floatation process (c) Copper (r) Thermite process
3. Match the Column-I with Column-II: (d) Chromium (s) Hydrometallurgical
Column-I Column-II process
(a) Van Arkel method (p) Purification of copper
(b) Poling (q) Refining of silver
6. Match the metals of List-I with the process of refining of 8. Match the metals of List-I with their distribution in India
List-II: List-II:
(a) Ni (p) Mond's process (a) Gold (p) Singhbhum
(b) Ti (q) Van Arkel method (b) Copper (q) Kerala coast
(c) Zr (r) .Distillation (c) Thorium (r) Kolar (Karnataka)
(d) Zn (s) Pyrometallurgical process (d) Calcium (Gypsum) (s) Khetri
7. Match the metals of List-I with the biolOgical origin of (t) Rajastl;l.an
List-II: 9. Match the Colurnn-I with Column-II: U.I.T. 2008J
List-I List-II Column-I Column-II
(a) Chromium (p) Chloroplast (a) PbS ------t PbO (p) roasting.
(b) Iron (q) Haemoglobin (b) CaC03 ------t CaO (q) calcination .
(c) Zinc (r) Eyes of cats and cows (c) Zns ------t Zn (r) carbon reduction
(d) Calcium (s) Prown (d) CuzS ------t Cu (s) self reduction
(t) Bones
1. (a-s) (b-s) (c-p, q) (d-.r) 6. (a-p) (b-q) (c-q) (d-r, s)

2. (a-p, q, s) (b-p, q, s) (c-q, s) (d-r) 7. (a-s) Urp, q) (c-rl (d-t)
3. (a-s) (b-p) (c-q) (d-r) 8. (a-r) Urp, 5, t) (c-q! (d-t)
4. (a-p, s) (b-p, 5) (c-q, r) (d-q, r) 9. (a-p) (b-q) (c-p, r) (d-p, s)
5. (a-p) Urp, q) (c-q, 5) (d-r)

The questions given below consist of an Assertion (A) and (R) The metals which are noble and chemically less reactive
Reason (R). Use the following key to choose the correct answer: are found in free state.
(a) If both (A) and (R) are correct and (R) is the correct 4. (A) Roasting is a' process 1n which the ore is heated in
explanation of (A). presence of air.
(b) If both (A) and (R) are correct and (R) is not the correct (R) Concentration of sulphide ore is c'one by calcination
explanation of (A). method.
(c) If (A) is correct but (R) is incorrect. S. (A) Carnallite is a nilneral of magnesium.
(d) If (A) is incorrect but (R) is correct. (R) Sodium is extracted by electrolysis of aqueous sodiun,
(e) If both (A) and (R) are incorrect. chloride solution.
1. (A) All nilnerals are ores. 6. (A) Ag and Au are extracted by leaching their ores with a
(R) Ores are nilnerals from which metal can be extracted dilute solution of NaCN is presence of oxygen.
conveniently and economically. (R) Gangue particles dissolve in NaCN solution.
2. (A) Metals of high purity are obtained by zone refining. 7. (A) Alunilna has high conductivity.
(R) Impurities are more soluble in the melt than in pure (R) The mixture of alumina and cryolite is used for
metal. electrolytic reduction in order to extract aluminium.
3. (A) Au, Pt, Ag, etc., are found in free state. 8. (A) Oxide ores are concentrated by froth floatation process.
(R) In froth floatation process, mineral oil is used.
1. (d) 2. (b) 3. (a) 4. (c) 5. (e) 6. (c) 7. (d) 8. (e)

lhe answer to each of the following questions is a single 2. In the bauxite ore, AI20&xH20, what is the value of x?
digit integer, ranging from 0 to 9. 3. Iron is ..... th most abundant element in the earth's crust.
1. Au + CN- +- H 20 + O2 ----:, [Au(CNhr -t: OW 4. In Goldschmidt aluminotherrnic process, therrnite mixture
How many CN- ions are involved in· the above balanced ('ontains--parts Fe2~ and 1 part aluminium.
equation? 5. How many different compounds are present in carnallite?
. 1. (8) 4Au + 8C~ + 2HP + 02 --; 4[Au(CNhr + 40H"" 4. (3) 3 parts Fe203 and one part AI.
2. (2) A1 203· 2H 20
5. (3) MgC12. KG. 6H 20
3. (4) Iron is 4th most abundant element in the earth's crust.
1 2 3
Rl!visioli·E"e.rci§1!
.~-> :·~::)(f·iC-·-. '.
r,.I[:hi:lp1:i:!r 1 1:0 4)
' .
i)
SINGLE CORRECT ANSWER TYPE (c) Mn, Cr, V, Sc-Decreasing number of oxidation states 0
1. The number of elements having 3d-electrons out of first 92 l,
(d) p6, d lO , d S-Decreasing relative stability 0
3
elements in the periodic table are : 9. 02-,F, Na+, Al + are isoelectronic ions. Their ionic sizes
(a) 80 0 (b) 78 0 follow the order:
(c) 76 0 (d) 72 0 (a) 02- > F > Na+ > Al 3+ 0
2
(b) 0 - < F < Na+ < A13+ 0
2 The element with atomic number 118(Uuo) has been dis-
covered recently. Which of the following statements is not (c) A1 3+ > 02- > Na+ > :F- 0
expected for this element? (d) Na+ < Al 3+< 02- < F 0
(a) It is a radioactive element 0 10. The first ionisation energy of B is less than that of .Be
It.
(b) is a solid at room temperature 0 because :
.It (c) It's ionisation energy is lowest in group 18 0 (a) boron has greater nuclear charge than beryllium 0
(d) It is more reactive than xenon 0 (b) In beryllium s-electron is removed and from.' boron
3. Actinides are all : p-electron is removed 0
(a) man-made elements 0 (c) p-electron of boron is more shielded from nucleus 0
(b) have only shortlived isotopes 0 (d) both (b) and (c) 0
(c) the elements from atomic number 90 to atomic number 11. The values of electronegativity of atoms A and B are 1.0 and
103 and show variable oxidation states 0 4.0 respectively. The percentage ionic character of A-B is :
(d) the elements from atomic number 90 onwards and upto (a) 90 0 (b) 75.5 0
the last element with atomic number 118 0 (c) 50.0 0 (d) 79.5 0
4. An element has the configuration, 12. Bond length of HCI is 1.275A. If 11 is 1.03 D, then HC} is :
Is2,2s2 2p6,3s
23p
63d S,4s2 (a) 100% ionic 0 (b) 40% ionic 0
(c) 83.18% covalent 0 (d) 50% covalent C
to which block and group of the long form of periodic table,
13. Which of following does not possess tetrahedral structure?
does this belong?
(a) d-block, 7th group 0 (b) d-block, 5th group 0 (a) S0zCl2 0 (b) SiOt" 0
(c) s-block, 2nd group 0 (d) p-block, 15th group' 0 . (c) SO~- 0 (d) SF4 0
5. Which one of the following statements is wrong? 14. A molecule which possesses both sp3 and sp3d 2 hybridi~
(a) Bromine is liquid at room temperature 0 sation is :
(b) Carbon has highest melting point amongsinon-metals (a) PCIs(g)· 0 (b) PCls(s) 0
o (c) PCl6 0 (d) none of these 0
(c) Fluorine has the highest electron gain enthalpy 0 15. The species which does not show paramagnetism?
(d) Osmium possesses highest density 0 (a) Oz 0 (b) 0; 0
6. The number ~of elements in each period is : (c) O~- 0 (d) H; 0
(a) twice the principal quantum number which is being filled
16. The bond angles of NH3, NH! and NH2 are in the order:
o
(a) NHZ>NH3>NH! 0 (b) ~>NH3>NH2 0
(by twice the number of atomic orbitals available in the
(c) NH3 > NH2 > NH! 0 (d) NH3 > NH! > NHz 0
energy level being filled 0
17. Iso-structural pair amongst the following is :
(c) twice the number of atomic mass of the elements 0
(d) none of the above 0
(a) XeF2, IF z 0 (b) NH3, BF3 0
7. The 4d-transition series contains elements having atomic . (c) CO~-, SO~- 0 (d) PCIs,ICls 0
numbers from: 18. Among KOz, AlOz, BaOz, NO; unpaired electron is present
(a) 40 to 49 0 (b) 39 to 48 0 in:
(c) 39 to 49 0 (d) 39 to 47 0 (a) NO; and Ba02 0 (b) K0 2 ~d AlO z 0
8. Which is not arranged in the correct sequence? (c) K0 2 only 0 (d) Ba02 only 0
(a) d 5, d 4, d 2, d1-Increasing magnetic moments 0 19. The correct hybridisation state of sulphur atom in SF2, SF4
and SF6 molecules is respectively :
(b) MO, M203, M02, M20S-Increasing acidic strength 0
(a) sld, sl, sld2 0 (b) sl, sp3d, sp3d2 0
(c) sp3d 2, sl, sld 0 (d) sp3 d 2, sld, sp3 0
210 GRB. Inorganic Chemistry for Competitions
20. The correct order of lattice energies of the following ionic (C) Therrnite process (3) . Extraction and
compounds is: purification of Ni
(a) NaCl > MgCl 2 > CaO > Al20 3 0 (D) Mond's process (4) ExtractionofCr
(b) NaO > Cao > MgCl2 > Al20 3 0 (a) A = 2, B 1, C = 4, D = 3 0
(c) Al2~ > MgCl2 > CaO > NaCl 0 (b) A= 1, B =2, C=3, D =4 0
(d) Al 20 3 >Cao > MgCl2 > NaCI 0 (c) A 4, B = 3, C = 2, D = 1 0
21. Which of the following can act both as a Bronsted acid and (d) A 3, B = 4, C J,D =2 0
a Bronsted base? 30. The metal obtained by seif reduction process is :
NHt
(al 0 (b) Coj- 0 (a) Cu 0 (b) Hg 0
(c) H2S04 0 (d) HS- 0 (c) Pb 0 (d) All of these 0
22. Among Al20 3, Si02, P 20 3 and S~, the correct order of acid
strength is : . ONE OR MORE THAN ONE CORRECT
(a) .AI20 3 < Si02 <: P 20 3 < S02 0 ANSWERS TYPE
(b) SiOz < S02 <Al2 0 3 <P203 0 31. The electronegativity of an element:
(c) AI2~ < Si02 < S02 < P203 0 (a) is its tendency to attract the shared electrons in a molecule
·(d) ~ <P20 3 <Si0 2 < Al20 3 0 towards itself 0
23. The strongest Bronsted base in the following anions is : (b) is always constant 0
(a) 00- 0 (b) 002 D (c) depends on the valency of the element 0
(c) 003 0 (d) 004 0 (d) depends on the percentage of s-character in the
24. The strength of the acid depends on the : hybridised state of the atom. 0
(a) number of hydrogen atoms present in the molecule 0 32. In which of the following arrangements, the order is correct
(b) density D for the property indicated against it?
(c) oxygen content D (a) Increasing size, Al3+ < Mg2+ < Na+ < F 0
(d) concentration of hydrogen ions furnished by ionisation (b) Increasing IE, B < C < N < 0 0
D (c) Increasing EA, 1< Br < F < CI 0
25. The reverse process of neutralisation is : (d) Increasing metallic radius Li < Na < K < Rb 0
(a) decomposition 0 (b) hydrolysis 0 33. Which of the following species have same shape and same
(c) dehydration 0 (d) synthesis D bond order?
26. The conjugate base of [AI(H20h(OHhl is : (i) CO2 (li) N:3 (iii) 0 3 (iv) NO z
(a) [AI(H20h(0H)21+ 0 (b) [AI(H20h(0H)20r D (a) (i) and (ii) o (b) (iii) and (iv) o
(c) [AI(HzOh(0H)4r D (d) [AI(H20h(0H)4r 0 (c) (i) and (iii) D (d) (ii) and (iv) o
27. Which of the following processes involves roasting? 34. Diamagnetic species are :
(a) Znc03 ---'; ZnO + CO2 D (a) N2 0 (b) N~- 0
(b) Fe203 + 3C ---'; 2Fe + 3CO D
(c) Oz 0 (d) O~- 0
(c) 2PbS + 302 ---'; 2PbO + 2S02 0
35. Mark the correct statements out of the following :
(d) AI2~·2H20 ---,;Al20 3 +2H20 D
(a) Helium has the highest first ionisation enthalpy 0
28. Match List-I (ores) with List-II(metalsYand select the correct
(b) Chlorine has the highest electron gain enthalpy 0
answer using the codes given below :
(c) Fluorine has the highest electronegativity 0
List-I List-II
(d) Hg and Br are liquids at room temperature 0
(A) Bauxite (1) AI
36. Which of the· following have sp3-hybridisation?
(B) Haematite (2) Pb
(a) NF3 0 (b) NO.3 0
(C) Galena (3) Cu
(c) BF3 0 (d) H30+ 0
(D) Chalcopyrite (4) . Fe
37. In the roasting process, the ore is heated :
(a) A 1, B =4, C 3, D = 2 0
(a) below its melting point D
(b) A =1, B =4, C =2, D =3 0
(b) for removing moisture and volatile matter D
(c) A=4,B 1,C=2,D 3 0
(c) in the presence of flux in order to remove gangue D
(d) A = 4, B 1, C = 3, D 2 D
(d) none of the above 0
29. Match List-I with List-II and select the :::orrect answer using
38. Therrnite is a mixture of :
the codes given below :
(a) oxides of Cr and Mn 0
List-I List·II
(b) oxides of Cr and AI D
(A) Poling (1) Refining of Ag
(c) 'AI powder and oxide of Cr 0
(B) Cupellation (2) Refining of Cu
(d) Al powder and oxide of Mn D
Revision Exercise: 1 (Chapter 1 to 4)' 211
39. Lewis acids are : 50. (A) o-nitrophenol has lower boiling' point than p-nitrophenol.
(a) BF3 D (b) Ba02 D (R). o-nitrophenol has lower boiling point due to presence of
(c) AI03 D (d) SnC4 D intramolecular H-bonding while p-nitrophenol has inter-
40. In the reaction; molecular H-bonding.
HC204+POt HPO~- + C20~-
MATRIX MATCHING QUESTIONS
the Bronstedbases are :
51. Match Column-I with Column-II:
(a) HC204" D (b) POt D
.CoIumn-I
(c) HPOa- D (d) c:pl- o (a) 4?4p6 (p) Metal
(b) 4j14Sd 106? (q) Non-metal
ASSERTION-REASON TYPE QUESTIONS
(c) 4lsd l 6? (r) Noble. gas
The following questions'. consist of an Assertion (A) and (d) 4dIOS?Sp5 (s) Lanthanide
Reason (R). Use the following key· to choose the appropriate
·answer. 52. Match Column-I with Column-II:
(a) If both (A) and (R) are correct and (R) is the correct CoIumn·I CoIumn-H
explanation of (A). . (a) NH3 (p) sp3 hybridisation
(b) Ifboth (A) and (R) are correct but (R) is not the correct (b) XeF6 (q) One lone pair is present
explanation of (A). (c) B2H6 (I:) multicentre bonds are prese.'l,t
(c) If (A) is correct but (R) is not correct. (d) NHt (s) pyramidal shape
(d) If (A) is incorrect but (R) is correct. 53. Match Column-I with Column-II:
41. (A) BeCl2 is covalent whereas BaCl2 is ionic. Column-I CoIumn-H
(R) Smaller is size of the cation, greater is. the polarising (a) Cyanide process (p) Extraction of Ag
power. (b) Electrolytic reduction (q) Extraction of Au
42. (A) Mn2+ is diamagnetic. (c) Carbon reduction (r) Extraction of Al
(R) All the orbitals except d-orbitals are doubly' occupied. (d) Self reduction (s) Extraction of Pb
43. (A) All F-S-F angles in SF4 are greater than 90" but less than (t) Extraction of Hg
180". 54. Match Column-I with Column-II:
(R) The lone pair-bond pair repulsion is weaker than bond CoIumn-I CoIumn·H
pair-bond pair repulsion. (a) O:l (p) Diamagnetic
44. (A) Basic nature of the following anions follows the order, (b) N2 (q) Paramagnetic
004 < SOa- < 0- < N03" (c) Cz (r) Double bond
(R) Stronger acid has its conjugate base weaker. (d) ~ (s) Triple bond
45. (Al Cao, which is a cheap and high melting compound, is 55. Match Column-I with Column-II:
used in the lining of the furnace. CoIumn-I CoIumn-H
(R) Cao is used as a flux for the removal of acidic impurities (a) H3P02 (p) Dibasic
like silica in the ore. (b) HI (q) Monobasic
46•. (A) Auto reduction of ores is used for cinnabar, copper glance (c) H2S04 (r) Reducing agent
and galena ores. (d) H2S03 (s) Oxidising agent
(R) The sulphide ores of Hg, Cu and Pb react with their
corresponding oxides to give respective metals. INTEGER ANSWER TYPE
47. (A) Electron gain enthalpies of halogens are maximum in their
56. The total number of d-block series in the periodic table are :
respective periods.
57. How many noble gases are known?
(R) Fluorine has maximum value of electron gain-enthalpy.
58. How mimy elements are present in third period of periocl.ic
48. (A) Bond order can assume any value including zero.
table?
(R) Lower the bond order, larger is the bond length and
59. What is the electronegativity of most electronegative element
smaller is the bond energy. on Pauling scale?
49. (A) Ina. change from PCl3 to PCIs, the hybrid state of P
60. The number of total lone pairs in ICli is :
remains the same. ' 61. The bond order of CO is:
(R) The shape. of PCl3 is pyramidal while that of PCIs is
62. How many ionisation energies can carbon have?
trigonal bipyramidal.
212 GR.B. Inorganic Chemistry for Competitions
(b) more shielding effect of d-electrons

CI
63. Lewis structure of the molecule, COCl2 is o=c( (c) poor shielding effect off-orbitals in Ga
(d) high shielding effect of 3s, 3p and 3d-electrons
Cl 70. The effective nuclear charge for 4s electron of Ca atom will
What is the fonnal charge on carbon? . . be:
64. An element has electroniC configuration, Ii, 2i2p6, (a) 17.15 (b) 20.0
3i3i3ti, 4s2. To which group of the extended fonn of (c) 2.85 (d) 2.2
periodic table does it belong? 71. The maximum atomic radius amongst the following is for:
65. In Goldschmidt-Aluminothermic process, thermite mixture (a) Na (b) Mg
contains ......... parts Fe203 and one part Al. (c) Al (d) Si
Passage 3
LINKED COMPREHENSION TYPE
Binary acids contain orily hydrogen and another non-metal.
Passage 1 Their strengths increase from top to bottom within a group and
- - from left to right across a period. Oxoacids, which contain oxygen
atoms in addition to hydrogen and another element, increase in
- - strength as the number of oxygen atoms on the same central atom
l- I- increases. Delocalisation of negative charge enhances the stability ,_
A F H
of the oxoacid anions, making them weaker bases and as a result,
G
their conjugate acids are correspondingly stronger. Oxoacids
B D having the same number of oxygen atoms generally increase in
J strength as the central atom moves from left to right.
C E I
Answer the following questions :
72. The strongest acid of the following is :
(a) H4S:i04 (b) H2S04
Analyse the table and answer the following questions :
(c) HCl04 (d) H#04
66. 'C' represents an element named : . 73. Which is the weakest base among the following?
(a) Y«:rium . . (b) Cerium (a) cr (b) Br-
(c) Lanthanum (d) Actinium . (c) F- (d) r
67. Which of the following elements is not found in nature but 74. Consider the following compounds:
has been obtained by artificial means?
(a) C (b) D HO-A HO-B HO C
I II III
(c) G (d) J The electronegativities of A, Band C are in the order
68: The element which is known in gaseous state at room C > B > A. The correct order of acid strength ·of the above
temperature is : compounds is :
(a) H (b) F (a) 1 < II > III (b) III> II > 1
(c) G (d) J (c) III < II <I (d) II < III < 1
Passage 2 Passage 4
The amount of positive charge felt by the valence electrons of According to valence bond theory, a covalent bond is formed
an atomjs the effective nuclear charge. This is less than the actual between two atoms when an atomic orbital of one atom overlaps
nuclear charge because core electrons partially shIeld the valence with an atomic orbital of the other and a pair of electrons with
electrons from the full positive charge of the nudeus. Shielding opposite spins is shared between the overlapping orbitals. In
effect is calculated by applying Slater's rules. Atomic radii depend general, the better the overlap of the orbitals, the stronger the
on the value of n of the valence shell orbitals and the effective bond.
nuclear charge experienced by the valence electrons. Atomic radii Hybrid orbitals are fOlmed by mixing pure s, p' and d orbitals.
decrease from left to right in a period and from bottom tq top in a Hybrid orbitals overlap better with other orbitals than the pure
group in the periodic table. '. . .... atomic orbitals from which they are formed, so the bonds fOlmed
Answer the following questions : ". by hybrid orbitals are stronger than those fOIDled by ordinary
69. The atomic size of galli'jm IS smaller than alurniniunibecause: atomic orbitals. Two types of bonds sigma and 1t-bonds are formed
(a) due to poor shielding effect of electrons ind-orbitals, by overlapping. Sigma bonds are always stronger than 1t-bonds.
effective nuclear charge increases in Ga
Revision Exercise: 1 (Chapter 1 to 4) 213
Answer the following questions : 77. A x-bond is formed by overlap of:

75. The orbitals of same energy level providing the most efficient (a) s-s orbitals
overlafpinf are : (b) s-p orbitals
(a) sp -:sp (b) sp2 -si (e) p-p orbitals in sidewise manner
(e) sp-sp (d) all of these (d) p-p orbitals in end to end fashion
76. Strongest bond is formed by the head on overlrpping of :
(a) 2s and 2s orbitals (b) 2p and 2p ort>itals
(e) 2s and 2p orbitals (d) all of these :
.:.
1. (d) Filling of 3d-orbital starts from the element with atomic number 21. (d) HS- ----7 H+ +S2-; HS- + H 2S
21. Acid Base
2. (b) 22. (a)
3. (c) These are Sf-elements from at. no. 90 to at. no. 103. Some of 23. (a) The weakest acid furnishes strongest base anion.
the members are found in nature and few of the isotopes are 24. (d)
long-lived. 25. (b)
4. (a) The last electron enters d-orbital, thus the element belongs to 26. (c) [Al(H 2 0h(OHh] ----7 [Al(H 20h(OH)4f + H+
d-block and the group (3d 5 4s 2) = 5 + 2 = 7 27. (c)
5. (c) Chlorine and not fluorine has the highest electron gain enthalpy. 28. (b)
6. (b) 29. (a)
7. (b)
,30. (d)
8. (a) Magnetic moment depends on the number of singly occupied
31. (a, c, d)
orbitals.
32. (a, c, d)
9. (a) Ionic size decreases in isoelectronic ions when z/e ratio increases.
10. (d) It is easier to remove an electron from p-orbital as it is far from 33. (a, b) CO 2 and Ni are linear with bond order 2 in each case, 0 3
nucleus than s-orbital. It is also easier to remove electron from and N02 are V-shaped with bond order 1.5 in each case.
a singly occupied orbital than a paired orbital. 34. (a, d)
11. (d) % ionic character = 16(4.0 - 1.0) + 3.5(4.0 -1.0)2 35. (a, b, c, d)
=48 + 31.5 79.5 36. (a, d)
18 37. (a, b)
12. (c) e=l!. 1.03 x 10- 1.03 X 10-10 esu 38. (c, d)
d1.275 x 10-8 1.275 10
39. (a, c, d)
~. .. h t - 100 x 1.03 x 10- = 16.82
o lome c arac er - 4.803 x 10-10 1.275 40. (b, d)
i.e., 83.18% covalent. 41. (a)
13. (d) S in SF4 undergoes sp3 d hybridisation. It has a see-saw snape. 42. (d) Mn2+ is paramagnetic as its configuration is Ii, 2s~p6,
14. (b) PCls(s) is an ionic species, i.e.,
[PCI 4t[PCI6f. In [PCI 4t, P undergoes sp3
hybridisation while
3hp 6
3d
5
, i.e., 111111\ 1111
3d
in [PCI 6f, P is in
2
s/
d hybridised state.
15. (c) O~- has configuration 43. (c) The lone pair-bond pair repulsions are greater than the bond
pair-bond pair repulsion,the bond angle F-S-F decreases from
KKO(2s)2 cr(2i)o(2Pi1t(2Px)21t(2p y Nc(2Px)21c(2Pi
180".
All the molecular orbitals are doubly occupied hence O~- ion 44. (a)
is diamagnetic. 45. (b) Both the assertion and reason are correct. C;aO is used for lining
16. (b) N in au the three species is in sp3 hybridised state but in NHt of the furnace as its lattice energy is high.
no lone pair is present on it but in NH3, one lone pair and in 46. (a)
NH2, two lone pairs of electrons are present. Thus, bond angle 47. (c) Assertion is correct but reason is wrong as chlorine has
subsequently decreases. maximum electron gain enthalpy.
17. (a) XeF2 -Linear; IF2 -Linear 48. (b)
NH3-Pyramidal; BF3- Triangular planar 49. (d) In change from PCl 3 to PCls the hybridisation from sl to sp3d
C01--Triangular planar; SO~--Pyramidal occurs.
PCls- Trigonal bipyramidal; ICis-Square pyramidal 50. (a)
51. (a-q, r); (b--p); (c-p, s); (d-q)
18. (c) KO z has K+02 structure. 02 possesses one unpaired electron.
52. (a-p, q, s); (b--q); (c-p, r); (d-p)
19. (b) SF2 -s/; SF4-s/d; SF6-s/d 2
53. (a-p, q); (b--r); (o--s); (d-s, t)
20. (d)
54. (a-q, r); (b--p, s); (c-p, r); (d-q)
55. (a-q, r); (1H:j, r); (c-p, s); (d-p, r, s) 66. 'C' represents actinium with which 14 actinides are accommodated.
56. (4) 3d-, 4d-, 5d- and 6d-series. 67. 'D' represents technetium which is not found in nature. and has
57. (7) He, Ne, Ar, Kr, Xe, Rn and Uuo. been obtained by artificial means. .
58. (8) Na, Mg, AI, Si, P, S, CI, Ar. 68. (a) 'H' represents chlorine which is known in gaseous state at room
59. (4) Fluorine is the most electronegative element. temperature.
60. (3) Total number of electrons in iodide ion =8 69. (a) Lesser the shielding effect more will be the force of attraction
Number of bond pairs 2 = between valence electron and nucleus, smaller will be the atomic
8-2 size.
• Number of lone pairs 2 = 3 .= 70. (c) Z* = Z - 0 = (20 1 x 0.35 + 8 x 0.85 + 1 xlO)
6': (3) CO has 14 electrons (6 + 8 = 14) = =
(20 -17.15) 2.85
M.o. configuration : 71. (a) Shielding effect is minimum in Na amongst these elements of
. a a
O(b)2 (li)o(2s)2 (2s)21t(2P:ti1t(2p/O(2Pi the same period, hence it has maximum atomic radius.
10-4 6 72. (c)
Bond order =-2-=2=3.
73. (d)
62. (6) 74. (b) Higher electronegatlvity will favour more acidic strength.
63.' (0) Formal charge on carbon = 4 - 0 + 112 x 8 =0 75. (c)
64. (7) 76. (b)
65. (3) 77•. (c)
CHAPTER 5
Hydrogen and
its Compounds
1
IA
13 14 15 • Introduction
iliA IVA VA
Hydrogen is the lightest element. It is most abundant element in the univt.<rse,
comprising nearly 90% of all atoms and is the third most abundant element after
oxygen and silicon on the surface of the earth. Most planets (stars), including
our source of energy the sun, consist primarily of hydrogen. The hydrogen in
the sun is the fuel for the fusion reactions that produce the life-sustaining
energy which reaches our planet, i.e., on the earth.-The most important source
of hydrogen on earth is water. The majority of hydrogen is found in oceans
combined with oxygen as water.
Hydrogen atoms are .the simplest of the all atoms. It is the fIrst member of
the periodic table as its atomic number is one. It has the simplest atomic
structure among all the known elements. In atomic form, it consists of only one
proton and· a single planetary electron. Hydrogen, therefore, has the simplest
Contents: electronic confIguration, lsI. The atomic form of the hydrogen exists only at
very high temperatures. Normally, the elemental hydrogen is a diatomic molecule,
5.1 Position of Hydrogen in Periodic Table H2 (commonly known as dihydrogen), the product of an exothermic reaction
5.2 Discovery and Occurrence between H-atoms: .
5.3 Preparation
5.4 Manufacture of Hydrogen H(g) + H(g) ~ H2 (g); Ml' = -436.4 kJ morl
s.s Properties of Hydrogen The combustion of hydrogen produces more heat per gram than any other
5.6 Industrial Applications fuel. As compared to hydrocarbons, it is a "Clean fuel" because the product,
SA.I Hydrogen Economy water is environmentally benign. Higher consumption and least supply of
5.7 Hydrides hydrocarbons fndicate that hydrogen gas may become the favourite fuel of the
5.8 Special Forms of Hydrogen twenty-fIrst century.
5.9 Isotopes of Hydrogen The reaction of hydrogen with oxygen to form water is an example of a
5.10 Heavy Hydrogen or Deuterium reaction that requires the input of energy to get started, however, once it does,
5.11 Tritium the reaction is rapid and exothermic. Because it is such an exothermic and.the
5.12 Heavy Water or Deuterium Oxide product is a gas, it is an ideal rocket fuel.
5.13 Water Hydrogen forms more compounds than any other element. These include the
5.14 Hard and Soft Water organic compounds, biologically important compounds and acids and bases.
5.lS Hydrogen Peroxide Hydrogen is of great industrial importance and it is said that global energy crisis
can be overcome to a great extent by the use of hydrogen as a source of energy.
Note: Unipositive hydrogen ion (W) i.e., proton has a very small size (- 1.5 x 10-3 pm) compared to normal atomic and ionic sizes of 50 to 220
pm. It does not exist freely and is always associated with other atoms or molecules.
POSITION OF HYDROGEN hydrogen and alkali metals combine with halogens to form
IN PERIODIC TABLE halides, with oxygen to give oxides and with sulphur to give
sulphides.
There are only two elements in the first period of the periodic HO; NaCl; KCI
table, hydrogen and helium. Hydrogen is quite reactive but
H20; Na20; K20
·helium is inert. There is no difficulty in relating the structure
and properties of helium with other noble gases in group 0 (or H2S; Na2S; K2S
18th), but properties of hydrogen are such that it cannot be (vi) Reducing nature: Hydrogen, like alkali metals, acts
correlated with elements of any of the main groups of the as a reducing agent. Oxides of less reactive metals are reduced
periodic table. by hydrogen.
The configuration of hydrogen (lsi) is responsible for its CuO + H2 ~ Cu + H20; CuO + 2Na ~ Cu + Na20,
dual uature, i.e., either the'·electroll.can be lost behaving as
electropositive element like alkali metals or the electron can be Il!j Differences with Alkali Metals
gained as to complete Is subshell behaving as electronegative (i) Ionisation energy: The ionisation energy of hydrogen
element like halogens. The position of hydrogen is not fixed in is very high in comparison to alkali metals.
the periodic table, sometimes it is placed with alkali metals in
IA group and sometimes with halogens in VITA (or 17th) group
Element . Hydrogen Lithium Sodium Potassium
IE (kJ morl) 1312 520 495 418
as it resembles with alkali metals as well as with halogens.
However, hydrogen exhibits other properties which differ from (it) Nonmetallic character: Hydrogen is a nonmetal while__
both alkali metals and halogens. alkali metals are metals.
(iii) Atomicity: Hydrogen is diatomic in nature (Hz) while
~ Similarities with alkali metals alkali metals are monoatomic.
(iv) Nature of oxide: The oxide of hydrogen is neutral
On account of the following similarities of hydrogen with
while oxides of alkali metals are basic in nature.
alkali metals, hydrogtin is placed on the top of IA group.
(v) Nature of compounds: The compounds of hydrogen
(i) Electronic configuration: Like the alkali metals,
with halogens (HF, HCI, HBr, HI) are low' boiling covalent
hydrogen has only one electron in the outer shell.
compounds while halides of alkali metals are high melting ionic
Element H Li Na K Rb Cs solids. LiF, NaCI, KBr, etc., are ionic solids.
1; 2, 1; 2, 8, 1; 2, 8, 8, 1; 2, 8, 18, 8, 1; 2; 8, 18, 18,8, 1
Electronic lsi; 2s1; 3s l ; . ii!iJ Similarities with Halogens
confi!juration ' ,.';1 On account of the following similarities and to avoid a long
(ii) Electropositive character: Like the alkali metals gap in the first period before the second member of the period
hydrogen has a tendency to lose its only one electron to form (helium),"it is placed in VITA (or 17th) group above fluorine.
unipositive ion. (i)' Nonmetallic character: Hydrogen is a nonmetal like
halogens.
H~H+
(it) Electronic configuration: Hydrogen resembles the
Li~Li+. halogens in having one electron less than the next inert gas in
its atom.
Na~Na+
Inert gas
Halides of both hydrogen and the alkali metals yield positive 1 H 1 2 He 2
ions in aqueous solutions. 9 F 2, 7 10 Ne 2, 8
HCI ~ H+ +cr 17 Cl 2,8,7 18 Ar 2, 8, 8
NaCI ~ Na+.j. CI- 35 Br 2, 8, 18, 7 36 Kr 2, 8, 18, 8
During electrolysis, these ions are discharged at cathode. (iii) Diatomic nature: Hydrogen forins a diatomic
This shows that hydrogen and alkali metals both have molecule in the elementary state similar to the halogens in
electropositive character. which two atoms are linked together by single covalent bond
(iii) Valency: Because of the formation of unipositive (H2, F2, C12, Br2)'
cation both hydrogen and alkali metals show electrovalency + I. (iv) Electronegative nature: Hydrogen can gain an
(iv) Oxidation state: Hydrogen, like alkali metals when electron and forms a negative ion like the halogens.
combines with electronegative elements shows +1 oxidation H + e ~ H- ; CI + e ~ CI-
state. .•."'
In the electrolysis of fused metal hydrides, hydrogen is
(v) AQinity for non-metals: Hydrogen as well as alkali
discharged on the anode like the halogens in the electrolysis of
metals have a strong affinity for nonmetals. For example, both the fused metal halides.
Hydrogen and its Compounds 217
NaH ~ Na+ + H- (Anode 2Ir ~ H2 + 2e) value of ioinsation potential, similarly it is not so electro-
NaCl ~ Na+ + Cl- (Anode 2CI- ~ Cl2 + 2e) negative as halogens due to low value of electron affinity.
(v) Ionisation potential: The ionisation potential of Both the characters are equally developed in hydrogen as evident
hydrogen is 13.5 eV. The value is nearer to the halogens. from the nature of its oxide which is neutral.
H 2O-neutral
Element H F Cl Br I Na20-basic (because sodium is highly electropositive)
IP.(eV) 13.5 17.4 13.0 11.82 10.43 Cl20~acidic (because chlorine is highly electronegative)
[Alkali metals have low values of ionisation potentials] It is, therefore, suggested that hydrogen he alloted a separate
(vi) Similar covalent compounds and mutual replace- position and not grouped with either alkali metals or halogens.
ment : Hydrogen forms several covalent compounds similar Thomson assigned a separate independent position to hydrogen
to those of halogens. For example: on the top of periodic table as shown below:
_--- _ - - - - --tl._- -- _____ He
I
Li Be B C N 0 F Ne
Hydrogen and halogens are mutually replaceable in many 1 I I I I I I I
covalent compounds of hydrogen and halogens. Na Mg AI Si P. S CI Ar
Cl Cl ,CI Cl This does not disturb the symmetry of the periodic table and_
Cl4 ~ CH3Cl ~ ~
CH2Cl2 CHC13 ~ CCl4
there is no violation of periodic law.
H H H H
In some respects, hydrogen also resembles carbon of the
(vii) Oxidation state or number: Hydrogen, like halogens
group IV, since both have a half filled shell of electrons.
show -I oxidation state in similar compounds.
H 1 (half of first shell maximum capacity of 2 electrons)
Compounds NaIl NaCl NaBr Nal C 2,4 (half of second shell maximum capaci ty of 8 electrons) .
. O.No. -1 -1 -1 -I There are a number of similarities between hydfogen and
(viii) Valency: Hydrogen, like halogens shows electro- organometallic compounds since the groups CH3- and H-
valency as well as covalency. Hydrogen forms electrovalent both have one remaining valency. Thus, the hydride is often
compounds with strongly electropositive elements like alkali considered as part of a series of organometallic compounds,
and alkaline earth metals. for example, LiH, LiMe, LiEt; NH3, NMe3, NEt3 or SiH4,
CH3SiH3~ (CH3hSiH2, (CH3)3SiH, (CH3)4Si. Thus, hydrogen
NaH CaH 2 NaCI CaCh position is not fixed and hydrogen is best treated as a group on
,
,....----------
Electrovalem compounds its own. Hydrogen is sometimes referred as a 'roque element'.
Hydrogen forms covalent compounds with nonmetals.
DISCOVERY AND OCCURRENCE
Cl4
CCl
NH3
NCl
PH3 }
PCl3 Covalent compounds Hydrogen was prepared by Henry Cavendish in 1766 by the
4 3
action of acids on metals. It was named 'inflammable air'.
~ Differences with Halogens' Lavoisier named it hydrogen (hydra:::: water, gennas :::: maker)
'. meaning water maker.
(i) Less electronegativ~:: Hydrogen is less electronegative Hydrogen is the most abundant element in the universe. It
than halogens as it has less'tendency to form H- ion. Halogens occurs in nature in the free state as well as in combined state. In
readily accept electron and form halide ions (Xl. free state, it is present in minute quantity in air, volcanic gases
(ii) Nature of oxides: The oxides of halogens are acidic and natural gas. Sun's atmosphere contains 90% of hydrogen, It
in nature while oxide of hydrogen is neutral. is found most commonly in combination with oxygen as water.
Hydrogen occurs in variety of compounds such as it occurs in
Cl 20 7 H20
Acidic Neutral mineral oils and is present in aimQst all the organic materials such
as hydrocarbons, carbohydrates, fats, proteins, etc. Hydrogen .
(iii) Absence of unsbared pairs of electrons: The
is, thus, an essential constituent of all living things along with
hydrogen molecule does not have any unshared pair of electrons
carbon, nitrogen and oxygen. Hydrogen is also an essential
while in the molecules of halogens unshared pairs of electrons
are present. constituent of aU acids and alkalies.
H:H :CI: CI: PREPARATION

No doubt, hydrogen resembles alkali metals and halogens There are three main sources from which hydrogen may be
both but it is not so electropositive as alkali metals due to high prepared. These are;
(i) Water (ii) Acids and (iii) Alkalies.
(i) Hydrogen from Water [SO~- ions are not discharged on anode as their discharge
potential is higher than that of OIr ions]
(a) Cold water reacts with alkali and alkaline earth metals
Water containing potassium hydroxide: Ion~ present
to evolve hydrogen. The reactions are vigorous. To minimis'e
are K+, OIr \~nd H+. When current is passed, OH- ions
the rate of reaction, alkali metals are used in the form of
move towards anode while. H+ and K+ ions move towards
amalgams. cathode. .
2Na(Hg) + 2H20 = 2NaOH + H2i At anode, OIr ions are discharged and oxygen is evolved.
Sodium amalgam
40Ir '----t 2H20 + O2 + 4e
.In the amalgam, only a small surface of the metal is exposed
At cathode, W ions are discharged and hydrogen is evolved.
and therefore, the reaction is slow.
(b) Hot water or steam, when passed over hot metals like 2H+ + 2e - 4 H2i
Zn, Fe, Mn, Co, Cr, Sn, etc., is decomposed to liberate hydrogen. [K+ ions are not discharged as their discharge potential is
higher than that of W ions]
Zn + H20 - 4 ZnO + H2i
3Fe + 4H 20 - 4 Fe304 + 4H2 i
Red hot Steam (ii) Hydrogen from Acids
When steam is passed over white hot coke, hydrogen is (a) The metals which are reactive and occupy their position
produced in the form of water gas. above hydrogen in the electrochemical series such as alkali
C + H20 - 4 CO+H2 metals, alkaline earth metals, Zn, Mg, Fe, etc., react with <:!i!c..
Hot coke Steam '-.r--'W
ater gas
HCI or dil. H2S04 to evolve hydrogen.
(C) By action of water on ionic hydrides: Ionic hydrides Mg + 2HCI-4 MgC12 + H2 i
on hydrolysis with water evolve hydrogen. The hydride ion is Fe + H2S04 - 4 FeS04 + H2 i
oxidised to hydrogen. These reactions may be regarded as
Zn+ H2S04-4 ZnS04 + H2 i
acid-base reactions.
M ~ M2+ + 2e [M is electropositive and b,as the tendency to
NaH + H20 - 4 NaOH + H2
2H+ + 2e ~ H2 lose electrons. These electrons are accepted by
LiH + H20 - 4 LiOH + H2
protons given by dil. acids to yield hydrogen.]
CaH2 + 2H20 - 4 Ca(OHh + 2H2
(Hydro lith) (b) Mn and Mg react with dil. HN03 to evolve hydrogen.
[H- + H20 - 4 H2 + OHl
Sodium borohydride also reacts with water to evolve (iii) Hydrogen from Alkalies
hydrogen. Zn, AI, Sn, Pb, Si (amphoteric metals) react with boiling
NaBH4 + 2H20 - 4 NaB~ + 4H2 NaOH or KOH to evolve hydrogen.
(d) By the reaction of methane and steam: Both react
Zn + 2NaOH = Na2Zn~ +H2 i
at high temperature in presence of suitable catalyst to form Sodium zincate
hydrogen along with carbon monoxide.
2AI +.2NaOH + 2H20 = 2NaAl02 + 3H2 i
CH4 + H20 - 4 CO + 3H2 Sodium meta-
. aluminate.
(e) By electrolysis of water: Water is a bad conductor Sn + 2NaOH + H20 = Na2Sn03 + 2H2 i
of electricity. Water is made a conductor either by addition of Sodium stannate
an acid or an alkali. The water containing a small amount of Pb + 2NaOH + H 20 = Na2Pb03 + 2H2 i
an acid or alkali (about 15-20%) is electrolysed in an electrolytic Sodium plumbate
cell. The anode and cathode are separated by asbestos Si + 2NaOH + H20 = Na2Si03 + 2H2 i
diaphragm. The cathode used is usually of iron and anode Sodium silicate
usually of nickel. The process is used at places where electric Uyeno's method: Very pure hydrogen is obtained with
supply is cheap and easily available. rapidity by the action of caustic potash on scrap aluminium.
Water containing sulphuric add: Ions present are H+,
OH- and sot. On passing electricity H+ ions move towards . ,-
This method is used for military purposes. ,.
cathode while OIr and SO~- ions move towards anode. 2Al + 2KOH + 2H20 = 2KAl02 + 3H2 i
At cathode, hydrogen ions are discharged to give hydrogen
gas. •. Laboratory Method
2W + 2e-42H-4H2 Hydrogen is prepared in the laboratory by the action of
At anode, OIr ions are discharged to give oxygeri gas. dilute sulphuric acid on granular (commercial) zinc in the woulfe-
OH--40H+e bottle. It is collected by downward displacement of air as it is
40H - 4 2H20 + O2
lighter than air. In place of woulfe bottle, Kipp's apparatus can gas through P20 S' Barium hydroxide, Ba(OHh is preferred to
also be used. The apparatus should always be air tight and sodium hydroxide or potassium hydroxide because if any
there should not be any flame near the apparatus otherwise amount of CO2 is absorbed, the BaC03 produced, being
explosion may occur. Dilute HzS04 does not react with insoluble: settles down and does not interfere with electrolytic
pure. zinc.* In case of pure zinc, the addition of few drops of process.
chloroplatinic acid or copper sulphate solution brings about the (ii) by action of water on NaH,
reaction. NaH + H20~ NaOH + H2i
Purification of hydrogen gas: Hydrogen prepared in the (iii) by Uyeno's method,
laboratory from granular zinc consists of a number of impurities
2Al + 2KOH + 2H20 ~ 2KAlOz + 3H2i
such as AsH3, PH3, H 2S, S02, CO 2, oxides of nitrogen, etc.
To remove these impurities, the hydrogen is passed through (iv) by the actionbf pure dilute H2S04 on magnesium
three bottles containing AgN03 solution, Pb(CH3COO)2 solution· ribbon.
and KOH solution, respectively. AgN03 solution removes PH3
and AsH3; Pb(CH3COOh solution removes HzS; and the KOH
solution removes CO2, S02 and. oxides. of nitrogen. Finally, MANUFACTURE OF HYDROGEN
hydrogen is collected over P20S or anhydrous CaCl2 as to Large quantities of hydrogen are required these days in industry
remove the traces of moisture present in the hydrogen. for various purposes. Water is found in abundance and is the
~-Example 1. In the laboratory, for the preparation of cheapest raw material from which hydrogen can be obtained.
hydrogen from granular zinc, why the following acids cannot Many methods have been proposed for the commercial
be used and which is the most suitable acid for this purposes: production of hydrogen, among which the important ones. are
(a) Cone. H2S04 (b) Cone. HCI (c) Nitric acid. described below:
Sohltion: (a) Conc. H2S04 is not used because a part of (i) Lane's process: In this process, steam is passed over
the acid gets reduced to sulphur dioxide. hot iron. Iron decomposes steam with the formation of magnetic
H2S04 + Hz ~ 2H20 + S02 oxide (Fe304) and hydrogen. The temperature· of iron is
(Cone.)
maintained between 550 to 800 aC. This reaction is termed
gassing reaction and time alloted for this reaction is about 10 .
(b) Hydrogen liberated by the action of conc. HCI on zinc
minutes.
will be impure as it wilIcontain fumes of volatileHCl. Moreover,
ZnCl2 formed is insoluble in conc. HCl. It will form a coating 3Fe + 4H 20 = Fe304 + 4Hzi } Gassing
Steam Magnetic
on zinc and the reaction stops after sometime. oxide
Zn + 2HCI ~ ZnCl2 + H2 .. Iron is regenerated by reducing magnetic oxide with water
gas (CO + H2). This reaction is. called vivifaction and time
(c) HN0 3 plays a double role. It acts as an acid and as an
alloted for this reaction is about 20 minutes.
oxidising agent. The hydrogen (nascent) first formed reduces
the nitric acid into various oxides. Fe304 + 4CO = 3Fe + 4C02 }
Vivifaction
2HN03 + 2H ~ 2N02 + 2H20 Fe304 + 4H2 = 3Fe + 4H20
2HN0 3 + 6H ~ 2NO + 4H20 This iron is again used for decomposition of steam. In order
to make the process continuous, the above two reactions are
Thus, the most suitable acid is dilute H 2SO4•
carried out alternatively using two or more furnaces.
• Preparation of Pure Hydrogen (ij) Bosch's process (water-gas reactions): The
considerable quantity of commercial hydrogen is obtained by
Pure hydrogen is obtained,· the use of this method. Water gas is produced first by passing
(i) by carrying electrolysis of barium hydroxide, Ba(OHh, steam over hot coke at 1000°C. The temperature is not allowed
solution in a U-tube using platinum electrodes or nickel to fall below lOOO°C.
electrodes. The gas liberated at the cathode is passed over
heated platinum gauze as to remove oxygen if present as an C + H20~ CO+H2
'----v--'
impurity in the form of water which is removed by passing the Water gas
"'Pure zinc reacts to produce hydrogen very slowly and in small amount. The reason is that the initially formed gaseous hydrogen forms an
extremely thin fIlm on the surface of zinc which prevents the further dissolution of zinc in acid. Moreover, as a result of high over voltage established
before the hydrogen can evolve from zinc surface, the discharge of W ions or at least the combination of hydrogen· atoms to fonn H2 molecules cannot
occur on pure zinc surface, so, granular zinc is preferably used. If a little CUS04 is added, a thin layer of copper is formed on zinc surface. Zinc-
copper couple reacts readily with dilute acid.
Water gas* is mixed with twice its volume of steam and (v) As a byproduct: Sodium hydroxide is manufactured
passed over a mixture of ferric oxide and chromium oxide by carrying electrolysis of an aqueous solution of sodium
heated to 500°e. The mixture acts as a catalyst and helps in chloride in Nelson cell (Fig. 6.1) or Castner-Kellner cell (Fig.
the conversion of carbon monoxide to carbon dioxide. 6.2). Hydrogen and chlorine are thebyproducts of this industry.
Catalyst Hydrogen is also obtained as a byproduct in the manufacture
H2 +CO + H 20 --~) CO2 + 2H2 of sodium by electrolysis of fused sodium hydroxide by
'-v---'
Water gas Stearn . Castner's process .
C02 dissolves in water under pressure. The mixture of CO2 . (vi) Relatively smaller quantities of hydrogen are obtained
and H2 is passed through water under a pressure of 25-30 by passing a 1 : 1 molar mixture of vapourised methanol and
atmospheres. CO2 dissolves completely in water. Traces of water over a base metal chromite type catalyst at 4000c. The
CO present in hydrogen are removed by passing the gas through mixture of hydrogen and carbon monoxide obtained is made to
ammonical cuprous chloride solution under a pressure of 200 react with steam to give CO2 and more hydrogen.
atmospheres. CH30H 400°C) CO + 2H
The hydrogen manufactured by this method is utilised for Catalyst 2
the synthesis of ammonia in which CO acts as a poison for the CO + H 20 400°C) CO + H

Catalyst . 2 2
catalyst. To make hydrogen completely free from CO, it is
passed over nickel catalyst where any amount of CO left is The CO2 and CO are removed by the method described in
converted to methane. Bosch's process. . --
CO + 3H 2 ----" CH4 + H20 These days about 77% of the commercial hydrogen is
produced from petrochemicals, 18% from coal, 4% from
electrolysis of aqueous solutions and 1% from other sources.
PROPERTIES OF HYDROGEN
Physical Properties
(a) It is a colourless, odourless and tasteless gas.
(b) It is only slightly soluble in water, about 2 volumes in
100 volume of water at O°e.
(iii) From natural gas using steam reforming process :
(c) It is lightest of all elements.
The hydrogen on a massive industrial scale is prepared by 1
using the steam-reforming process. This is a recent method. Density = 0.08987 gL-
In this process steam and hydrocarbons from natural gas or (d) It is diatomic in nature.
petroleum react at high temperature and pressure in the presence = =
CplCv Y 1.40
of catalyst to form carbon monoxide and hydrogen. Natural (e) It has low melting and boiling points,
gas mainly consists of methane (C~). Hydrogen is obtained b.pt. = -252,SOC (20.5 K)
from natural gas either by partial oxidation or by cracking. m.pt.= -259.0"C (14~0 K)
CH4 + H20 ~~~~ CO + 3H2 (f) The various physical constants are :
Stearn Ionisation potential 13.54 eV or 313 kcal mol- 1
Ni-'Cr ) CO2 + H2 Electron affinity 17.3 kcal mol-lor 12kJ mol- l
Cracking Electronegativity 2.1
lOOO"C ) C + 2H2
Methane Critical temperature -236.9°C
C2H 6 ~cking ) 2C + 3H2 Bond energy, H-H 436 kJ mor l
Ethane Bond length, H-H 74 pm
(g) Certain metals like palladium, platinum, iron, cobalt,
Propane Propene etc., can adsorb large quantities of hydrogen. Palladium can
Natural gas is mixed with steam and passed over a catalyst adsorb 1000 times its own volume of hydrogen. The adsorbed
at about 800-900°C. The C02 and CO are removed by· the hydrogen is called occluded hydrogen and is more active than
method as described in Bosch's process. . ordinary hydrogen. This property can be used for the purification
(iv) Electrolysis of water: See section 5.3 (i) (e). of hydrogen because only pure hydrogen is adsorbed.
*All mixtures of CO and H2 irrespective of their composition are called now-a-days synthesis gas or Syn gas. Syn gas can also be produced from
sewage, sawdust, scrap wood, newspaper, etc.
Chemical Properties electropositive metals such as copper, tin, iron, lead, etc., are
reduced to the metals when heated in hydrogen.
(a) Combustion: Hydrogen is inflammable or combustible
gas. It bums' with blue flame in oxygen atmosphere. Hydrogen, PbO,+ H2 = Pb + HzO
however, does not help in burning. If a burning splinter is CuO + H2 = Cu + H 20
introduced in a jar full of hydrogen, the splinter goes out while Fe304 + 4H2 = 3Fe + 4H 20
the gas bums on the mouth of the jar. On account of hydrogen [Note: The oxides of strongly electropositive metals such as those of
burning, water is formed. alkali and alkaline earth metals are not reduced by dihydrogen.J
2H2 + O2 = 2H20 Numerous substances are reduced or hydrogenated by
(b) Combination reactions: Hydrogen is not a very hydrogen in presence of suitable' catalysts. The unsaturated
active element and does not react readily with other elements. fats are changed' to saturated fats in the presence of finely
The H-H bond dissociation enthalpy (436 kJmol-1) is the divided nickel.
highest for a single bond between two atoms of any element. Unsaturated + H2 CataN:yst) Saturated fat
It's dissociation is only 0.081% at 2000 K and increases to (Oil) (Vanaspati ghee)
95.5% at 5000 K.
CH 2 =CH 2 +H 2 Ni or Pt or Pd CH CH
473K ) 3- 3
H 2 (g) 5000K >2H(g) Ethene Ethane
CH==CH +2H2 Ni or Pt or Pd CH' CH

Therefore, most of the reactions of dihydrogen occur at 473K ) 3- 3
Ethyne Ethane
high temperatures.
Under suitable conditions, hydrogen can be made to combine (d) Reaction with carbon monoxide: At about 700 K
with metals and nonmetals both. (i) Alkali and alkaline earth and under high pressure and in presence of a catalyst (ZnO/
metals (with the exception of beryllium) directly combine with Cr203), dihydrogen combines with CO to form methanol.
hydrogen when heated in its atmosphere. The compounds CO + 2H? 700K, 200atm, ) CH OH
- ZnO/Cr203 3
formed are called hydrides.
(e) Hydroformylation of olefins to aldehydes : Olefms
2Li + H2= 2LiH; Ca + H2 = CaHz combint:( with carbon monoxide and hydrogen in presence of .
2Na + H2 = 2NaH; octacarbonyldicobalt, CO2(CO)g, as catalyst under high
These hydrides are electrovalent compounds, conduct temperature and pressure to form aldehydes which can be
electricity in fused state. (ii) Non-metals like halogens, oxygen, further reduced to alcohols.
sulphur, nitrogen, etc., directly combine with hydrogen under R-CH = CH 2 + H2 + CO ~ RCH 2-CH 2 -CHO
definite set of conditions and form stable covalent compounds. Olefin Aldehyde
With fluorine, hydrogen combines readily even at low ~ RCH2-CH2-CH20H

Alcohol
temperature while the combination with chlorine takes place in
presence of sunlight or on heating. Similarly, with bromine it 5_ INDUSTRIAL APPl-)CATIONS
combines on heating while with iodine it combines when heated
Very large quantities of hydrogen are required for synthesis of
in presence of a catalyst.
a numb~r of products.
H2 + X2 = 2HX X F, CI, Br or I (a) Synthesis of ammonia: A mixture of N2 and H2 in
The reactivity of halogens towards dihydrogen decreases ratio of 1 : 3 is compressed to 200 atmospheres and passed
in the order: over heated catalyst at 500°C. About 8% NH3 is formed. It is
F2 > Cl2 > Br2 > 12 known as Haber's process.
Hydrogen combines with sulphur on ignition. Catalyst
N2 +3H 2 \ \ 2NH 3 ; Ml = -22.4 kcal mol- l
H2 + S = H2S 500°C
It combines with nitrogen under high pressure and in Catalyst-Freshly reduced iron having Mo as promoter.
presence of a catalyst at 500°C. (~,:, Manufacture of methyl alcohol: Water gas enriched
Fe as catalyst \ with H2 is compressed to 200 atmospheres and then passed

N 2+ 3H2\ 2NH3 over catalyst ZnO and CrG3, when CH 30His formed.
200 atm.
It combines with carbon at about 1200°C to form methane
CO + 2H,., Cal,lJyst )CH OH
in small amounts. ~ 3000C 3
C + 2H2 = Cf4
(c) Manufacture of hydrogen chloride: Large quan-
(c) Reducing nature: As hydrogen has great affinity for tities of H2 and el2 obtained as byproducts during manufacture
oxygen, it is suitable,for removing oxygen. The oxides of less
of NaOH are made to combine to form HCI by burning one in (j) In petrochemical industry: One major use of hydrogen
the other. is in the petrochemical industry. In many cases the reaction is
on~ where hydrogen is added to hydrocarbon compound
H2 + Cl 2 ~ 2HCI (absorbed in water)
containing carbon-carbon double bonds to produce compound
(d) In food processing industry by hydrogenation of that contain carbon-carbon single hondo For example, I-butene
oils: Hydrogen is chiefly used in catalytic hydrogenation of can be reacted with hydrogen using a platinum or palladium
unsaturated (liquid) oils into solid fats for the production of catalyst to produce butane.
vegetable ghee.
(e) Synthetic petrol: Petrol substitutes are obtained by CH3CH2CH = CH2 + H2 ~ CH3CH2CH2CH3
Butene Butane
subjecting a paste of powdered coal in crude oil to the action
Butane is the constituent of petro1.
of hydrogen under pressure and in presence of a catalyst.
(f) Oxyhydrogen Dame : Oxyhydrogen flame produces
a temperature of 2800°C while oxyatornic hydrogen flame
HYDROGEN ECONOMY
produces a temperature of 4000°C. This temperature is required (Use of hydrogen as a fuel)
for melting substances having very high melting points such as The world's fossil fuel reserves are being depleted at' an
quartz, platinum, etc., and also for welding purposes. alarmingly fast rate. Faced with this. dilemma, scientists have
(g) With helium, it is used for filling balloons employed for made intensive efforts in recent years to develop alternative
atmospheric study. sources of energy. Hydrogen has been considered as _one of
(h) Hydrogen is used for creating a reducing atmosphere in the alternate source of energy.
processes like annealing and deoxidising. One major advantage of using hydrogen as a fuel is that it
0) As fuel for space shuttle's main rocket engine : The isenvironrnentally clean, giving only water as a combustion
density of liquid hydrogen is very low (0.08987 gL- I ), which product. If hydrogen is burned in air, small amount of nitrogen
is less than one-tenth that of water. This low density makes oxides can be produced because of high temperature
hydrogen a very light weight but bulky fuel. Hydrogen has the combination of nitrogen and oxygen, but the combustiori
highest specific enthalpy of any known fuel, The low density products are free from CO, CO2, SOb unburned hydrocarbons
and highest specific enthalpy of liquid hydrogen makes it a and other environmental pollutants that result from the
valuable fuel for space mission, so liquid hydrogen storage combustion of petroleum fuels.
tank with liquid oxygen is used to power the main rocket The second advantage with hydrogen is that the heat of
engine of space shuttle (Fig. 5.1). combustion of hydrogen per gram is higher than any other fuel
as tabulated below :
liquid Oxygen H2(g) + (D02(g) ~ H20 (l) ; ,~JJ.O = -284 kJ mor l
Tank
Energy released by combustion of some substances
Substance Energy reieased (k.Jfg) .

Hydrogen [combustion product H 20(l)] 142
liquid Hydrogen Gasoline 48
Tank
Crude petroleum 43
- Typical animal fat 38
Coal 29.3
Charcoal 29
Paper 20
Wood or 15
There has been much talk of the hydrogen economy_The

idea is that hydrogen could replace coal and oil as major sources
of energy. Our energy needs can be met by gaSeous, liquid and
solid hydrogen. For heating homes, gaseous hydrogen could
be conveyed through underground pipes, while liquid hydrogen
(a) (b) could be shipped by truck or rail in large vacuum insulated
tanks. Automobiles might be powered by solid hydrogen in the
Fig. 5.1 (a) A liquid hydrogen storage tank : Liquid
hydrogen is used as a rocket fuel. (b) The arrangement form of solid interstitial hydrides. Prototype cars have already
of fuel tanks in the space shuttle been built with their engines modified to run on hydrogen.
Hydrogen-oxygen fuel cell Thus, there is a transfer of electrons-from H2 to 02. The
above equation is clearly the equation for the burning of .
There is a safer way to combine H2 and O 2 to form water
hydrogen in oxygen but in this cell, it is burning without a
.and extract energy in the form of electricity. The device is
flame and with relatively little heat. Water is the only product
termed as a hydrogen-oxygen fuel cell (Fig. 5.2). A hydrogen-
besides a transfer of electrons, which is what we call electricity.
oxygen fuel cell is a galvanic cell in which one of the reactants
Hence, fuel cells are a more enviromnentally friendly way to
is a traditional fuel such as hydrogen. In a fuel cell, the
produce electricity.
chemical energy of a fuel is· converted directly into.
Fuel cells provide electricity and pure water during space
electricity without burning the fueL Such a cell was invented
. flights: Fuei cells are very efficient, converting about 75% ~f
in 1839 by William Grove but it remained a mere curiosity
bond energy of fuel into electricity. In· contrast, an electnc
until the advent of a U.S. programme in 1960. A fuel ceU is
power plant converts 40%·ofbond energy of coal into electricity.
used as a source of electrical energy in the space vehicles.!t
However, fuel cells cannot store electrical energy. They only
differs from an ordinary battery that the reactants are not
operate with the continuous flow of reactants~ The electrode
contained within the cell but instead are continuously supplied
materials are short lived and expensive.
from an external reservoir.
A major advantage of the fuel cell is that there is no electrode
The fuel cell contains porous carbon electrodes impre-
material to be replaced as there is in all ordinary battery. The
gnated with metal catalysts usually platinum and an electrolyte
fuel can be fed in continuously to produce power. In fact,
consisting of hot (2000C) aqueous KOH or molten Na2C03.
hydrogen-oxygen fuel cells were used in the Gemini and~
Proton Exchange Membrane (PEM) is used for this purpose·
Apollo missio~ in the second half of the twentieth century
now-a-days. The fuel (gaseous H 2) and the oxidising agent
and other space programmes.
(gaseous ~). do not react directly but instead flow into
Because of cost, large scale applications of fuel cells have
separate cell compartments where gaseous hydrogen is oxidised
been limited. The use of fuel cells is still in its infancy but will
at anode and O2is reduced at the cathode. The overall cell reaction
surely, grow.
is simply the conversion of hydrogen and oxygen to water.
. At the anode,· hydrogen gas enters a chamber where a HYDRIDES
porous platinum catalyst oxidizes the hydrogen.to H\aq) ions
at the anode. The hydrogen ions (H+) then migrate through a Binary compounds of the various elements with hydrogen, in
'special proton exchange membrane (PEM), which works as which hydrogen has usually an oxidation number of -1 are
an electrolyte and move to the cathode. called binary hydrides. The type of hydride which an element
forms depends upon its electronegativity and hence on the type
2H2(g) Pt ) 4H+(aq) + 4e- . ...... ( anod)
e
catalyst of bond formed. Hydrides are conveniently studied under three
The proton exchange membrane allows a very small quantity classes.
of H\aq) ions for the passage from the anode to the cathode. (A) Ionic or Saline or Salt like hydrides
At cathode oxygen gas enters the cell, where it comes in (B) Covalent or molecular hydrides
contact with a platinum catalyst that facilitates the reduction of (C) Metallic or interstitial hydrides
02(g) in the presence of W(aq) and the electrons produced at
-18
anode from oxidation reactions and produce water. 13 14 15 16 17
02(g) + 4W(aq) + 4e
Pt
catalyst
) 2H20(l) ...... (cathode)
. IT
, 3 4 5 6 7 8 9 10 11 12 I
I
, ... "
1-' Ionic D Covalent
Pt(catalyst)
'D Metallic
0' Uncharacterized
or unknown
Proton exchange Fig. 5.3 The different classes of binary hydrogen

membrane (PEM) compounds and their distribution in the periodic table
O 2 out 4--._J.!!I!::::~====~
---JIiI> H2 gas + water
vapour out
(A) Ionic or Saline or Salt Like Hydrides
The saline hydrides are compounds of hydrogen with a
strongly electropositive metals, i.e., alkali and alkaline earth
Fig. 5.2. A hydrogen-oxygen fuel cell metals and some highly positive members of lanthanide series
224 GR.B. Iilorganic Chemistry for Competitions
with the exception ofBe* and Mg* which c~n transfer electrons metals from which they are fonned. This is because that H-
easily to hydrogen atoms. ions occupy holes in the lattice of metal.
These hydrides are generally prepared by heating the metal (vii)The stability of the hydrides decreases as the size of the
with hydrogen under pressure at temperatures between 150° cation increases.
to 600°C. LiH > NaH >KH > RbH > CsH
2Li + H2 -----7 2LiH CaH2 > SrH2 > BaH2
Dissociation Dissociation
H2 + 2Na, K, Rb or Cs 4()()OC) 2NaH, 2KH, 2RbH or 2CsH 'Hydride Hydride
(K) temp.
150-3()()OC
H2 + Ca, Sr or Ba ) CaH2, SrH2 or BaH2 LiH 823 CsH 443
NaH 483 CaHz 1158
KH 473 SrH z 858
• Properties RbH 443 BaH2 503
(i) They are colourless or greyish coloured crystalline solids. (viii) They burn in air on strong heating due to their decom-
Alkali metal hydrides have rock-salt structure (Fig. 5..4). position into metal and hydrogen. Both readily combine with
They are non-conducting substances. They consist of ions oxygen.
and behave as salts and, thereby called as ionic hydrides. ~2 M + H2
102
1 02
MO H20
(ix) These hydrides readily react with H20, C2H50H, CO2,
SOb diL acids, NH3, ,etc.
LiH + H 20 -----7 LiOH + H21
LiH + C2HsOH -----7 C2HSOLi + H21
LiH + CO 2 -----7 HCOOLi
Lithium formate
(b) 2LiH + 2S0 2 -----7 Li2S20 4 + H2 t
Lithium
Fig. 5.4 The arrangement of ions in the rock-salt structure. sulpbosulphite
(a) The unit cell, showing the packing of the individual ions. LiH + NH3 -----7 LiNH2 + H21
(b) In line diagram the red spheres are cations and the blue
spheres are anions. LiH + HCl-----7 LiCI + H21
(X) Alkaline earth metal hydrides and LiH combine with
(ii) They have high melting and boiling points. nitrogen when heated in its atmosphere.
(iii) They conduct electricity in molten state (fused state) 6LiH + N2 -----7 2Li3N + 3H21
liberating hydrogen at anode. This confinns the presence of
3CaH2 + N2 -----7 Ca3N2 +' 3H21
hydride (Hl ions in them. For example molten LiH undergoes
electrolysis. (xi) Ionic hydrides show reducing properties.
2CO + NaH -----7 HCOONa + C
LiH~Li+ +H-
SiC4 + 4NaH -----7 SiH4 + 4NaCI
/ ~ PbS0 4 + 4NaH -----7 PbS + 4NaOH
'Cathode Anode
Fe304 + NaH -----7 3Fe + 4NaOH
(xii) LiH and NaH have been used for preparing valuable
(i\l) Ionic hydrides can undergo an oxidation-reduction
reducing agents, e.g., LiAIH4 (lithium aluminium hydride) and
reaction with water to produce hydrogen and a basic solution.
NaBH4 (sodium borohydride) by the following reactions:
LiH(s) + H20(l) -----7 H2(g) + LiOH(aq)
4LiH + AlCl3 Ether) LiAlH4 + 3LiCI
For this very reason? these hyarides can be used as a source
of hydrogen gas where transportation of H 2(g) is impractical, B2H6 + 2NaH -----72NaBH4
such as for inflating weather balloons. Uses: Ionic hydrides are used as reducing agents (a
(v) They have high heats of fonnation. source of electrons during chemical reactions), as solid fuels
(vi) The density of ionic hydrides is higher than those of and for ready synthesis of .hydrogen via hydrolysis.
*MgH2 and BeH2 show significant covalent nature.
Note : Binary molecular compounds of hydrogen are often called molecular hydrides, but they are not strictly hydrides as the oxidation number
of hydrogeri is +1 as in hydracids of halogens, oxygen, nitrogen, etc.
(B) Covalent or Molecular Hydrides* Some of these molecular compounds can be prepared by
protonation, or proton transfer from an acid to a base, such as
Covalent hydrides are molecular compounds in which S2-.
hydrogenjs covalently bonded to another element. For example
some covalent hydrides are NH3, H20, H202 and HE These FeS(s) + 2HCl(aq)
hydrides are formed by all the true nonmetals (except zero group· Some of these compounds can be formed from the direct
elements) and the elements like AI, Ga, Sn, Pb, Sb, Bi, Po, etc., reaction of the elements with hydrogen. If the nonmetal reacting
wllich are normally metallic in nature, i.e., this class includes the with hydrogen is reactive, the reaction will readily occur without
hydrides ofp-block elements. Except third group elements, each the need for elevated temperatures or a catalyst.
other element forms a simple mononuclear hydride of the F2(g) + H2(g) ---1 2HF(g)
formula, MHs-x where x is the number of electrons present in The reaction of hydrogen with oxygen to form water is an
the outermost orbit of the element M. The simplest hydride of B example of a reaction that requires the input of energy to get
and Ga are dimeric materials, B2H6 (diborane) and Ga2~ started. However" once it does, the reaction is rapid and
respectively and the hydride of aluminium is polymeric in exothermic.
nature, (AlH3)n' In addition to mononuclear hydrides, the elements
like Si, Ge, N, P, 0, S, B, etc., form polynuclear hydrides.
2H2(g) + 02(g) ---1 2H20(g) tJl =
484 kJ
Because it is such an .exotherinic reaction and the product
Molecular hydrides are further classified according to their
is a gas, it is an ideal rocket fuel.
relative numbers of electrons and bonds in their Lewis structures.
(I) Electron deficient molecular hydrides: These have
• Properties
too few electrons for writing its conventional Lewis structure.
Diborane (B2~) is aD example of this type. (i) In these hydrides, hydrogen atoms are covalently bonded
(II) Electron-precise molecular hydrides: These are to the central atom. The hydrides consist of discrete covalent
formed by elements of group 14. The molecules are tetrahedral. molecules held together by weak van der Waals' forces and in
Methane (CI-4) is an example of this type. some cases by hydrogen bonds. As a result, these hydrides are
(16) Electron-rich· molecular hydrides: The excess gases, liquids and in few cases solids of low melting and
electrons are present as lone· pairs. The examples ate NH 3, boiling points.
H20, HF, etc. The hydrides NH 3, H20 and HF due to the (ii) In general, these hydrides are volatile in nature.
presence of highly electronegative atoms possess hydrogen (iii) They have low electrical conductivity.
bonding also. (iv) The thermal stability in a group decreases as the
These hydrides can be obtained by direct combination of electronegativitydecreases with an increase in size of the central
elements or by hydrolysis of compounds such as borides, atom. The thermal stability decreases in VA or 15th group
silicides, phosphides, sulphides, carbides, etc., or by use of hydrides.
~. Nfl3 > PH3 > As~ > SbH3 > BiH3
N2 + 3H2 2NH3 )
---1 (v) Covalent hydrides with one or mor~10nepairs of electrons
. Direct combination behave as Lewis bases. Along any· given period of periodic
X2 + H2 ---1. 2HX table, these hydrides become· increasingly. acidic as we move
Mg3B2 + HCI(dil.) ---1 A nllxture of boron hydrides from left to right.
Mg 2Si + HCI(dil.) ---1 A mixture of silicon hydrides HF
Acidic
Al4C3 + 12H20 ---1 4AI(OHh + 3CH4
(vi) The hydrides of third group or 13th group are electron
CaC2 + 2H20 ---1 Ca(OHh + C 2H2
deficient and hence behave as Lewis· acids.
Mg3N2 + 6H20 ---1 3Mg(OHh + 2NH3
B2~ + 2NH3 ---1 2[BH3·NH3]
FeS + '2HCl(dil.) FeCl2 + H2S
---1
(vii) Some hydrides act as reducing· agents.
Ca3P2 + 6H20 ---1 3Ca(OHh + 2PH3
4AgN03 + Si~ ----7 4Ag + Si + 4HN03
SiC4 + LiAlH4 ..:;;:.:.;:.~ Si~ + LiCI + AICl3 (viii) The lighter elements of groups 14, 15 and 16 form
4BCh + 3LiAlH4 2B2~ + 3AICl3 + 3LiCI polynuclear hydrides. For example, C2~' C3H~, C4HlO, etc.
for carbon; Si2~' Si3H s,S4H lO , etc. for silicon; N2~' N3H
GeCl4 + LiAI~ LiCI + AlCl 3 + GeH4 for nitrogen; H20 2, H 20 3 for oxygen.
*The systematic names ~f covalent or molecular hydrides are usually derived from the name of the element and suffix -ane as :
PH3 Phosphane H 20 Oxidane NH3 Azane
Uses: Molecular hydrides have wider applications. Some the composition ofthe metallic hydride is variable. For example
of them are mentioned here. Boron hydrides are used as high under one pressure of H2 the composition of the metallic MHx
energy fuels and propellants. Ammonia is the source for might be MHo.4. whereas at a higher pressure of H 2, it might
hydrogen at any destination. Phosphine is used. for making be MH o.5. One way to think about these compounds is to
Holme's signals. H 2S is an important laboratory reagent. HF is consider the metal crystal to be similar to an apartment building
used for etching of glass. with the lattice holes representing the individual apartments.
The occupancy of an apartment building is not fixed; it is
~ (C) Metallic or Interstitial Hydrides instead a function of factors like the rent, conditions of the
Metallic hydrides are compounds containing a transition building and so on.
metal and hydrogen. Commonly, the formula of these com- Some important examples of metallic hydrides are : ScH2,
pounds is MH x , where x is often not an integer. The metallic YH2, YH3,Lill2,LaH3, TiH2,ZrH2,HfH2•VH, VH2.NbH.NbH2.
hydrides are so called because they are electrically conducting. TaH, CrH, etc. Some examples of non-stoichiometric hydrides
Many transition and inner transition metals of d-block form are : PdH(O.6 0.8)- NbHo.ll, ZrH(l.30 1.9)' TiHO.7 - 2), ClH2.7,
black powdery, metallic or interstitial hydrides on reacting with La2.8, etc.
hydrogen. However, the metals of groups 7, 8 and 9 do not
form hydrides at all. Even from group 6, only chromium forms
Properties
hydride (CrH). This region of periodic table from group 6 to (i).They:are black powdery, hard, have a metallic lustre and
9 is referred to as the hydride gap. Metallic hydrides of groups magnetiC properties.
3,4 and 5 are common. The elements of groups 10,11, 12 and (ii) They are good conductors of electricity. the conductivity,
I-block elements (Ce, Eu, Yb, Th, U, etc.) on heating with H2 however, decreases with increase in temperature.
under pressure form hydrides. (iii) The density of these hydrides is lower than those of
Earlier it was thought tha1'in these compounds, hydrogen metals from which they are formed since the crystal lattice
occupies interstices (Fig. 5.5) in. the metal lattice producing expands due to absorption of H2.
distortion without any change in the metal itself. Con~equently, (iv) They have high thermal conductivity.
they were termed as interstitial hydrides. However, recent (v) They generally undergo reversible decomposition into
studies have shown that except for hydrides of Ni, Pd, Ce and H2 gas and metal.
Ac, other hydrides have lattice different from that of the parent
Cool
metal. Re4 hot metal + H2 -,----=..::..::.:.....~) Interstitial
Occlusion
hydride
Strong
1 heating
Metal+H2
UseS: (i) Metal hydrides formed as a result of occlusion

can be used as hydrogen storage media.
(ii) Metallic hydrides are widely used in catalytic reduction
and hydrogenation for preparing large number of useful
compounds.
(iii) Since ~e metallic hydrides release their hydrogen (as
Fig. 5.5 In a metallic hydride, the small hydrogen atoms (the
small grey spheres) occupy gaps-called interstices-between H2) when heated or treated with acid, they are also being
the larger metal atoms (the large grey spheres) investigated for storing and transporting hydrogen. Both saline
and metallic hydrides have the high enthalpy densities desirable
These hydrides are prepared by adsorbing hydrogen directly in a portable fuel. .
at appropriate temperatures by metals. In some cases, the
metals axe used as cathodes in the electrolysis of aqueous (d) Polymeric and Complex hydrides
solutions so that hydrogen evolved at cathode is adsorbed.
. Besides ionic, covalent and metallic hydrides, there are two
The composition of these hydrides may not correspond to
more types of hydrides which are called as polymeric and
~. simple whole number ratio and therefore, they are called non-
complex hydrides.
stoichiometric hydrides. Their. composition varies with the
Polymeric hydrides: These are formed by elements
conditions of temperature and pressure.
having electr~negativity in the range of 1.4 2.0. These are
This'shows that hydrogen atoms occupy some and not all
generally solids. Examples are : (BeH2)m (MgH 2)n, (AIH3)n'
the interstitial sites in the metallic lattice. Often hydrogen atoms
(InH3)n> (Si~)n> etc. These hydrides Consist of molecules
enter the holes in nonstoichiometric amounts. The result is that
held together in two or three-dimensions by hydrogen bridges The life period of atomic hydrogen is 0.3 second. It readily
(Three-centre-two electron bonds.) returns to ordinary form. This conversion is highly exothermic
and used for welding purposes. This form of hydrogen is more
~ /H~ /H~/H~ / active than ordinary hydrogen.
Be Be Be Be Note: (i) Atomic hydrogen can be produced at very high temperatures
/ ~H/ ~H/ ~H/ ~
tiut nascent hydrogen is formed even at ordinary temperature.
(ii) The reducing power of atomic hydrogen is more than nascent
Complex hydrides: These are the compounds which hydrogen.
contain hydride ions (Hl coordinated to metal atom. Examples
are: LiAIl4, LiBH4' NaB~, etc . ~~ (C) Ortho and Para Hydrogen
.5_ SPECIAL FORMS OF HYDROGEN
Hydrogen molecule is diatomic, i.e., it contains two hydrogen
atoms. Each atom has one proton in the nucleus with an
electron moving around it. Like electron, the proton is also
(a) Nascent Hydrogen spinning about an axis. Two protons in the hydrogen molecule
Hydrogen at the moment of formation is known as nascent may have either their spins in the same direction or in opposite
hydrogen. It is more active than ordinary hydrogen. For directions giving rise to two forms ortho and para. When the
example, when ordinary hydrogen is passed through acidified proton spins are in the same direction, the form is termed as
potassium permanganate solution or ferric chloride solution, ortho hydrogen and when the proton spins are in the opposit~ __
neither of them is reduced. However, when zinc pieces are directions, the form is known as para hydrogen.
added, both get reduced.
Ordinary ~ KMn04l12S04 ~ No change in colour as

hydrogen Purple coloured reduction does not occur
solution
uu UU Ortho Hydrogen Para Hydrogen
1 + Zn pieces
(Zn+dil. H2S04 -7 Hydrogen liberated)
Decolourisation occurs,
Fig. 5.7 Ortho and para hydrogen
Ordinary hydrogen is a mixture of these two forms. Ordinary

i.e., liberated hydrogen hydrogen consists of 75% ortho and 25% para under ordinary
reduces acidified KMn04 atmospheric conditions. At very low temperature say about
20 K, 99.82% para and only 0.18% ortho is present but as the
It is believed that a part of energy liberated in the reaction
temperature rises, toe percentage of ortho form increases while
producing hydrogen become associated with hydrogen
that of para form decreases reaching to a limiting ratio 75%
molecules and thus make them hyper active.
ortho and 25% para under ordinary atmospheric conditions ..
This shows that intrinsic energy of ortho form is higher than
~ (b) Atomic Hydrogen
para form.
When hydrogen is passed through an electric arc established The two forms differ in their physical properties like specific
between two tungsten filaments, hydrogen is dissociated into heat, thermal conductivity, boiling point, etc., but show similar
atoms. This form of hydrogen is known as atomic hydrogen. chemical properties. Ortho form is more stable than para form.
H2 \ Electric arc \ 2H + 104.5 kcal mol- l Pure para form can be obtained at low temperature (20 K) but
pure ortho form is very difficult to obtain.
5:1 ISOTOPES OF HYDROGEN

There are three known isotopes ,of hydrogen, each possessing
an atomic number 1 and atomi~masses 1,2 and 3 respectively,
these are named as protium, deuterium and tritium.· .
(a) The most common is the ordinary hydrogen usually
called protium with atomic mass 1.008123. It consists of one·
proton in the nucleus arid an electron revolving around it. This
isotope constitutes 99.984 per cent of the total hydrogen
available in nature. It is represented as tHo
(b) The second isotope of hydrogen is called heavy
hydrogen or deuterium. It consists of one ·proton and one
Crack to be welded neutron in the nucleus and an electron revolving around it. Its
Fig. 5.6 Atomic hydrogen welding torch / .
atomic mass is 2.0142. ~t constitutes onlY 0.016 per cent of (i) Separation from ordinary hydrogen:
the total hydrofen occurring in nature. ItlS: represented by the
symbol D or IH. ,'"','
(a) From liquid hydrogen: Deuterium was obtained
by Urey and his co-workers by the evaporation of liquid
(c) The third isotope of hydrogen is\called tritium. It
hydrogen near its triple point 13.9 K under reduced pressure.
consists of one proton and two neutrons in the nucleus and an
4 'litres of liquid hydrogen are concentrated to 1 mL. The
electron revolving around it. Its atomic mass is 3.0170. It
resulting liquid is found to be rich in deuterium.
constitutes 1 x 10-15 per cent of the total natural hydrogen.
(b) By diffusion: .Deuterium can be separated from
Unlike the above two isotopes, this isotope is unstable and
ordinary hydrogen by the application of diffusion method.
shows radioactivity. It is represented by the symbol Tor IH.
Protium being lighter diffuses more readily than deuterium.
Protium Deuterium Tritium The diffusion is carried out .under reduced pressure. This
method is slow and tedious but produces pure deuterium.
088
(c) By adsorption on charcoal: It is observed that
protium, the lighter isotope, is adsorbed more readily and more
strongly on charcoal. Thus, the ordinary hydrogen is passed
over charcoal kept at liquid air temperature, most of the lighter
@) Electron • Proton • Neutron isotope gets adsorbed and the fraction richer in deuterium
passes out unchanged.
Fig. 5.8 Isotopes of hydrogen
(ii) Preparation from heavy water
The three isotopes have same chemical properties as they
have same electronic configuration 1sl . Their physical properties Ordinary water contains about one part of heavy water in
are, however, different due to differences in their atomic masses. 6000 parts of ordinary water. Heavy water is. obtained from
The atomic structures of three isotopes are shown in Fig. 5.8. ordinary water by continuous electrolysis method in which 20
Owing todifferen~ masses, the rates with which the three isotopes litres of water reduced to I, mL. Now-a-days, heavy water is
react are different. This type of difference in properties due to the important source of deuterium. The following methods can
difference in atomic masses is called isotopic effect. be used for the preparation of deuterium from heavy water.
Since, the percentages of deuterium and tritium present in These methods can be even used in laboratory.
natural hydrogen are very small, the properties of ordinarily (a) By action of sodium: A pure sample of deuterium
hydrogen, are mainly due to protium. Some of the important is obtained by the action of sodium on heavy water.
points regarding the ,three isotopes are tabulated below:
2Na + 2D20 = 2NaOD + D2
Protium' Deuterium Sodium
or, deuteroxide
Property or heavy Tritium
ordinary , hydrogen
hydrogen (b) By using red hot iron or tungsten: Gaseous
deuterium may be prepared by decomposing heavy water with
Atomic number 1 1
red hot iron or heated tungsten, ,
Mass.
." number 1 2 3
4D20(vapours) + 3Fe. (red hot) ~ Fe304 + 4D2
:~>.
Exact atomic mass 1.008123 ' 2.0142 ' 3.0170

Symbol iH 2H
1 ,or 2D
I, {H or iT 3D 20 + W 1000·C) W0 3 + 3D2
Molecular formula H2 ·D2 T2 Vapours Heated
electrically
No. of protons in the nucleus 1 1 1
No,. of neutrons in the nucleus Nil 2 The W03 formed distills over at the working temperature,
No. of electrons 1 1 exposing a frebh surfaCe for further oxidation.
Electronic configuration Isl Isl (c) By electrolysis: The solution of sodium carbonate
0.016% 10-15 % (anhydrous) in heavy water on electrolysis between nickel
electrodes yield deuterium on cathode.
2D 2 0
Electrolysis
)
2D
2 +
°
2
HEAVY HYDROGEN OR DEUTERIUM
Properties of Deuterium
Pr,eparation
, ,
(a) Physical Properties: (i) It is a colourless,
.Therearetwo sources fromwhicbdellteriumcan beobtaif!.ed odourlessandtasteless gas. It is insoluble in water. (ii) It is
(i) Ordinary hydrogen, (ii) Heavyw.af:\;r. bad conductor of
heat and electricity. (iii) its density is twice
that of ordinary hydrogen. The density at NTP is 0.18 gllit.
. f;~
(iv) The atomicity like ordinary hydrogen is 2 and its molecule 2Na + DZ 360°C) 2NaD
is diatomic (Dz). (v) The various physical constants are Sodium deuteride
tabulated below: Ca + Dz~ CaDz
Deuterium (vii) Excb reactions: In a number of reactions,
Property
'Dz' deuterium occupies the place of hydrogen in an ion or a molecule.
I, Boiling point rC) -249.5 -252.6 The exchange reactions usually occur in presence of a catalyst
2. Melting point rC) -254.5 -259.1 like platinum black, finely divided nickel, palladium, etc. '
3. Latent heat of fusion (ca1/mo1e) 52.3 28.0
4. Latent heat of vaporisation 293.0 216.0 HzO + Dz Pt) DzO + Hz
(ca1/mole) zOO°C
N'
5. Dissociation energy (kcal/mole) 104.5 102.5 2NH3 + 3Dz ~ 2ND3 + 3Hz
6. Density at NTP (gIL) 0.18 0.09 Pt
zoo0c) CD 4 + 2Hz
The physical constants of deuterium are somewhat higher Deutero
methane
than protium.
(vi) The deuterium molecule, like hydrogen, also exists in Hz + D z 600"C) 2HD
Deutero hydrogen
ortho and para fonns. At ordinary temperature, it is a mixture A number of compounds are known in which ordinary
of 2 parts of ortho and 1 part of para. hydrogen has been replaced by heavy hydrogen, e.g., DN03,~
(b) Chemical Properties: Chemically deuterium is D ZS04 , D 3P04 and also the organic compounds such as DCN,
similar to ordinary hydrogen. It enters all the reactions CH3COOD, C2DZ, C~6' etc., are fonned.
characteristic of the ordinary hydrogen and fonns completely
equivalent compounds. However, it reacts slowly and less :;2~ Uses
completely than ordinary hydrogen due to heaviness.
(i) Burning: Like hydrogen, it burns in air or oxygen, (i) It has been widely used for the preparation of deutero
forming deuterium oxide, DzO (heavy water), compounds.
(ii) Deuterium and its compounds are used as tracers in the
2D z + Oz 560°C) 2DzO study of mechanism of chemical reactions and biological
(ii) Action with halogens: It reacts with halogens under systems.
suitable conditions to fonn deuterium halides which are similar (iii) One of the most important use of deuterium is, as a
to the halogen hydracids. bombarding agent in the artificial transmutation of elements.
In dark For Example,
DZ + Fz ) 2DF
At low temp. Deuterium fluoride HNa + lH ~ fiNa + lH
In light
) 2DCI
1~0 + 1H ~ liN + iHe
Deuterium chloride I~C + 1H ~ I~N + 6n
Heating 7L1· zH ~31+1 6L · 3H
2DBr 3 +1
Deuterium bromide (iv) It is ijsed in fusion reactions, i.e., in hydrogen bombs.
(ill) Combination with nitrogen: Deuterium combines jH + tH ~ iHe + 6n + energy
with nitrogen in the presence of a catalyst to fonn heavy
ammonia.
Catalyst ,
~al TRITIUM ~H or ~T)
3D z + N z \ 2ND3
Deutero ammonia
, Tritium is the isotope of hydrogen having mass 3. The existence
of this isotope was conflmled by Bleakney and Gould in 1934,
(Iv) Deuterium is occluded by metallic surfaces more slowly
by spectrometric studies on samples rich in deuterium. It occurs
than hydrogen.
in ordinary hydrogen in very minute quantity, i.e.,7 parts are
(v) Actionwitbunsaturatedhydrocarborts: Deuterium
present in 107 parts of ordinary hydrogen. Its oxide, TzO, is
reacts more slowly with unsaturated hydrocarbons in presence
present in water in extremely minute traces and, therefore, its
of a catalyst.
recovery either from ordinary hydrogen or ordinary water is
CHz
not possible. Artificial transmutation reactions or nuclear
, II reactions are used to produce tritium in very small quantities:
CHz CHzD (a) Oliphant, Harteck and Rutherford (1934) prepared
Ethene Deutero ethane tritium by bombarding deuterium compounds with high energy
(vi) Adion with metals: It combines with alkali and deuterons.
alkaline earth metals at higher temperatures. The compounds
are similar to corresponding hydrides.
(b) Tritium is produced by a number of nuclear reactions. fraction (H 20) is distilled first while the heavierfraction (D20)
is left behind. The heavier fraction becomes richer in D20.
~Be + 1H ----t ~Be + 1H (ii) By fractional freezing: The freezing points of
I §B + An ----t ~Be + 1H ordinary water and heavy water are O°C and 3.82°C, respec-
6 · I tively. Thus, the two materials are separated by fractional
3L 1 + On ----t iHe + 1H
(Slow) freezing. The process is repeated several times.
This is probably the best nuclear reaction of obtaining (iii) Taylor, Eyring and Frost method: (Multistage
tritium. electrolysis of ordinary water): Heavy water is mainly prepared
by this method these days. The method is based on continuous
Properties and prolonged electrolysis of ordinary water containing NaOH.
It is a gas. It boils at -248.1 o C and freezes at-252.4°C. It

is diatomic in nature. It is radioactive in nature. It undergoes
a ~-ray change. It'~ half life period is 12.4 years.
iT ----t ~He + Je -~Gasel'>
Chemically it is similar to ordinary hydrogen.
~1i1 Uses
It is used in several tracer experiments. It is used in fusion tft~;WIiI~I~~I~~If-- Steel
~ cell
(cathode)
reactions when large amount of energy is released. Water
3 2 4 1 Nickel
IH + IH ----t 2He + on + energy
(anode)
Physical-constants of H2, 02 and T2
Property Protium (Hz) Deuterium .(02) Tritium (Tz) Fig. 5.9 Electrolytic cell for the preparation of heavy water
Boiling point eC) -252.6 -249.5 -248.1 The cell used in this method is shown in Fig. 5.9. The cell
Melting point (0C) -259.1 -254.5 -252.4 dimensions are 45 cm long and 10 cm in diameter. It is made
Density at NTP (gIL) 0.09 0.18 0.27 of steel. The cell itself acts as a cathode while a perforated
Enthalpy of fusion 0.117 0.197 0.250
l cylindrical sheet of nickel acts as the anode. The electrolysis
(kJ mor )
Enthalpy of vapo- 0.904 1.226 1.393 is completed in seven stages and in actual practice a number
risation (kJ morl) of electrolytic cells are used.
Enthalpy of disso- 435.88 443.35 446.9
dation (kJ mol-I) I Properties of HeaVy Water
Constants are in increasing order Physical Properties : (a) Heavy water is a colourless,
)
odourless and tasteless mobile liquid, (b) Nearly all the physical
5. HEAVY WATER OR constants are higher than the corresponding values of ordinary
water. The comparison of physical constants is tabulated below:
DEUTERIUM OXIDE (020)
Physical Property H2 O DzO
The credit for the di,;,covery of heavy water goes to Urey who
first proved that ordinary water contains one part of heavy Maximum density (g/mL) 1.00 at 277 K 1.1073 at 284.6 K
water in 6000 parts of it. Lewis and Donald, in 1933, were Melting point O°C or 273 K 3.82°C or 276.82 K
able to isolate _few mi1lilitres of pure D 20 by continuous Boiling point 100°C or 373K 101.42 or 374.42K
electrolysis of water containing alkali. Specific heat 1.00callgK 1.01 callg K
Latent heat of fusion 79.7 callg 75.5cal/g
Preparation ' Latent heat of vaporisation 539callg 557 callg
Heavy water is prepared by following methods: Viscosity at 20"C 10.09 millipoise ,12.6 millipoise
(i) By fractional distillation of ordinary water: Surface tension at 20°C 72.8 dynes/cm 67.8 dynes/cm
The boiling points of ordinary water (H20) and heavy water Dielectric constant 78.39 78.06
(D 20) are 100°C and I01.42°C, respectively. Since, the differ- Solubility of NaCl (per lit.) 359 g 305 g
ence in boiling points is very small, the fractional distillation of Molecular mass 18.016 20.03
ordinary water is done in a very long fractionating column (13 Dissociation constant or ionic 1.0 x 10-14 OJ X 10-14
metre long) and the process is repeated several times. The lighter product at 25°C
Chemical Properties: Heavy water is chemically NaOH + D20 ~ NaOD + HDO
similar to ordinary water. However, D20 reacts more slowly
than H20 in chemical reactions.
HCI(aq) + D20 ~ DCI + HDO
(a) Action with metals: D20 reacts with alkali and NH4CI (aq) + 4D 20 ~ ND4CI + 4HDO
alkaline earth metals liberating heavy hydrogen. '.
(g) Deutero-hydrates: Heavy water like ordinary
2D20 + 2Na ~ 2NaOD + D2 water may be associated with salts as water of crystallisation,
Sodium
deuteroxide giviqg deutero-hydrate, e.g., Na2S04'lOD20, CuS04'5D20,
MgS0 4'7D20, etc.
2D20 + Ca ~ Ca(ODh + D2
Calcium (h) Deuterolysis: Water brings hydrolysis of certain
deuteroxide inorganic salts. D 20 gives similarreactions which are termed
Vapours of heavy water are decomposed by hot metals like deuterolysis.
Zn, Fe, etc.
D20 + Zn~ ZnO + D2 AICl3 + 3D20 ~ AI(ODh + 3DCI
Aluminium Deuterium
4D 20 + 3Fe ~ Fe304 + 4D2 deutero chloride
Magnetic hydroxide
oxide
(h) Action with metallic oxides: D20 reacts slowly BaS + 2D20 ~ Ba(ODh + D2S
Barium deutero Deuterium
with basic oxides to form heavy alkalies.
hydroxide sulphide
Na20 + D20 ~ 2NaOD
(i) Biological and physiological etTects: It has been
CaO + D20~ Ca(ODh
established that heavy water of high concentration retards the
(c) Action with non-metallic oxides: D 20 reacts slowly growth of plants and animals. It has been confIrmed by Lewis
with acidic oxides to form deutero acids. that tobacco seeds do not grow in heavy water. Pure heavy
N20S + D20 ~ 2DN0 3 water kills small fIshes, tadpoles and mice, when fed on with it.
Deutero nitric
,acid Taylor has shown that heavy water has germicide and
P20S + 3D20 ~ 2D3P04 bactericide properties. Water containing small quantity of D 20
Deutero acts as atonic and stimulates vegetable growth. Certain moulds
phosphoric acid
have ~een f<?und to develop better in heavy water in comparison
S03 + D20 ~ D2S04 to' ordinary water:
Deutero
sulphuric acid
(d) Action with metallic carhides, phospbides, nitrides, Uses
arsenides, etc.: Like H20, heavy water reacts with carbides, The' following are the important uses of heavy water:
phosphides, nitrides, arsenides, etc., to form corresponding (i) As a neutron moderator:, Fission in uranium-235 is
deutero compounds. brought by slow speed neutrons. The substances which are
CaC2 + 2D20 ~ Ca(ODh + C2D2 used for slowing down the speed of neutrons are called moder-
Deutero acetylene ators. Heavy water is used for this purpose in nuclear reactors.
AI4C3 + 12D20~ 4Al(ODh + 3CD4 . ' (Ji)For the preparation of deuterium: Heavy water on '
Deutero methane electrolysis or by its decomposition with metals produces
Mg3N2 + 6D20~ 3Mg(ODh -.: 2ND3 . deuterium.
Deutero ammonia
, '·(iii) As a tracer compound: Heavy water is commonly
AlN + 3D20~ AI(ODh + ND3 used as a tracer compound for studying various reaction
Deutero ammonia
mechanisms. It has also been used for studying the structure
Ca3P2 + 6D20~ 3Ca(ODh + 2PD 3 of some oxyacids of phosphorus such as H 3P02 and H 3P0 3
Deutero phosphine
as to determine the number of ionisable hydrogen atoms.
Na3As + 3D 20 ~ 3NaOD + AsD3
Deutero arsine Production in India: Various units have been set in India
(e) Electrolysis: A solution of heavy water containing to manufacture heavy water. These are situated at Nangal,
Na2C03 when electrolysed evolve heavy hydrogen at cathode. Trombay, Rourkela, Namrup and Neyveli.
Electrolysis
2D20 ) 2D2 + 02 WATER
(Cathode) (Anode)
Water is one of the most plentiful and readily available of all
(f) Exchange reactions: When compounds having labile chemicals. Almost three-fourth of the earth's surface is covered
hydrogen react with heavy water, hydrogen is exchanged by with water. It is essential to life. Two-third of the human body
deuterium partially or completely.
. is water. It has special importance to a chemist because of its Zn + H20~ Zno + H2

ability to dissolve so many other substances. As a result, water 3Fe + 4H20 ~ Fe304 + .4H2
serves as a medium in which a great variety of chemical Mg + 2H20 ~ Mg(OH)z + H2
reactions occur. Although it is most often perceived as a liquid
Pb and Cu decompose water only at a white heat. Ag, Au,
at normal atmospheric pressure, water exists asa solid below
Hg and Pt metals do not decompose water.
O°C and as a gas above 100°C. The terms ice and steam are
(iii) Reaction with nonmetals : Fluorine decomposes
used to describe the solid and gaseous states of water.
cold water.
II Properties of Pure Water 2F2 + 2H20 ~ 2H2F2 + 02}
Ozonised oxygen
(a) Physical Properties: (i) Pure water is colourless, 3F2 + 3H20 ~ 3H2F 2 + 0 3
tasteless and odourless. It gives bluish tinge in thick layers. Chlorine decomposes cold water forming HCI and HCIO.
(ii) It freezes at O°C and boils at 100°C. (iii) Its maximum Cl2 + H20~ HCI + HCIO
density is 1.00 gcm-3 at 4°C. (iv) It is a polar molecule and Hypochlorous
has V-shaped structure. The bond angle is I04S. (v) It has acid
a high dielectric constant. The polar character of water makes However, in presence of sunlight only HCI is formed with
it an excellent solvent for polar and ionic substances. (vi) It is liberation of oxygen. "
a poor conductor of electricity. (vii) It has the tendency to
associate. It exists in the liquid state not as a single H 20
molecule but as associated molecules through hydrogen bonding When steam is passed over red hot coke (lOOO°C), water
[Fig. 5.11 (b)]. The existence of hydrogen bonding is responsible gas is formed.
for high values of specifll heat, the latent heat of fusion and
C + H20 ~ CO + H2
latent heat of vaporisation. '----v---'
Water gas
Phystcal Constants of Water (iv) Action on nonmetallic oxides: Acidic oxides
combine with water to form acids.
M.pt.lK 273.0
B.pt.lK 373.0 CO2 + H20;;:::::::'!: H 2C03 (Carbonic acid)
Enthalpy of fonnationIkJ mol- i
-285.9 S02 + H20 ~ H2S03 . (Sulphurous acid)
l
Enthalpy of fusionIkJ mor 6.01 S03 + H 20 ~ H2SO4 (Sulphuric acid)
Enthalpy of vaporisationIkJ morl 40.06 P20S + 3H20 ~ 2H3P04 (Orthophosphoric acid)
Viscosity (centipoise) 0.89 N20 S + H20 ~ 2HN03 (Nitric acid)
Dielectric constant 78.39 Cl20 7 + H20 ~ 2HCI04 (Perchloric acid)
Density (g cm-3) 1.00
(v) Action on metallic oxides: Basic oxides combine
Temp. of max. density (K) 276.98 with water to form alkalies.
(b) Chemical Properties : (I) Water is neutral in nature. Na20 + H 20 ~ 2NaOH
pH of the pure water is 7. It is a weak electrolyte and feebly
CaO + H20 ~ Ca(OH)z
ionises into H+ and OH- ions.
(vi) Action on hydrides, car~ides, nitrides, phosphides :
H20 ;;:::::::'!: H+ + Orr- Water decomposes these compounds with liberation of
In pure water [H+] = [Orr-] 10-7 at 25°C. hydrogen, acetylene (or methane), ammonia, phosphine
(ii) It reacts with active metals and evolves hydrogen. The respectively. .
reaction is exothermic in the case of alkali and alkaline earth CaH2 + 2H20 ~ Ca(OHh + 2H2
metals. CaC2 + 2H20 ~ Ca(0H)2 + C2H2
2Na + 2H20 ~ 2NaOH + H2
A4C 3 + 12H20 ~ 4Al(OHh + 3CH4
Ca + 2H20 ~ Ca(OH)z + H2
It is pecomposed by metals like Zo, Mg, Fe, etc., when Mg3N 2 + 6H20 ~ 3Mg(QH)z + 2NH3
steam is passed over hot metals. Ca~2 + 6H20 ~ 3Ca(OHh + 2PH3
(vii) Hydrolysis: Many salts specially the salts of strong fiI Tests of water
bases with weak aCids, weak bases with strong acids and
(i) A drop of water when added to anhydrous copper sulphate,
weak bases with weak acids undergo hydrolysis with water.
changes its colour from white to blue.
CH3COONa + H20 ~ CH3COOH + NaOH (ii) Water reacts with CaC2 to evolve acetylene which bums
CH3COONH4 + H20 ~ CH3COOH + NH 40H with bright flame.
FeS04 + 2H20 ~Fe(OHh + H2S04 i¥il Structure of Water Molecule

Some salts on hydrolysis form oxy compounds. Oxygen atom in water molecule is si hybridized, four
hybrid orbitals directed towards the comers of a tetrahedral
BiCl3 + H20 ~ BiOCI + 2HCI
Bismuth
are formed. Two of the hybrid orbitals having one electron
oxychloride each overlap with two hydrogen atoms and form two sigma
SbCl3 + H20 ~ SbOCl + 2HCI bonds. Thus, the molecule has a bent structure with a bond
Antimony angle of 104S (Fig. 5.10) . The bond angle is less than the
oxychloride
expected angle in tetrahedron due to the presence of two lone
Halides of nonmetals are decomposed by water. pairs of electrons on two .uncombined hybrid orbitals which
PCIs + 4H20 ~ H3P04 + SHCI repel each other and the bonded pairs cause them to come
closer and thereby reducing the bond angle from 109°28' to
PCl3 + 3H20 ~ H3P0 3 + 3HCI
104S. Because of high electronegativity of oxygen, the--
S02Cl2 + 2H20 ~ H2S04 + 2HCI O-H bonds are polar, i.e., oxygen is partially negatively charged
SiCl4 + 3H20 ~ H2Si03 + 4HCI and each hydrogen is partially positively charged. The molecule
(viii) Decomposition: Water containing either alkali or is polar and possesses dipole moment (1.84 D). Molecules are
acid when electrolysed gets decomposed intD H2 and O2. linked with each other by hydrogen bonding [Fig. 5.11 (b)].
2s 2p
2H20 ~ 2H2 + O2
O-atom ,[IT] r:1t.o,-j,-'-1--:-j-rl-=-j---;I ,
When heated at 2S00°C, it breaks up into hydrogen and
oxygen to a small exteht(4%). sp3 hybridization
(ix) Water of crystallisation: It combines with many
salts during crystallisation to form hydrates, e.g.,
CuS04'SH20; MgS04'7H20; FeS04·7H20
The water present in the hydrates is called water of hydration
or water of crystallisation.
The hydrates can be classified into the following three
categories:
(a) Water molecules are coordinated to the central metal ion H
to form complex ions. For example, in chromic chloride
hexahydrate, the six molecules are linked to the central Cr3+ ~ig. 5.10
ion, [Cr(H20)6]CI3'
-.·'Example 2. Explain, why the density of ice is less than
(b) Water molecules are linked to some oxygen containing
water? or why there is decrea,se in volume when ice melts?
anions by hydrogen bonding. For example, in CuS04·SH20,
Solution: In ice each molecule of H20 is surrounded by
four H20 molecules are coordinated to the central Cu 2+ ion
three H20 molecules in hexagonal honey comb manner as
while the fifth H20 molecule is linked to soi- ion by hydrogen
shown in Fig. 5.11 (a). On the other hand in water, each
bonding.
molecule is surrounded by four neighbouring molecules
(c) Water molecules are present in interstitial sites or voids randomly [Fig. 5.11 (b)]. This arrangement gives rise to an
in the crystal lattice. For example, in barium chloride dihydrate, open-cage like structure. There are evidently, a number of
BaCI2·2H20, the two water moelcules occupy the voids in the 'holes' or open spaces. In such a structure lesser number of
crystal lattice. molecules are packed per mL. When ice melts a large number
(x) Water as a catalyst: Water acts as a catalyst in of hydrogen bonds are broken. The molecules, therefore, move
many reactions. Perfectly dry gases generally do not react but into the holes or open spaces and come closer to each other
the presence of moisture brings the chemical change. than they were in solid state. This results sharp increase in the
Ammonia and hydrochloric acid gas combine only in presence density. Thus, ice has lower density than water and there is
of moisture. contraction in volume. The contraction continues from O°C to
4"C as the hydrogen bonds are broken progressively. The CaC03 + H20 + CO2 = Ca(HC03h
density of water is maximum at 4"C. Temporary hardness in water is easily removed by boiling,
as the bicarbonates decompose readily and the insoluble
.carbonates are precipitated.
. Boil '
Ca(HC03h ---7 CaC03 + H20 + C02
(Insoluble)
Boil
Mg(HC0 3h ---7 MgC03 + H20 + CO2
(Insoluble)
Temporary hardnesscan also be removed by Clark's process
which involves the addition of slaked lime [Ca(OHh].
Ca(HC03h + Ca(OHh ~ 2CaC03 + 2H20
Fig. 5.11 (a) Hexagonal honey comb structure of ice. In ice (Insoluble)
each molecule of H20 is surrounded by three neighbouring
H2 0 molecules (b) In water, each H2 0 molecule is surrounded
v
by four neighbouring H20 molecules randomly (Insoluble)
It is essential to add only the calculated amount of Ca(OHh
HARD AND SOFT WATER because excess will cause artificial hardness.
A water is said to be the soft if it produces sufficient lather (b) Permanent Hardness
with the soap and water is described as being hard if it forms
an insoluble scum before it forms a lather with soap *. The Permanent hardness is introduced when water passes over
hardness of natural water is generally caused by presence of rocks containing the sulphates or chlorides of both of calcium
the bicarbonates and sulphates of calcium and magnesium but and magnesium. This type of hardness cannot be-removed by
infact all soluble salts that form a scum with soap cause boiling or by the addition of slaked lime. Many substances are
hardness. used for the removal of this type of hardness. The substances
used to remove the hardness of water are known as water
Ca2+(aq) + 2C 17H 35 COO-(aq) ~ (C 17H35COOhCa softeners. The various water softeners are:
2+ . (i) Washing soda: It removes both the temporary and
Mg (aq) + 2C17H35COO-(aq) ~ (C17H35COOhMg
Anion of soap Insoluble precipitates pennaneut hardness by converting soluble calcium and
magnesium compounds into insoluble carbonates.
Soap will not produce lather with water until all the calcium
and magnesium ions have been precipitated. Hard water thus CaCl2 + Na2C03 = Caco 3 + 2NaCl
wastes soap. Hardness of water is of two types: CaS04 + Na2C03 = CaC03 + Na2S04
(a) Temporary hardness
(b) Permanent hardness.
Ca(HC03h + Na2C03 = CaC03 + 2NaHC0 3
(Insoluble) (Soluble)
(a) Temporary Hardness In place of sodium carbonate, caustic soda or sodium

phosphate -can also be used.
This is due to the presence of bicarbonates of calcium and
MgCl 2 + 2NaOH ~ Mg(OHh+ 2NaCI
magnesium. Rain water dissolves small quantities of CO2 from
(Insoluble)
the atmosphere forming a very dilute solution of carbonic acid.
This water attacks calcium and magnesium carbonates in any 3MgS04 + 2Na3P04 ~ Mg3(P04h + 3Na2S04
rocks over which it flows and the soluble hydrogen carbonates (Insoluble)
o~ bicarbonates are formed.
*Ordinary soap is the sodium salt of fatty acids. It is used as cleaning agent. The basis for cleaning action of soaps is that they contain a long
hydrocarbon chain with an ionic group at one end.
/0
CH3CH2.........................: ................... CH2C~
Long hydrocarbon chain O-Na+
Ionic group
The ionic group is water soluble and the hydrocarbon group is oil soluble. The dirt particles are usually oil containing. As a consequence the
hydrocarbon end of the soap is attached to and dissolve in the dirt particles, leaving the ionic end exposed to water. The net effect is to make the dirt
particle disperse in the water as a stable emulsion and thus remove it from the object to be cleaned.
(0) Pennutit: Pennutit is the technical name given to insoluble organic acid resin having giant molecules with
ceJtrin hydrated silicates of aluminium and sodium. It is obtained -S03H or -COOH groups while the anion exchanger contains
by fusing sodium carbonate, china clay, silica or quartz. The giant organic molecules with basic groups derived from amines.
product is washed with water to remove soluble portion. The Ion exchange resins remove all soluble minerals from water.
remaining crystalline mass sodium aluminosilicate or sodium The hard water is first passed through a bed of cation exchanger,
zeolite (Na2Al2Si20S'xH20) is technically called as pennutit.
The sodium ions of pennutit are exchanged with calcium and
magnesium ions, removing the hardness of the water, when
hard water is passed through it (Fig. 5.12).
Na2Al2Si20S·xH20 + Ca2+ ~ CaA12Si20 S·xH20 + 2Na+
sodium aluminosilicate Calcium aluminosilicate
c
(Permutit) or or .9
Mg2+ MgAl2Si20s·xH20 t eIii (1)
Magnesium aluminosilicate
These ions can be re-exchanged by treating it with brine

(NaCl) solution.
- .. Ol
~
s
-<l-
~
CaAI2Si20S·xH20 + 2NaCI ~ Na2Al2Si20S·xH20 + CaCl2
This method is useful for the removal of both temporary
t l.::::=::;p;u::re=w=-~r
and pennanent hardness of water. Waste
Fig. 5.13 Ion exchanger
which removes the cations like Na+, Ml+, Ca2+ and others by
exchanging with H+ ions.
Ca2 + 2RH + ea2+ ~ (RhCa + 2W

Ca2+ions -+--Ca2+ Resin
stay on resin Ca2+ . The water coming from cation exchanger is acidic on
Ca2+ions Na+ Na+ Na* Na+
in hard water account of free H+ ions. This wateris then passed through another
Na+ Na+ Na+ Na+
bed containing anion exchanger. This exchanger removes
Na+ions Na+ Na+ Na+ Na+
on resin anions like Cl- , sot NO) by exchanging with OH- ions.
~
8 ~
8 R-NH30H + cr~ R-'NH3Cl + OIr
Na+ Na+ Na+ Na+
Rcsin
The OH- ions neutralise the H+ ions.
H+ + OH-= H20
Na+ ions in the This process gives distilled water and can be used in
softened water laboratories.
The cation exchanger is regenerated by the action of an
acid and the anion exchanger is regenerated by pouring a
Fig. 5.12 The exchange of one type of ions solution of a suitable sodium salnhrough it.
.in a solution by another
(iii) CaJgon: The complex salt of metaphosphoric acid, Disadvantages of Hard Water
sodium hexametaphosphate (NaP03)6, is known as calgon.1t is (i) In domestic use: Water is required for cooking,
represented as Na2[N~(P03)6]' Calcium and magnesium salts bathing and washing of clothes, etc., in our daily life. Hardness
present in hard water react with calgon to give complex salts. upto 100 to 150 ppm in water is tolerable, but if the hardness
2CaS04 + Na2[N~(p03)6]'~ Na2[Ca2(P03)6] + 2Na2S04 is more than this, the water is not suitable for domestic use.
Pulses and vegetables do not cook well in hard water. Hard
2MgS04 + Na2[Na4(P03)6] ~ Na2[Mg2(P03)6] + 2Na2S04
water spoils the lustre of utensils. Scales are fonned in cooking
This method is especially used softening· water for boiler vessels which cause wastage of fuel and cleaning of the vessels
use. becomes difficult.
(iv) By ion exchange resins: Ion exchange resins are Hard water is not fit for bathing as it does not produce
the most popular water softeners these days. These resins are sufficient lather with soap. It makes the skin' dry. Hard water
synthetic substances. The cation exchanger consists of granular
is unfit for laundry purposes. There is a considerable loss of 100

soap due to formation of insoluble compounds. Yellow stains
.. 1 mg of CaCl2 =:; ill x 1 mg of CaC03
are formed on the clothes if iron salts are present in hard water. == 0.9 mgof CaC03
Oi) In industrial use: Industries like dyeing, printing
95 grams of MgCl2 =:; 100 grams of CaC03
textiles, sugar, etc., require large quantities of water. Water
100
containing iron and manganese salts is unfit for use in dyeing . . 1 mg of MgCl z =:; 95 x 1 mg of CaC03
and printing textiles because these produce insoluble lakes with == L05 mg of CaC03
dyes.
(iii) In boiler use: Water is used in producing steam. Thus, one litre of hard water contains (0.9 + 1.05) = 1.95
When hard water is used for production of steam in boilers, mg of CaC03
it presents three main difficulties: One litre water = 103 grams == 106 mg
(a) Fonnation of scales: It is the deposition of dissolved Degree of hardness = 1.95 ppm
minerals in the form of crust within the boiler shell. The
crust is hard and heat insulating. It makes wastage of fueL
HYDROGEN PEROXIDE
Sometimes the crust breaks at certain place which leads to an Hydrogen peroxide was discovered by the French chemist,
accident. L.J. Thenard, in 1818, by ·the action of sulphuric acid on
(b) Corrosion: MgCl2 present in hard water gets barium peroxide. It was called oxygenated water.
hydrolysed with formation of free HCL This attacks the metal It occurs in traces in air, rain, snow, some' naniril' waters
surface of the boiler and thereby shortens its life. and juices of certain plants.
MgCl2 + H20 ~ Mg(OH)CI + HCI
Laboratory Preparation
Corrosion is also affected by the presence of dissolved
(i) From sodium peroxide: It is prepared in the
gases like C02, H2S, S02, etc., in hard water. Corrosion can
laboratory by adding small amounts of sodium peroxide to
be prevented by the addition of suitable amounts of alkalies like
ice cold water.
NaOH or Na2C03'
(c) Foaming: It is the formation of bubbles on the surface Na20z + 2H20 ---7 2NaOH + H202
of the water in the boiler. This occurs due to the presence of In place of cold water, dilute sulphuric acid (20%) can be
suspended particles in water. It causes wastage of fuel. used. Sodium peroxide in small amounts at a time is added to
cold 20% sulphuric acid.
~ Degree of Hardness
Na202 + H2S04 ---7 Na2S04 + H20 2
The degree of hardness is defined as the number cif parts
The crystals of hydrated sodium sulphate (Na2S04·lOH20)
of calcium carbonate or equivalent to various calcium and
are removed by cooling the solution. The solution of hydrogen
magnesium salts present in a million parts of water by mass.
peroxide obtained always consists some dissolved sodium
It is expressed as ppm.
sulphate. The concentration of H202 is about 3%.
Example 3. Find the degree of hardness of a sample of (ii) From barium peroxide: Hydrogen peroxide can be
water containing 12 mg of MgS04 (Mol. mass 120) per kg of obtained by adding barium peroxide to dilute sulphuric acid at
water. O°C. The reaction between anhydrous barium peroxide and
Solution; 12 mg of MgS04 is present in 103g of water. sulphuric acid is, however, slow and practically ceases after
Thus, 106 g of water contains = 12000 mg of MgS04 some time due to the formation of a prote(;tive coating of
120 g MgS0 4 =:; 100 g of CaC03 barium sulphate on barium peroxide. This difficulty can be
overcome if hydrated barium peroxide is used in place of
So, 12000 mg of MgS04 = 100 12000
120 x 1000 = 10 g CaC03
anhydrous barium peroxide.
Ba02·8H20 + H2S04 = BaS04 + H20 Z + 8HzO
Hardness of water == 10 ppm
The barium sulphate formed is filtered off and a solution of
':EDmple 4. One litre of a sample of hard water contains HzOz is obtained.
1 mg of CaClz and 1 mg of MgCI 2 . Find the total hardness in The use of sulphuric acid has a disadvantage as it catalyses
6
terms of parts of CaC03 per 10 parts of water by mass. the decomposition of hydrogen peroxide formed. In place of
Solntion: sulphuric acid, weak acids like orthophosphoric acid, carbonic
Mol. mass of CaClz = 111, MoL mass of MgCl2 = 95 acid are preferred. Barium peroxide on treatment with
orthophosphoric acid gives a precipitate of barium phosphate
111 grams of CaClz =:; 100 grams of CaC03
and H20z which goes into the solution.
Hydrogen and its Comp~unds 237
3BaCh + 2H3P04 ~ Ba3(P04h + 3H20 2 as an initiator. The alcohol gets oxidised giving acetone and
ppt. hydrogen peroxide.
Insoluble barium phosphate is filtered off. The filtrate consists CH3CHOHCH3 + O2 ~ CH3COCH3 + H 20 2
of hydrogen peroxide.
Acetone and unreacted isopropyl alcohol distil over leaving
The barium pho!--phate is decomposed by dilute sulphuric
behind the aqueous solution of hydrogen peroxide.
acid. ""
(iii) Electrolytic process: In this process, the electrolysis
Ba3(P04b + 3H2S04 ~ 3BaS04 + 2H3P04 of 50% sulphutic acid is carried out at low temperature using
BaS04 is removed by filtration and orthophosphoric acid platinum .electrodes and a current of high density. Peroxy
is used again. disulphuric acid is formed.
(iii) Merck's process: H20 2 can be obtained by passing 2H2S04 ~ 2W + 2HS0'4
a current of CO2 through a cold pasty solution of barium
peroxide in water. 2HS0'4 ----:-t H2S20S +2e- (At anode)
Peroxy
Ba02 + CO2 + H20 ~ BaC0 3 + H20 2 disu\pburic acid
Barium carbonate being insoluble is filtered off. Peroxy disulphuric acid is distilled. Hydrolysis occurs and
a distillate containing about 30% H20 2 is obtained.
~ Manufacture of Hydrogen Peroxide H2S20 S + 2H20 ~ 2H2S04 + H 20 2
(i) Auto-oxidation of 2.butyl antbraquinol: This is In place of 50% H 2S04, ammonium hydrogen sulphate
the most recent process for the manufacture of hydrogen dissolved in excess of sulphuric acid can be used for
peroxide. 2-Butyl anthraquinone is catalytically reduced to electrolysis.
2-butyl anthraquinol in an organic solvent by passing hydrogen NH4HS04 ~ ~SO'4 + H+
in presence of palladium. It is then oxidised by passing air. The At anode 2NH4S04 ~ (NH4hS20S + 2e-
H 20 2 is extracted with water to give about a 20% solution. Ammonium peroxy
2-Butyl anthraquinone is reformed which is again used. The disulpbate
method, thus, involves alternate oxidation and reduction steps, At cathode 2H+ + 2e- ~ H2(g)
only hydrogen is consnlUed in this method (Fig 5.14).
The solution containing ammonium peroxy disulphate is
a CYYC
o OH heated at 43 mm pres,ure when its hydrolysis occurs forming
I I hydrogen peroxide.
a
~
CI(YC~7:d)~
l 'C~
I
o
~.
l
OH
C~
I
4 9
H
(~hS20S + 2H20'--7 2N~·HS04 + H 20 2
Hydrogen peroxide along w.ith wat~r distils over. Ammonium
bisulphate can be used again. This m~thod gives 30-40%
aqueous solution of hydrogen peroxide.
D 20 2(Deutero peroxide) can also be prepare.d by this
2-Butyl anthraquinone 2-Butyl anthraquinol method.
t'02(Air)
o ~ Concentration of H20 2 solution

II Hydrogen peroxide obtained by the above methods is always
I .I + H20 2
in the form of dilute aqueous solution .. The concentration of
this solution is difficult due to explosive nature of hydrogen
'IT &7 peroxide. The explosive decomposition is catalysed by the
presence of organic matter and metallic ions. The concentration
o
of the aqueous dilute solution having H202 is done carefully by
Fig. 5.14 the application of following steps:
(i) The dilute solution is concentrated at 60-70°C on a
(ii) By oxidation of isopropyl alcohol: . This industrial water bath. Water being more volatile than hydrogen peroxide,
. method of manufacture of hydrogen peroxide involves the a considerable amount of water gets evaporated and the
oxidation of isopropyl alcohol with oxygen under slight pressure. concentration of the solution becomes 30%. It is not advisable
The isopropyl alcohol is mixed with a small amount of H 20 2 to concentrate the solution beyond 30% as there is possibility
and oxygen is passed through at 70°C. The H202 added acts of an explosion by this step:
(ii) The above solution is distilled at 35-40°C under reduced divided metals like Pt, Au, Ag accelerate its decomposition.
pressure of about IS mm in the apparatus shown in Fig. 5.15. Traces of acid, acetanilide, alcohol or stannates increase its
Repeated distillation gives 90% H202. stability. .
Distilling flask (0) Acidic nature: The pure liquid has weak acidic nature
Manometer but its aqueous solution is neutral towards litmus. It reacts
with alkalies and carbonates to give their corresponding
peroxides.
H 20 2 + 2NaOH = Na202 + 2H20
H202 + Ba(OHh = Ba02 + 2H20
H 20 2 + Na2C03 -:- Na202 + CO2 + H 20
(iii) Oxidising nature: It is a powerful oxidising agent.
It is an electron acceptor in acidic and alkaline solutions.
H20 2 + 2W + 2e .2H20 (In acidic solutions)
Fig. 5.15 Under low ptessure concentration of H20 2
H 20 2 + 2e- = 20H- (In alkaline solutions)
(iii) Further concentration is achieved by cooling 90% The reactions. are generally slow in acid solutions but fast
solution with the help of solid CO 2 and ether bath till in alkaline solUtions.
crystallisation sets in. Crystals are separated, melted and refrozen Oxidising nature of hydrogen peroxide can be interpreted on
to get 99% pure H202. account of the possession of labile oxygen atom. The potential
equation for its oxidising nature can be written as,
Storing
H202 ----? H 20 + 0
The decomposition of H 20 2 is easily catalysed by metals,
rough surfaces, sunlight, dust particles, glass and alkali. It is The following examples show the oxidising nature ofH202:
stored in vessels of pure aluminium or in stone jars in dark. (a) It oxidises black lead sulphide (PbS) to white lead
Concentrated solutions of hydrogen peroxide are stored these sulphate (PbS04).
days in polythene bottles kept in refrigerators. Small amounts [H202 ----? H20 + 0] x 4
of stabilizers such as orthophosphoric acid, acetanilide or PbS + 40 ----? PbS0 4
sodium stannate are added to the solutions to be stored.
PbS + 4H20 2 ----? PbS04 + 4H20
Properties of H 20 2 (b) It oxidises nitrites to nitrates.
Physical Properties: (i) Pure anhydrous hydrogen H 20 2 ----? H 20 + 0
peroxide is a syrupy liquid. It is colourless but gives a bluish NaN02 + 0 ----? NaN03
tinge in thick layers. It is odourless.
(ii) Its specific gravity is 1.45 at O°C. NaN02 + H 20 2 ----? NaN0 3 + H 20
(iii) It is soluble in water, alcohol and ether. (c) It oxidises sulphites into sulphates.
(iv) It has bitter taste. It is injurious to skin (blisters are
H202 ----? H20 + 0
formed).
(v) It boils at 152°C and freezes at -O.89°C. It begins to Na2S03 + 0 ----? Na2S04
decompose at boiling point, however, it can be distilled under Na2S03 + H 20 2 ----? Na2S04 + H 20
redu~d pressure.
(d) It oxidises arsenites into arsenates.
(vi) It is an associated liquid due to hydrogen bonding.
(vii) The dipole moment of H 20 2 is little more (2.1 D). than H20 2 ----? H 20 + 0
that of H 20 (1.84 D). Na3As03 + 0 ----? Na3As04
Chemical Properties: Na3As03 + H 20 2 ----? Na3As04 + H 20
(i) Stability: It is unstable in nature. It decomposes on (e) It liberates iodine from potassium iodide.
standing and heating. It is an example of auto oxidation-reduction H202 ----? H20 + 0
reaction.
2KI + H2S04 + 0 ~ K2S04 + 12 + H 20
2H2~ = 2H20 + 02
The oxidation number of oxygen changes to 0 and -2 2KI + H2S04 + H20 2 ----? K2S04 + 12 + 2H20
from -1. Presence of traces of Mn02, carbon, alkali or finely or 2r + H 20 2 + 2It" ---7 12 + 2H20
Hydrogen and its Compounds . 239
(I') It oxidises H 2S into sulphur. Peroxide of chromium is represented as
H202~H20+0 o 0
H2S + 0~H20 + S
H:!S + H 20 2 ~ 2H20 + S l>rr~
o
(g) It oxidises acidified ferrous sulphate to ferric sulphate.
(Butterlly shape)
H202~H20 +0 (m) In alkaline medium, it oxidises manganese sulphate (a
2FeS04 + H2S04 + 0 ~ Fe2(S04h + H 20 manganous salt) to manganese dioxide.
2FeS04 + H 2S04 + H2~ ~ Fe2(S04h + 2H20 MnS0 4 + H 20 2 + 2NaOH ~ Mn02 + Na2S04 + 2H20
or 2Fe2+ + H2~ + 2H+ ~ 2Fe3+ + 2H20 or Mn2+ + H202 ~ Mn4+ + 20H-
(n) In acidic solution, mercury is oxidised to mercuric
(h) It oxidises acidified potassium ferrocyanide to potassium .
oxide.
ferricyanide.
Hg + H 20 2 _H-=-2S_0 -7) HgO + H 20
..:....4
H2~~H20+0
(0) Bleaching action: Due to its oxidising nature, it acts
2~Fe(CN)6 + H2S04 + 0~2K3Fe(CN)6 + K2S04+H 20 asa bleaching agent.
2~Fe(CN)6+H2S04+H202 ~ 2K 3Fe(CN)6 +K2S04+2H20 Coloured material + 0 ~ Colourless
It bleaches materials like silk, hair, ivory, cotton, wool, etc.
or 2[Fe(CN)6]4- + H 20 2 + 2H+ ~ 2[Fe(CN)6]3- + 2H20
When used as a hair bleach (a 6% solution), it acts by
(i) It oxidises formaldehyde to formic acid. This oxidation oxidizing the pigments in the hair.
occurs in pres~nce of pyrogallol and in alkaline medium. (iv) Reducing nature: It can also act as a reducing
H202~H20 +0 agent towards powerful oxidising agents.
H202 ~ 2H+ + O2 + 2e-
HCHO + 0 ~ HCOOH
In alkaline solution, however, its reducing action is more
HCHO + H20 2 ~ HCOOH + H20
effective.
or 2HCHO + H202 ~ 2HCOOH + H2 H202 + 20Ir ~ 2H20 + O2 + 2e-
(j) Benzene in presence of ferrous sulphate is oxidised to The potential equation when H20 2 acts as a reducing agent
phenol. can be expressed as,
OH H20 2 + 0 ~H20 + O 2
20 +H202--~ o
(k) It dissolves Ii'le chromic hydroxide precipitate present
(a) Ag20 is reduced to SilV€f.
Ag20 + H 20 2 ~ 2Ag + H 20 + O2
(b) It reduces ozone to oxygen.
in Na.oH solution forming a yellow solution of sodium H202 + 0 3 ~ H20 + 202
chromate. (c) Manganese dioxide in acidic medium is reduced to
[H202 ~ H20 + 0lx 3 manganous salt. ,
2Cr(OHh + 4NaOH .+ 30 ~ 2Na2Cr04 + 5H20 Mn02 + H 2S04 + H20 2 ~ MnS04 + 2H20 + O2
(d) Lead dioxide is reduced to lead monoxide.
2Cr(OH)rt4NaOH+3H202 ~ 2Na2Cr04 + 8H20
Pb02 .f H 20i. ~ PhO + H 20 + O2
(1) A solution of chromic acid in sulphuric acid or acidified
(e) Red lead in ·presence of HN03 is reduced to plumbous
potassium dichromate is oxidised to blue peroxide of chromium
salt.
(cr05) which is unstable, however,it is soluble in ether and
produces blue coloured solution. +
Pb 30 4 6HN03 + H 20 2 ~ 3Pb(N03h + 4H20 + O2
(f) Chlorine and bromine are reduced to corresponding
K2Cr207 + H2S04 ~ K2S04 + H2Cr2~
hydracids.
[H202 ~ H20 + 0] x 4 Cl2 + H20 2 ~ 2HCI + O2
••"'A"'I7 + 40 ~ This reaction can be shown in following steps:
K2Cr2~ + H2S04 + 4H202 ~ 2Cr05 + K2S04 + 5H20 Cl2 + H20 ~ HCI + HCIO
Peroxide of chromium decomposes to form chromic sulphate HCIO + H 20 2 ~ HCI + H20 + O2
and oxygen. Cl2 + H20 2 ~ 2HCl + 02
4Cr05 + 6H2S04 ~ 2Cr2(S04h + 6H20 + 702 Similarly, Br2 + H 20 2 ~ 2HBr + O2
(g) It reduces acidified KMn04 solution, i.e., acidified (viii) It. is used to produce sodium peroxoborate.
KMn04 is decolourised by H 20 2. Na2B2(02h(OH)4 in hexahydrate state, it is used as a brightner
2KMn04 + 3H2S04 ~ KiS04 + 2MnS04 +3H 20 + 50 in washing powders.
2NaB0 2 + 2H20 2 + 6H20 ~
5H20 2 + 50 ~ 5H20 + 502
Na2 [(OHhB (O-OhB (OHhl 6H 20
2KMn04 +3H 2S04 + 5H20 2--7 K2S04+ 2MnS04 + 8H20+50 2 Structure of peroxoborate ion may be given as,
or 2Mn04+ 6H+ + 5H20 2 ~ 2Mn2+ + 8H 20 + 502
(h) Potassium ferricyanide (alk. solution) is reduced to
potassium ferrocyanide.
2K3Fe(CN)6 + 2KOH ~ 2K4fe(CN)6 + H20 + 0
H 20 2 + 0~H20 + O2 !If Tests of Hydrogen Peroxide
2K3Fe(CN)6 + 2KOH+H20 2 ~2~Fe(CN)6 +2H 20 + O 2
(i) A filter paper with a stain of black lead sulphide (PbS)
or 2[Fe(CN)6]3- + 20H- + H20 2 --7 2[Fe(CN)6]4- + 2H20 + O2 when brought in contact with a solution of H 20 2, the black
.stain turns white.
(i) Hypohalites are reduced to halides.
[PbS ~ PbS0 4]
NaOCI + H2Ch ~ NaCI + H 20 + O2
(ii) An acidified solution of titanium salt when treated with
(j) Kl04 is reduced to Kl0 3, . H20 2, yellow or orange colour is developed due to formation
Kl0 4 + H 20 2 ~ Kl0 3 + H 20 + O 2 of pertitanic acid,
(v) Addition reactions: Hydrogen peroxide is capable [Ti(S04h + H 20 2 + 2H20 = H2Ti04 + 2H2S04]·
of adding itself to ethylenic linkage. Pertitanic acid
r
CH2
2
+ HI
HO
~ F2
0H
CH20H
(iii) H 20 2 when shaken with acidified K2Cr207 with little
ether, blue colour is produced. This is due to the formation of
peroxide of chromium (perchromic acid).
• Ethylene Ethylene glycol (iv) It liberates iodine from Kl solution which gives blue
colour with starch solution.
~ Uses (v) It decolourises acidified potassium permanganate
Hydrogen peroxide in the form of aqueous solution is used: solution.
(i) in the bleaching of delicate materials such as wool, silk,
cotton, bone, ivory, hair, etc.
Ilil Strength of H202 solution
(ii) as a valuable antiseptic and germicide for washing Strength of the sample of hydrogen peroxide is generally
wounds, teeth and ears under the name of perhydroI. expressed in terms of the volume of oxygen at NTP that one
(iii) In general a 3% H 20 2 aqueous solution is used as a mild volume of hydrogen peroxide gives on heating. The
antiseptic. Contact of H 20 2 with blood catalyzes its dispro- commercial samples are marked as '10 volume', '15 volume'
portionation into oxygen and water, which cleanses the wound. or '20 volume'. '10 volume' means that one volume of hydrogen
(iv) As it oxidizes unpleasant effluents without producing peroxide on heating gives 10 volume of oxygen at NTP. 10 rnL
any harinful by-products, H 20 2 is widely used as an oxidizing of a '20 volume' solution of H20 2 will liberate 10 x 20 = 200
agent in the control of pollution. mL of oxygen at NTP.
(vi) for restoring colour of old paintings. Sometimes the concentration of H20 2 in a solution is
(v) as an oxidising agent in the laboratory. expressed as percentage of H20 2 in solution, i.e., g/100 mL.
(vi) as 'antichlor' to remove traces of chlorine and Thus, 30% hydrogen peroxide means that 30 g of H 20 2 is
hypochlorite. present in 100 mL of solution. '10 volume' solution of H 20 2
(vii) highly concentrated solution (about 40%) of H20 2 is is 3.035% solution, i.e., 3.035 g of H20 2 present in 100 rnL
used to oxidise petrol, alcohol and hydrazine hydrate for the of the solution. This calculation can be made in the following
propelling of rockets and torpedoes. manner.
NH2·NH2 + 2H 20 2 ~ N2 + 4H 20 2H20 2 ~ 2H20 + O2
The reaction is highly exothermic and is accomp~nied by a 2(2 + .32) 22400 mL
large increase in volume. . = 68 g at NTP
(Vll . 0 f T·4+
.. ).In the detectlOn I ,V5+
a nd er3+ Ions.
.
22400 mL of oxygen is obtained at NTP from
= 68 g of H 20 2
H , H
10 mL of oxygen is obta1nedat NTP from =2;kox 10
)O-tO ~ )0+0
= 0.03035 g HzOz H H
1 mL of H20Z solution contains = 0.03035 g H202 Evid~nce inJavour of Baeyer's formula: (i) Hydrogen
100 mL 0f HZ0 2 solution contains = 0.03035 x 100 peroxide behaves as weak dibasic, acid as one or both the
hydrogen atoms can be' rep1aced't,y univalent basic atoms'
= 3.035 g H 20z forming salts like Na-O-O-;.·:H and Na-O-O--Na
or the solution is 3.035%
(Na202)' This suggests that the one molecule of hydrogen
or concentration or strength of 10 volume of H 20 2 solution
peroxide consists of two hydroxyl groups. ,
=
= 3.035 x 10 30.35 g/litre (ii) Th~ formation of ethylene glycol from ethylene supports
Normality of this solution can be calculated if we know the Baeyer's formula.
equivalent mass of hydrogen peroxide.
=~~x 8 = 17.0
CH
r· ,HO
Equivalent mass of hydrogen peroxide II·· + I ~
HO
[ 2H20z~2H20+021 ~ .
68 g 3Z g It is proposed,' therefore, that hydrogen peroxiqei~ a
tautomeric mixture of two forms in equilibrium.
Number of gram equival~llts in 10 vQ}ume hydrogen peroxide H ",.. '
solution H-O-O--H ~---?) H/'
'" O~
= concentration or strength per litre 30'735 = 1.785
The calculated value of the single bond 0--:-0 distance is
equivalent mass 1
1.48A and X-ray measurements do show that in hydrogen
Normality of 10 volume solution = 1.785 N peroxide, 0--0 bond distance is 1.46 ± 0.03 A. The value of
Similarly, the concentration of '20 volume' hydrogen peroxide dipole moment of HzOz is 2.1 D. This suggests that all the four
solution means 6.070% or 60.70gffitre or 3.57 N. atoms do not lie in the same plane. The molecule can be
Let volume strength is 'V'. pictured as lying on the spine of a book open to an angle of
V litre Oz will be given by 1 litre then at NTP 94 0 • The hydrogen atoms are present one on each cover and
gffitre strength of HzOz =2~~4 x V

H--O bonds making angles of 97° with the 0--0 bond as
shown in Fig. 5.16. The bond distance between O-H is 0.97 A.
N = Strength = 68 Vl17 = Y.
EM 22.4 5.6
i.e., Volume strength = 5.6 x Normality 00 00
Similarly, Volume strength = 11.2 x Molarity o g 0 ~ t\
m Structure of Hydrogen Peroxide

The vapour density as determined by Victor Meyer method
at 90°C is 17. Hence, the molecular mass of HzOz is 34. This
value has been confirmed by depression of freezing point method
also. Thenard found that 17 parts by mass of hydrogen peroxide
gives 9 parts by mass of water and 8 parts by mass of oxygen.
Thus the empirical formula is OH and the molecular formula Fig.5.16 Structure of H202
is HZ02.
Two formulae have been suggested for hydrogen peroxide. Structure of HzOz is slightly different in gas phase and
crystalline phase.
H
H)O~O
1--~----------------1
Baeyer's fonnula
!:
I HI
r2
!:
I
I I
Kingzett's formula I r I
l, 0 1 0 ~61
Evidence in favour of Kingzett's formula: This formula
explains the oxidising properties of H20z as the oxygen linked
'~'
\\
,,
6
\
, 2 \
\
\
\
by coordinate bond is easily lost. \. H \

\_------------------~
Fig. 5.17 Gas phase structure of H20 2
( rl =147.5 pm, rz = 95 pm, 9 1 = IllS, 9 z = 94.8° )
r-H"----------------7 2RCOONa + Mg2+ ~ (RCOOhMg + 2Na+
I
,.
I . ,I
I
I I (ii) Temporary hardness of water is due to the presence of
! r2 /
I
I
I
I soluble bicarbonates of calcium and magnesium. On boiling,
I . ' I
r1 ') the bicarbonates are converted into insoluble carbonates which
O.~'
.... e29.;\~1
I
(\\ can be removed by filtration.

\
\., . ....
-
\
\ Ca(HC0 3h ~ CaC03 + H 20 + C02
\~- '.' ." -.. ' 'H '\
,---_.:------..;....;;-_:...-._---,.,) Mg(HC0 3h ~ MgC0 3 + H 20 + CO2
Soluble Insoluble
Fig. 5.18 Crystalline phase structure of H202 (iii) When water poured over petrol fIre, petrol being lighter
(rl = 98.5 pm, r2 = 145.8 pm, 8 1 = 90.2°, 82 = 101.9°) than water floats over water and fIre spreads instead being
extinguished.
Example 5. Explain the following: (iv) Hard water consists bicarbonates and other soluble
(i) Why hydrated barium peroxide is used in the preparation salts of calcium and magnesium. When hard water is evaporated
of hydrogen peroxide instead of the anhydrous variety? in boilers, scales of precipitated carbonates of calcium and
(ii) Phosphoric acid is preferred to sulphuric acid in the magnesium along with other salts such as sulphates, chlorides,
preparation of H20 2 from barium peroxide. etc., are formed. In order to avoid the formation of scales hard
(iii) Statues coated with white lead on long exposure to water is fIrst softened before use in boilers.
atmosphere turn black and the original colour can be restored
Example 7. Explain the following:
on treatment with H202. lRool"kee 19871
(i) A small amount of acid or alkali is added before
Solution: (i) If anhydrous barium peroxide is used in the
electrolysis of water.
preparation, the barium sulphate, thus formed, forms an insoluble
(ii) The electrolysis of water for trUlnufacturing hydrogen
protective coating on the surface of solid barium peroxide.
gas is always carried out in the presence of acid (H2S04) or
This prevents the further reaction of the acid, i.e., causing the
reaction to stop. If, however, hydrated barium peroxide (in the
alkali (KOB), yet no sot or r ions are discharged.
(iii) A solution of ferric chloride acidified with Hel is
form of thin paste) is used, the water causes to dislodge the
unaffected when hydrogen is bubbled through it, but gets reduced
insoluble BaS04 from the surface of Ba02. BaS04 thus settles
when zinc is added to some acidified solution.
at the bottom of the reaction vessel and the reaction continues
without any difficulty. (iv) When sodium hydride in fused state is electrolysed,
(ii) When phosphoric acid is used in the preparation of hydrogen is discharged at anode.
H 20 2 from Ba02, it plays the double role. It liberates H 20 2 and Solution: (i) Pure water being a weak electrolyte and
also acts as a preservator by retarding its decomposition. feebly ionised is bad conductor of electricity. In order to make
(iii) White lead is used as a pigment. The statues coated with it a good conductor, a small amount of acid or alkali is added
white lead get blackened due to the action of H 2S present in before electrolysis.
atmosphere in traces. (ii) Sulphate and potassium ions are not discharged as the
Pb(OHh-2PbC0 3 + 3H 2S ~ 3PbS + 2C0 2 + 4H 20 discharge potential of SO~- is much higher than OS- ions and
White lead Black the discharge potential of K+ ions is much higher than H+ ions.
When blackened statues are treated with H202, the PbS is (iii) Molecular (ordinary) hydrogen is not so reactive as
oxidised to PbS04 which is colourless (white). hydrogen at the moment of formation. Zinc reacts with the
acid to produce nascent hydrogen which reduces ferric chloride
PbS + 4H 20 2 ~ PbS04 + 4H 20 into ferrous chloride.
White
(iv) Sodium hydride is an electrovalent compound in which
hydrogen is present as an anion, H"". On electrolysis, it is
(i) Soft water lathers with soap but not hard water. discharged at anode.
(ii) Temporary hard water becomes soft on boiling. NaH~Na+ +
(iii) Water can extinguish most fires but not petrol fire.
(iv) Hard water is softened before use in boilers. CathOde/
Solution: (i) Hard water contains calcium and magnesium
salts. These react with soap to form insoluble calcium and
magnesium salts of fatty acids, i.e., form scum and not , , EXample 8. What happens when?
lather.
(a) An alkaline solution of potassium ferri cyanide is reacted
2RCOONa + Ca2+ ~ (RCOOhCa + 2Na+ with H202.
Soap Insoluble
(b) Hydrogen peroxide is added to acidified potassium 254 g of 12 is obtained from 34 g H20 2
permanganate.
(c) Hydrogen peroxide is added to ferrous ammonium sulphate 0.508 g of 12 is obtained from H202 =i5~ x 0.508
solution. [Roorkee 1985] = 0.068 g
(d) Chromium hydroxide is treated with hydrogen peroxide
in the presence of sodium hydroxide. [M.L.N.R. 1992]
5 mL of the solution contains = 0.068 g H2~
(e) Concentrated caustic potash solution is spilled on 0.068
1 mL of the solution contains =-5-· g H202
granulated zinc.
(f) Hydrolith is treated with water. = 0.0136 g H2~
(g) Heavy water reacts with aluminium carbide. 2H202 ~ 2H20 + O2

68g 22400 mL
Solution:
(a) Potassium ferricyanide is reduced to potassium 68g of H20 2 gives oxygen at STP = 22400 mL
ferrocyanide. 0.0136 g of H20 2 will give oxygen at STP
2K3Fe(CN)6 + 2KOH ~ 2~Fe(CN)6 + H20 + 0 22400
= ~x 0.0136
H20 2 + 0~H20 + O2
= 4.48 mL
2K3Fe(CN)6+ 2KOH +H2~~ 2K4Fe(CN)6+ 2H20 + O2
i.e., 1 mL of H202 solution gives 4.48 mL of oxygen.
(b) .Potassium permanganate is decolourised due to So, strengthofH20 2 solution;:;; 4.48 volume.
reduction.
{~Example 10. Calculate the hardness ofwater sample which
2KMn04 + 3H2S04 ~ K2S04 + 2MnS04 + 3H20 +50 ~ontains 0.001 mole ofMgS04 dissolved per litre of water.
[H202 + 0 ~ H20 + O2] x 5 Solution: .
0.001 mole MgS04 = 0.001 x 120 g MgS04
2KMn04 + 3H2S04 +5H202~
K2S04 + 2MnS04 + 8H20 + 502
= 0.120 g MgS04
We know that, 120 g MgS04 == 100 g CaC03
(c) Ferrous ammonium sulphate is oxidised to ferric salt.
So, 0.120 g MgS04 0.1 g CaC03
H202~H20
+0
103 g of water(one litre) contains =0.1 g CaC03
2FeS04 + H2S04 + 0 ~ Fez(S04h + H20
2FeS04 + H2S04 + H20 2 ~ Fez(S04h + 2H20 106 g 0 f water contams OJ x 106
. = 10
3 = 100 g CaC03
(d) Chromium hydroxide is converted into soluble yellow So, the hardness of water = 100 ppm
sodium chromate. Example 11. Aqueous solution of an inorganic compound
[H2~ ~H20 + 0] x 3 (x) shows the following reactions:
2Cr(OHh + 4NaOH + 30 ~ 2Na2Cr04 + 5H20 (z) It decolourises an acidified KMnO4 solution accompanied
by the evolution of oxygen. .
2Cr(OHh +4NaOH +3H2~ ~ 2Na2Cr04 +8H20
(ii) It liberates iodine from an acidified KI solution.
(e) Zinc dissolves in caustic potash solution evolving
(iii) It gives a brown precipitate with alkaline KMn04 solution
hydrogen.
with evolution of oxygen.
Zn + 2KOH ~ K2Zn~ + H2i
Pot. zincate
(iv) It removes black stains from old oil paintings.
(f) Hydrolysis of CaH2 occurs with evolution of H2. Identify, (x) and give chemical equations for the reactions
at steps (i) to (iv). [Roorkee 1993]
CaH2 + 2H20 ~ Ca(OHh + 2H2i
Solution: In reactions (i) and (iii) (x) acts as a reducing
(g) Deuteromethane is evolved. agent while in reaction (ii) it acts as an oxidising agent. Thus,
Al4C3 + 12D20 ~ 4AI(ODh + 3CD4 these reactions indicate that (x) is H20 2 which is further
Heavy water Deuteromethane confrrmed from reaction (iv).
3
Example 9. A 5.0 cm solution of H202liberates 0.508 g (i) 2KMn04 + 3H2S04 + 5H20 2 ~
of iodine from acidified KI solution. Calculate the strength of PurpJe coloured
H20 2 solution in terms of volume strength at STP. [I.I.T. 1995]
Solution: .
Soluble, colourless
H2~ + H2S04 + 2KI ~ K2S04 + 12 + 2H20 .
34 g 2 x 127
=254g
(iii) 2KMn0 4 + 3H202 ~ 2KOH + 2Mn02 + 2H20 + 302

Brown
• •
·0· H~4.80
o
H~H
0
(iv) PbS + 4H202 ~ PbS04 + 4H20 94.8° H
Black White
(b) AlCl3 is a salt of a weak base and a strong acid.
Example 12. Hydrogen peroxide acts both as an oxidising
In normal water, it undergoes hydrolysis.
and as a reducing agent in alkaline solution towards certain
first row transition metal ions. Illustrate both these properties AlCI 3(s) + 3H 20(l) -----7 Al(OHh(s) + 3HC1(aq)
Base Acid
of H 20 2 using chemical equations. [I.I.T.1998]
Solution: Chromium hydroxide is oxidised by H 20 2 in In acidic water, H+ ions react with Al(OHh giving Al3+(aq)
ions. .
presence of NaOH into sodium chromate
3
AlCI (s) Acidified) Al + (a ) + 3Cl- (a )
[H20 2 -----7 H 20 + 0] x 3 3 water q q
2Cr(OHh + 4NaOH + 30 -----7 2Na2Cr04 + 5H20 In alkaline water, Al(0H)3 reacts to form soluble
2Cr(OHh +4NaOH +3H20 2 -----7 2Na2Cr04 +8H20 tetrahydroxo-aluminate complex or meta-aluminate ions
[AlO2"(aq)].
Potassium ferricyanide is reduced to ferrocyanide in presence
of KOH by H 20 2. Al(OHh + OH-(aq) -----7 [Al(OH)4f(aq) or Al02:(aq) + 2H20
2K3Fe(CN)6 + 2KOH -----7 2~Fe(CN)6 + H 20 + 0 AICI3(S) Alkaline) AI02: (aq) + 2H 20(l) + 3Cl-(aq)
water i
H202+ 0--;-:--7 H 20 + O2 1'---&ample -15.' Would you expect the hydrides ofN, O-and-
2K3Fe(CN)6 +2KOH +H20 2 -----7 2~Fe(CN)6+2H20 +02 F to have lower boiling points than the hydrides of their
~:Example 13. (a) A mixture of hydrazine and H 20 2 with
subsequent group members? Give reasons.
Cu(II) catalyst is used a rocket propellant. Why? Solution: On the basis of molecular masses of NH 3,
(b) Can concentrated H2S04 be used for drying H2 gas? H20 and HF, their boiling points are expected to be lower than
Justify. subsequent group member hydrides. However, on account of
(c) The process !H2(g)+e -----7 8-(g) is endothermic high electronegativity ofN, 0 and F, the magnitude of hydrogen
bonding is appreciable in their hydrides, i.e., aggregation of
(IJB =+151 kJ morl), yet salt like hydrides are known. How molecules occurs. Hence, the boiling points of NH3, H 20 and
do you account for this? HF will be higher than the hydrides of their subsequent group
Solution: (a) The reaction between hydrazine and H20 2 members.
is highly exothermic and is accompanied by a large increase in Example 16. What do you understand by (i) electron
the volume of the products. Hence, the mixture is used as deficient (ii) electron precise and (iii) electron rich
rocket propellant. compounds of hydrogen? Provide justification with suitable
N 2H4 (I) + 2H 20 2 (I) cu(ll) N 2 (g) + 4H 20(g) examples.
(b) Concentrated H 2S04 cannot be used for drying H2 gas Solution: (i) The hydrides which do not possess sufficient
as the absorption of moisture by H 2S04 is highly exothermic number of valence electrons to form normal covalent bonds ,
in nature. The heat so produced causes hydrogen to catch fire are termed electron deficient hydrides. Examples are the hydrides
as hydrogen is highly inflammable. of group 13 such as BH3, AlH3; etc. They generally exist in
(c) Alkali and alkaline earth metals combine with hydrogen polymeric fonns.
and form ionic hydrides in spite of the fact that formation I)f (ii) The hydrides which possess exact number of electrons
H- ions is an endothermic process. This is due to the reason to form covalent bonds are termed electron precise hydrides.
that high lattice enthalpy released during formation of solid Examples are the hydrides of group 14 such as CH 4, Si~,
hydride from M+ or M2+ and H- ions is more than needed for GeH 4 , etc.
(iii) The hydrides which have lone pair or pairs of electrons,
the formation of H- ions from H 2.
i.e., have more electrons than required to form normal covalent
Example 14. (a) Compare the structures ojH20 and H 20 2. bonds are termed electron rich hydrides. Examples are the
(b) Do you expect different products in sol~tion when AlCl3 hydrides of group 15, 16 and 17 such as NH3, H 20, HF, etc.
is treated separately with (i) normal water, (ii) acidified water
Example 17. What do you understand by the term non-
. and (iii) alkaline water?
stoichiometric hydrides? Do you expect these types of hydrides
Solution: (a) H20 has a bent structure with HOH bond
to be formed by alkali metals? Justify your answer. '
angle is 104S. H 20 2 has an open book structure with
Solution: The hydrides in which the ratio of the metal and
H-O-O angle equal to 94.8° and dihedral angle equal to
hydrogen is found to be fractional are called non-stoichiometric
IllS in gaseous phase.
hydrides. It is also observed that this fractional ratio is not fixed
Hydrogen and its Compou!1ds 245
but ~arie~s . with .the temPetatUre ~d pres~.ure. S.uch hydrides ~ Alkali metals do 'not form non-stoichiometric hydrides as
are formed by dd_ and I·block elements>'jn these. hydrides; eachSQdium atomlQsisits'valency electron which is accepted
hydrogen atoms occupy holes iQ"tlte Q1etallatti~~ Usu.<.illy,m .»),y:
t
hyi:kogen atom' to foim H- io~. In this way, an ionic
_Jo:-..+ _.
the holes are .not oc;oopied, i.e., some hoies.arw~s· remain
o \_ <t,
~ompound,;N:~,. l:I , 1S formed.

;''' •
vacant and thus, these compounds are non-stoicl1iometric.
aSUMMARY AND IMPORTANT POINTS TO REMEMBER a

1. Hydrogen is the lightest element. Its atom consists of a single (b) Metals like Zn, Fe, Mn, Co, Cr, Sn, etc., decompose steam
proton and a single planetary electron. Hydrogen is the only or hot water forming dihydrogen.
element whose atom does not have neutrons in its nucleus. (c) Reactions of steam on hydrocarbons or coke at high
It has the simplest electronic configuration, lsI. temperatures produce dihydrogen.
2. Hydrogen was prepared by Cavendish in 1766 by the action 1270 K
of acids on metals. It was named 'inflammable air' . Lavoiser C nH2n+2 + nH20 ) nCO + (2n + I)H2
Catalyst
named it hydrogen (hydra = water, gennas = maker) meaning C+H20~ CO+H2
water maker. '--v---'
Water gas
3. Hydrogen is the most abundanfelerrient iIi theumverse'(70%
(d) Water containing a small amount of acid or alkali on
of the universe's total mass). Sun and some other stars
electrolysis in an electrolytic cell produces dihydrogen
consist mostly of hydrogen. Free hydrogen is present in
at cathode. The cathode used is usually of iron and
minute quantity in air, volcanic gases and natural gas. In the
anode usually of nickel. The two electrodes are separated
combined state, it constitutes 15.4% of the earth's crust and
by an asbestos dipbragm.
oceans as water, mineral oil, organic materials such as
(e) Ionic hydrides on hydrolysis with water evolve
hydrocarbons, carbohydrates, fats, proteins, etc. Hydrogen
dihydrogen.
is an essential constituent of all acids and alkalies.
4. Hydrogen shows dual nature. It behaves as electropositive CaH2 + 2H20 ~ Ca(0H)2 + 2H2
element like alkali metals as it can lose the planetary electron. Hydrolith
It also behaves as an electronegative element like halogens (f) The metals which occupy their position above hydrogen
as it can gain one more electron to saturate Is subshell. It is in the electrochemical series such as Zn, AI, Mg, Fe, etc.,
the fIrst member in the periodic table but its position is not react with dil.HCI or diL H2S04 to evolve dihydrogen.
fixed. Sometimes, it is placed with alkali metals in IA subgroup Mn and Mg react with wI. HN0 3 to evolve dihydrogen.
and sometimes with halogens in VIlA (l7th) subgroup. (g) Zn, AI, Sn, Si, Pb react with boiling NaOH or KOH to
S. The atomic form of hydrogen exists only at high tempera- evolve dihydrogen. Uyeno's method is used for military
tures. Normal elemental hydrogen is the diatomic molecule, purposes for rapid and pure production of dihydrogen
called dihydrogen, H2. when scrap aluminium reacts with caustic potash.
The ordinary hydrogen at room temperature is a mixture of
2Al + 2KOH + 2H20 ~ 2KAl02 + 3H2
ortho-form and para-form in the ratio of 3 : 1. The nuclei of
ortho hydrogen spin in the same direction while that of the· (h) Dihydrogen is produced in the laboratory by action of
para hydrogen spin in the opposite directions. dilute H2S04 on granular zinc. The dihydrogen produced
6. Hydrogen exists in three isotopes. It is the only known element contains a number of impurities. To remove these
whose isotopes have the unique mass ratio of 1, 2, 3 dH; impurities, the evolved dihydrogen is passed through
1H;~H). The predominant form is iH (protium). 1H or D three bottles containing AgN03 solution (removes PH3
and AsH3), Pb(CH3COOh solution (removes H2S) and
(Deuterium) is present upto 0.0156% in terrestrial hydrogen, KOH solution (removes CO2, S02 and oxides of nitrogen)
mostly in the form ofHD. Tritium (Tor1 H) is radioactive. It emits respectively.
~-particles and its half life period is 12.33 years. 'The three (i). Pure dihydrogen is obtained· either (i) by carrying
isotopes have same chemical properties but their physical , -. electrolysi~ of barium hydroxide solution using platinum
p!'operties are different due to different atomic masses. .electrodes or nickel electrodes or (ii) by action of water
Deuterium and tritium are used as tracers, bombarding projec- on sodium hydride (NaH) or (iii) by Uyeno's method.
tiles especially in fusion reactions, i.e., in hydrogen bombs. S. Large quantities of dihydrogen are required these days in
7. There are three main sources from which dihydrogen industry for various purposes. About 77% of the industrial
(ordinary hydrogen) may be prepared. These are (i) Water, dihydrogen is produced from petro-chemicals, 18% from coal,
(ii) Acids and (iii) Alkalies. 4% from electrolysis of aqueous solutions and 1% from other
(a) Alkali and alkaline earth metals react with cold water sources.
producing dihydrogen. The reactions are vigorous. To Natural gas mainly consists of methane. Dihydrogen is
minimise the rate of reactions, usually amalgams are used. obtained from natural gas either by partial oxidation or
cracking. Natural gas is mixed with steam and passed over a
catalyst (Ni-Cr alloy) at 1200 K. The CO is converted into regularly with increase in atomic number of the element.
C02 by passing the gases and steam over iron oxide or cobalt Metallic or interstitial hydrides are formed by many d-block
oxide catalyst at 750 K resulting in the generation of mo~ and f-block elements at elevated temperatures. These
H2· hydrides are often non-stoichiometric and have metallic
1200K appearance. They possess reducing properties probably due
CH4 +H2 0 Ni-Cr) CO+ 3H 2 to presence of free hydrogen. These hydrides are used for
the ultrapurification of hydrogen and as hydrogen storage
CH4 Ct<lCking) C+2H2 media.
13. Complex metal hydrides such as ~ and NaBI4 are power-
CO+H 0 750K) CO +H· ful reducing agents and are widely used in organic reactions.
2 FeZ03 2 2
14. Hydrogen has been considered as one of the alternate sources
(C02 is removed by dissolving it in water under pressure of of energy. The advantage of using hydrogen as a fuel is that it is
about 25-30 atmosphere.) environmentally clean. The second advantage with hydrogen
Bosch's process is used to obtain dihydrogen from coke. .is that the heat of combustion of hydrogen per gram is higher
than any other fuel. Our energy needs can be met by gaseous,
C+H20 1273K) CO+H2 liquid and solid hydrogen. However, cheaper methods of
9. Dihydrogen is a colourless, odourless and tasteless gas. production of hydrogen are to be developed and problems in
l storing and transportation are to be tackled.
Hydrogen has high heat of dissociation (436 kJ mor ). This
property is made use of in the atomic torch which generates 15. DihYdrogen has following industrial applications:
temperatures of about 4000 K and is ideal for welding of (a) Synthesis of ammonia
metals of high melting points. It has low melting and boiling (b) Manufacture of methyl alcohol
points. It is only slightly soluble in water. It is diatomic in (c) Hydrogenation of oils
nature and bond length is 74 pm. (d) Manufacture of hydrogen chloride
10. Certain metals like palladium, platinum, iron, etc., can adsorb (e) Production of synthetic petrol
large· quantities of hydrogen. The adsorbed hydrogen is (f) fuy-hydrogen flame
called occluded hydrogen. This property can be used for the (g) Fuel for rockets
purification of hydrogen because only pure hydrogen is (h) With helium, it is used for filling balloons employed for
adsorbed. atmospheric study
11. Dihydrogen is inflammable or combustible gas. However, it 16. Water is most common and abundant compound of
does not help in burning. It burns with blue flame in oxygen hydrogen. Water occupies the major part of the earth. It is
atmosphere forming water. Dihydrogen is not a very active essential to life. 'l\vo-third of human body is water. Water has
element and does not react .readily with other elements. Under the ability to dissolve a number of substances. Water has
suitable conditions, it can be made to combine with metals unique properties. Its transformation from liquid to solid and
and non-metals both. It forms compounds by losing, gaining to gaseous states is easy. Water exists as a liquid under normal
or sharing of its only electron. It shows oxidation states of atmospheric conditions. It exists as a solid below O"C and as
+1,0 and -1. H2 has great affinity for oxygen. Thus, it acts a gas above l00"C. The unique properties in the liquid and
as a reducing agent. The oxides of less electropositive metals solid phase are a result of extensive hydrogen bonding .
such as copper, tin, iron, lead, etc., are reduced to the metals between water molecules. Water molecule forms four
when heated in hydrogen. Numerous substances are H~bonds. Water has a higher specific heat, thermal
hydrogenated in presence of suitable catalysts. conductivity and surface tension than most of the other
12. Dihydrogen forms three types of hydrides : ionic, covalent .liquids. Because of these properties water plays an important
and interstitial. Ionic or salt like (saline) hydrides are formed role in the biosphere. The density of water is maximum at 4°C.
by alkali metals, alkaline earth metals· with exception of ·17. Pure water is colourless, tasteless and odourless. It is neutral
Be .and Mg and some highly electropositive members of in nature, pH of pure water is 7. It reacts with active metals
lanthanide series. These are colourless crystalline compounds . when hydrogen is evolved. It is decomposed by metals like
with electrovalent nature in which hydrogen acts as an anion. Zn, Mg, Fe, etc., when steam is passed over hot metals.
All ionic hydrides react with H20 to produce dihydrogen. Fluorine decomposes water forming ozonised oxygen.
Ionic hydrides are powerful reducing agents. Chlorine decomposes water in presence of sunlight. Acidic
Covalent or molecular hydrides are formed by all the true non- oxides combine with water to form oxy-acids while basic
metals (except zero group elements) and the elements such oxides form alkalies. Water decomposes a number of
as AI, Ga, Sn, Pb, Sb, Bi, Po, etc., which are normally metallic hydrides, carbides, nitrides, phosphides with liberation of
in nature, i.e., p-block elements. In these hydrides, hydrogen hydrogen, acetylene (or methane), ammouia, phosphine,
atoms are covalently bonded to the central atom. The boiling respectively. Water forms hydrates of different types.
points of the simple hydrides of first elements of group 15 18. Oxygen atom in water molecule is sp3 hybridized, four hybrid
(NH3), 16 (H20) and 17 (H2F2) are abnormally high due to orbitals directed towards the comers of a tetrahedron are
intennolecular hydrogen bonding. The boiling points· of formed. Two of the hybrid orbitals having one electron each
remaining hydrides within the group, however, increase overlap with hydrogen atoms and form two sigma bonds.
Thus, the molecule has a bent (V-shaped) structure with a
Hydrogen and its Compounds . 247
bond angle of 104.5". The bond angle is less than the expected alcohol distil over leaving behind the aqueous solution
due to presence of two lone pairs of electrons on two of H202.
uncombined hybrid orbitals. The molecule is polar due to (iii) Electrolytic process: 50% H2S04 solution or equimolar
difference in the electronegativities of hydrogen and oxygen mixture of H2S04 and (NH4hS04 is electfolysed at low
and possesses dipole moment. Water molecules are linked temperature using platinum electrodes and a current of
with each other by hydrogen bonding. high density. Peroxy disulphuric acid (H2S20 g) or
19. Ice has open cage like structure with a number of vacant ammonium peroxy disulphate is formed which on
spaces in the crystal lattice. As a result, the density of ice is hydrolysis gives H20z solution.
lower than that of water. 27. H20z is stored in the vessels of pure aluminium or in stone
20. Water is tested by the following tests: jars in dark. Concentrated solutions of H202 are stored these
(i) A drop of water when added to anhydrous copper days in polythene bottles kept in refrigerators. Small amounts
sulphate, change its colour from white to blue. of stabilizers such as orthophosphoric acid acetanilide or
(ii) Water reacts with calcium carbide to evolve acetylene sodium stannate are added.
which bums with bright flame. 28. Pure H202 is a syrupy liquid. It is soluble in water, alcohol
21. Water is said to be soft if it produces sufficient lather with and ether. Its specific gravity is 1.45. It is injurious to skin. It
soap. Hard water does not form lather readily with soap as it has bitter taste. Hydrogen bonding is present, thus it is an
forms an insoluble scum. Hardness of water is of two types: associated liquid.
(i) Temporary: This is due to presence of bicarbonates 29. It decomposes on standing and heating. Presence of traces
of calcium and magnesium. It can be easily removed of MnOz, carbon, alkali or finely divided metals like Pt, Au,
by boiling or by adding slaked lime; Ag, etc., accelerate its decomposition. The pure liquid~has--
(ii) Permanent: It is caused by the presence of chlorides weak acidic nature. Ka = 1.55 X 10-12 . It is less acidic than
and sulphates of calcium and magnesium. Many carbonic acid, i.e., H2C03 > H20 2 > H20. It acts as an
substances can be used for the removal of permanent oxidising agent as well as a reducing agent both in the acidic
hardness. Those are termed water softeners. The as well as in the basic medium.
various water softeners are:
(0 Washing soda (ii) Permutit-hydrated silicates of H202 + 2H+ + 2e ~ 2H20 (In acidic medium)
aluminium and sodium (Na2Al2Si20S·XH20) (iii) Calgon- 2 2 + 2e
Oxidising nature { H 0 ~ 20H- (In alkaline medium)
sodium hexa-meta-phosphate (NaP03)6 (iv) Ion- H20z ~ 2W +02 +2e
22.
exchange resins.
Degree of hardness is defined as the number of parts of calcium
carbonate or equivalent to calcium and magnesium salts
present in million parts of water by mass. It is expressed in ppm.
Reducing nature
l
H20 2 + 20H- ~
(In acidic medium)
2H20 + O2 + 2e
(In alkaline medium)
23. Heavy water (D20) was discovered by Urey. One part of 30. H20z acts as a bleaching agent for delicate articles like hair,
heavy water is present in 6000 parts of ordinary water. It is silk, wool, ivory, etc. The bleaching action is due to oxidation
obtained by repeated electrolysis of water containing alkali. by nascent oxygen and hence is permanent.
Like ordinary water, it is also colourless, odourless and H202 ~ H20 + [0]
tasteless. Nearly all the physical constants are higher than
the corresponding values of ordinary water. It is used as a 31. H20 2 is a valuable antiseptic and germicide for washing
moderator in nuclear reactors. wounds teeth and ears under the name perhydrol. It is used
24. Hydrogen peroxide was discovered by Thenard on treating for restoring colour of old paintings as it oxidises black PbS
barium peroxide with sulphuric acid. It was called oxygenated to PbS04. Highly concentrated solutions (about 40%) of
water. . H20 2 are used to oxidise petrol, alcohol, hydrazine hydrate
25. HZ02 is prepared by adding ice cold dilute H2S04(20%) on for the propelling rockets and torpedoes.
Na20z or Ba02' As H2S04 catalyses the decomposition, some 32. X-ray measurements show that bond distance between
weaker acids such as H3P04 or H2C03 (H20 + CO2) are 0-0 is 1.46 ± 0.03 A. The value of dipole moment is 2.m.
preferred. This suggests that H202 molecule is a non-linear molecule.
26. Manufacture of H20 2 is done by following methods : In gas phase, the molecule can be pictured as lying on the
(i) Auto-oxidation of 2-butyl anthraquinol. It is the most spine of the book open to an angle of IlLS". The hydrogen
recent method. 2-butyl anthraquinone is catalytically atoms are present on each cover and LOOH = 94.8".
reduced to 2-butyl anthraquinol in an organic solvent 33. Strength of the sample of hydrogen peroxide is generally
in presence of palladium by passing hydrogen. It is then expressed in terms of volume of. oxygen at NTP that one
oxidised by passing air. The H20 2 is extracted with water volume of hydrogen peroxide on heating gives. The commer-
to give a 20% solution. 2-butyl anthraquinone is cial samples are marked as '10 volume', '15 volume' or '20
reformed which is again used. volume'. '10 volume' solution means that one volume ofH20 z
(ii) By oxidation of isopropyl alcohol: The isopropyl gives 10 volume of oxygen at NTP on decomposition.
alcohol is mixed with a small amount of H 20 2 and Sometimes the concentration of H202 is· expressed as
oxygen is passed at 7O"C. Acetone and unreacted percentage of H202 in solution, i.e., g 11 00 mL. 30% hydrogen
peroxide means that 30 grams of H202 is present in 100 mL Normality of '10 volume' H20z solution 1.785=
of solution. i.e., Volume strength = 5.6 x Normality
'10 volume' solution ofH202 is 3.035% solution. S~ly =
Volume strength 11.2 x Molarity.
Strength of '10 volume' H2dz solution is 30.35 gIlitre. = =
1M H202 2N H 20 2 11.2 volume H202 3.4% =
r- ••• - PRACTICE PROBLEMS r- ~._._-

• Subjective Type Questions (xiii) What is the difference between the rates of reactions
of D20 and H20z ?
1. Answer the following: (xiv) How heavy water is obtained from ordinary water?
(a) Which isotope of hydrogen contains equal number of (xv) Why has D 20 more density than H20?
protons and neutrons? (xvi) What chemical change does occur when temporary
(b) What is Syn. gas? hard water is boiled?
(c) Name two complex metal hydrides which are used as (xvii) What is calgon?
reducing agents in organic reactions. (xviii) What type of overlapping of orbitals occur in the
(d) What is hydride gap? formation of peroxo linkage (-0-0-) in H20 2
(e) What is autoprotolysis of water?
molecule?
(f) What common coinpounds ofhy<lrogen are more powerful
(xix) Name the chemical compound used in the preparation
reducing agents than hydrogen itself?
of H202 by auto-oxidation.
2. (a) Which is heavier, ice or water?
(xx) Name the blue coloured compound formed in the
(b) What is deionised water? Can distilled water be called as
reaction of H202 with acidified K2Cr2~ in ether.
deionised water?
(xxi) How H 20 2 acts as an antiseptic?
(c) What name is given toa water softener, sodium poly-
(xxiI) What volume of oxygen at NTP is obtained from 10
metaphosphate?
mL of 10 volume H 20 2?
(d) What gases are evolved when the following react with
water? (xxiii) What is the principle in bleaching action of H20z?
(i) Mg~2 (ii) Cac2 (iii) Ca3P2 (xxiv) How is concentration of H20 2 done?
3. (a) Give three characteristics in which hydrogen resembles (xxv) Which acts as an oxidising agent in the reaction of
halogens. H202 and 03?
(c) Give three characteristics inwhich hydrogen resembles 5. What happens when?
alkali metals. (a) An alkaline solution of potassium ferricyanide is treated
(c) Give four industrial uses of hydrogen. with hydrogen peroxide. [I.I.T. 1989]
4. Answer the following: (b) Chromium hydroxide is treated with hydrogen peroxide
(i) In which group of the periodic table, hydrogen is in the presence of NaOH. [M.L.N.R. 1992]
, placed? (c) Concentrated solution of NH~S04 in H2S04 is
. (ii) Which metals react with H 20 or dilute HCI or dilute electrolysed using current of high density.
H2S04 to evolve hydrogen? (d) Hydrazinereacts with hydrogen peroxide.
(iii) Very pure hydrogen is obtained with rapidity by the (e) Be~eneis treated with H202 in presence of FeS04.
action of caustic potash on scrap aluminium. What is (f) Lactic acid is treated wuq Fenton's reagent.
the name of this method? (g) Tin tetrabalide is treated wIth lithium aluminium hydride.
(iv) Which zinc. (pp.i:-e or commercial) is used for the (h) Sodiuin hydride reacts with diborane.
preparation of hydrogen in laboratory? . (i) Hydrogen peroxide reacts with Ba(0H)2'
(v) Which solution is used f9l" 'the removal of AsH3 and (j) Sodium hypochlorite reacts with H202.
., PH3 present in very Sn;l~ amounts in hydrogen 6. (i) Give two reactions in each case to show that H202 .
sample? behaves as,
(vi) How is hydrogen obtained from natural gas? (a) an acid, (b) a reducing agent, (c) an oxidising agent.
(vii) What type of hydrides are formed by the elements (ii) Mention one catalyst in each case..
having low electronegativity? (a) Which retards H20z decomposition.
(viii) What is the temperature of oxy-hydrogen flame? (b) Which accelerates H202 decomposition.
(Ix) What is percentage of ortho form in ordinary hydrogen 7. (i) Name the isotopes of hydrogen.
at room temperature? (ii) How many protons, neutrons and electrons are present
(x) Which form of hydrogen is used for welding purposes? in the isotopes of hydrogen?
(xi) Which isotope of hydrogen is radioactive in nature? (ill) What is the molecular mass of heavy water? Give one
(xii) What is the use of heavy water in nuclear reactors? chemical reaction only for the preparation of deuterium
from heavy water.
(iv) Give two uses of heavy water.
(v) Write two important uses of heavy hydrogen. NUMERICAL PROBLEMS
(vi) How many different combinations of water are possible
from 1HI, 1H2, 1H3 and 8016'8017 and 8018? 1. What mass of CaO will be required to remove the hardness
(vii) How does heavy water react with the following? of 1OOOlitres of water containing 1.62 g of calcium bicarbonate
per litre?
(a)CaC2 (b) Mg3N2 (c) P20 S (q) H2S04 [Hint : Ca(HC03h + CaO -----7 2CaC03 + H20 + C~]
8. Write short notes on: 162g 56g .
(i) Nascent hydrogen [ADs. 5.6 x Ht g]
(li) Atomic hydrogen 2. 100 mL of tap water containing Ca(HC03h was titrated with
(iii) Ortho- and para- hydrogen NI50 HCl with methyl orange as indicator. If 30 mL of HCI
(iv) Bosch's process were required, calculate the temporary hardness as parts of
(v) Lane's process (vi) Calgon CaC03 per 106 parts 8f water.
(vii) Permutit method of softening water . [Hint : 30 mL NISO HO == 30 mL NI50 Ca(HC03h ,..
(viii) Ion-exchange method for removal of hardness of water == 30 mL NI50 CaC03 == 100 mL tap ~ater
(ix) Industrial applications of hydrogen . .' ExNxV
Mass of CaC03 in 100 mL tap water =. 1000
(x) Strength of hydrogen peroxide .
(Xl) Zeolite " 50x30
9. Explain thefollowing:
= 50xl000
[ADs. Hardness = 300 ppm]
(i) Why are the melting and boiling points of D 20 are
higher than those of ordinary water? 3. 20 mL of H202 after acidification with dilute H2S04 required
(li) Presence of water is avoided in the preparation ofH20 2
30 mL of NIl2 KMn04 for complete oxidation. Calculate the
percentage of H202 in the solution. Equivalent mass of
from Na202'
(iii) A mixture of hydrazine and H20 2 is used as a rocket-
H 20 2 =17.
propellant. [Hint : 30 mL .~ KMn04 ;;;; 20 mL NxH202 ...
(iv) Hydrogen peroxide acts as an oxidising agent as well
N ali f 30· 1
onn ty 0 H20 2 soln., Nx = 12 x 20= 8
as a reducing agent. . [I.I.T. 1992]
(v) Hydrogen peroxide gives acidic properties. . l ' .
10. The following statements are true under certain conditions.
Strength =Nonnality x Eq. mass =gX 17 =2.1~.~gL-l .
Mention the condition in each case in a few words. 2.125 - ]
. % = 1000 x l00·:=~.2125
(i) Hydrogen reacts with oxygen to form water.
(n) Hydrogen reacts with nitrogen to form ammonia. 4. 25 mL of hydrogen peroxide solution were added to ~;cess' of
(iii) Hydrogen can be prepared from water at ordinary
acidified potassium iodide solution. The iodine so liberated
~uired 20 mL ofO.l N sodium thiosulphate solution. Calculate
temperatures.
(iv) A metal will liberate hydrogen by its reaction with dil. strength in terms of normality, percentage and volume.
[M.L.N.R. 1996]
H2SO4' [Hint : Let the nonnality of H202 soln. be N;<-
(v) The unsaturated hydrocarbon, ethylene, is saturated
,20 mL 0.1 N Na2S203 20% mL 0.1 N 12
to ethane by hydrogen.
= 25 mL Nx H202
• Matching Type Questions . Nonnality of H 0 N
. 22, x
x 0.1 = ~
= 2025 25 = 008
.
Match the following: Strength = Eq. mass x nonnality
(a) Manufacture of Hydrogen (i) Boron hydride = 17 x 0.08 = 1.36 gL- 1
(b) Ionic hydride (n) Oxide of heavy . . Percentage = 0.136
h~drogen ." 68 g H20 2 give oxygen at NTP = 22400 mL
(c) Preparation of H20 2 (iii) . Ant;:septic and . 22400
I' :
0.00136 g H20 2 gIve oxygen at NTP =~ x 0.00136
germicide
• :;;(d) Electron deficient hydride (iv) An artificial zeOlite = 0.448 mL
1 mL of H202 solution ~ves 0.448 mL oxygen.]
. ':(e) Hard water . (v) Mercks' process
(t) Heavy water (vi) Bosch's process 5. What is the volume strength of a molar solution of hydrogen
(g) Permutit (vii) Hydrolith peroxide?
(h) Perhydrol (viii) Scale in boilers [Hint : 1 molar solution consists 34 g H20 2 per litre.]
[Ans. 11.2 volume] .
6. Calculate the mass of H20z present in 600 mL of a 10 volume 8. Calculate the volume strength of a 5 N hydrogen peroxide
hydrogen peroxide solution. solution.
[ADS. 18.2 g] [Hint : 5 N solution consists 85 g H 20 2 per litre.]
7. 10.2 g of pure H202 are heated strongly till completely [ADS. 28 volume]
decomposed. Calculate the volume of oxygen evolved at 27°C 9. There is a sample of 10 volume of hydrogen peroxide solution.
and 740 mm pressure. Calculate its strength in (i) per cent of hydrogen peroxide and
[ADS. 3792 mLl (ii)grams of H 20 2 per litre.
[ADS. 3.035%, 30.35 gL-1] {M.L.N.R.lmJ
Answers : Subjective Type Questions (xxii)100 mL.

1. (a) Deuterium (xxiii)Oxidising nature.
(b) It is a mixture of CO and H 2. (xxiv) Concentration is done by vacuum distillation.
(c) LiAlH4 and NaB~. (xxv) 03 acts as an oxidising agent while H20 Z acts as a reducing
(d) Elements of groups 7,8 and 9 do not form hydrides and even the agent, HzOz+ O(given by 0 3) ----*HzO + 02'
elements of group 6 except chromium do not form hydride. This 5. (a) Potassium ferricyanide is reduced.
region of periodic table from group 6 to 9 is termed hydride gap. 2K3Fe(CN)6 + 2KOH + H 20z ----* 2~e(CN)6 + 2H20 + O 2
(e) Autoprotolysis of water means self ionisation of water. (b) Cr(OHh is converted into yellow co)oure~.t:'l~f<::rOL._
H 20 + H 20 ~ H30+ + OH- 2Cr(OHh + 4NaOH + 3H20 2 ----* 2Na2Cr04 + 8H20
(f) The saline hydrides (c) NH~S04 ~ if + NH4S0'4
2. (a) Water (b) Water free from all types of cations and anions is At anode :. 2NH4S04 ----* <NH4hS20s + 2e-
called deionised water. Yes. Ammonium
(c) Calgon (d) (i) NH3 (li) C2H 2 (iii) PH3 peroxydisulphate
4. (i) No fixed position, sometimes placed in IA with alkali metals At cathode. 2W + 2e- ----* H2(g)
and sometimes in VITA (or 17th) group with halogens. (d) Hydrazine is oxidised to N z and H20
(li) Metals having positive oxidation potential values or placed N z14 + 2H20z ----* N2 + 4H20
above hydrogen in the electrochemical series evolve hydrogen (e) Benzene in presence of FeS04 is converted into phenol.
with water or dilute HC) or dilute H2S04.
CJi6 + H202 ----* C~50H + H 20
(iii) Uyeno method,
(f) Lactic acid is oxidised to pyruvic acid
2Al + 2KOH + 2H20 ----* 2KAIOz + 3Hzi FeS04
CH3CHOHCOOH + H20z ~ CH3COCOOH + 2HzO
(iv) Commercial zinc.
(v) AgN03 solution. (g) Tin hydride is formed.
(vi) Either by partial oxidation or cracking. SnC4 + LiAll4 Ether) SnH4 + LiCl + AlCl3
(vii) Ionic hydrides. (h) Sodium borohydride is formed.
(viii) 2800°C;
B2~ + 2NaH ----* 2NaB~
(ix) 75. (i) HZ0 2 + Ba(OHh ----* BaOz + 2H20
(x) Atomic hydrogen.
(j) NaOCI + HZ0 2 ~ NaCl + HzO + O 2
(xi) Tritium.
6. (i) (a) Na2C03 + H20 2 ~ Na20z + H 20 + CO2
(xii) Heavy water is used as a moderator. It slows down the speed
2NaOH + H20z ~ Na202 + 2HzO
of fast neutrons.
(b) 0 3 + H202 ~ 20z + H20
(xiii) The rates of reactions of D20 are slower than H20.
Ag20 + H202 ~ ZAg + H20 + 02
(xiv) By exhaustive electrolysis of ordinary water.
(xv) The density of heavy hydrogen is twice that of hydrogen,
(c) H2S + H20Z ~ S + 2H2,?
PbS + 4H20 2 ~ PbS04 + 4H20
hence the density of D20 is more than H 20.
(li) The decomposition of H 20z is retarded by orthophoSphoric
(xvi) Bicarbonates of Ca and Mg (soluble) are converted into
acid while it is accelerated by presence of alkali or finely divided
insoluble carbonates.
metals like Pt. Ag, Au, etc.
Ca(HC03h ----* CaC0 3 + H 20 + CO2 7. (i) Three isotopes (a) Protium (b) Deuterium (c) Tritium
(xvii) It is a complex salt used as water softener. It's chemical name (li) I proton 1 proton 1 proton
is sodium hexatnetaphosphate, Na2[N~(~)61. 1 electron I electron I electron
(xv'Ji) pop overlapping. no neutron I neutron 2 neutrons
(xix) Anthraquinone. (iii) 20; 3Fe + 4D20 ----* F~04 + 4D2
(xx) crOs, chromium peroxide, (iv) (a) As a moderator (b) for the production of deutero compounds ..
Ether .
K2CrZ07 + 4HzOz + HZS04--~ K2S04+2CrOs+5H20 (v) (a) For tracer studies (b) for fusion reactions.
(xxi) H20z gives nascent oxygen that kills bacteria. (vi) 18
(vii) (a) CaC 2 + 2D2O ~ Ca(ODh + CZD2 H20 2 + 2H++ 2e- ~ 2H zO (acidic medium)
(b) MgiN2 + 6D 2O ~ 3Mg(ODh + 2ND3 H20 2 + 2e- ~ 20H- (alkaline medium)
Reducing agent:
(c) P20 S + 3D2O ~ 2D 3P0 4
H 20 Z ~ 2H+ + 02 + 2e-
(d) H2S04 + D20 . ~ D2S04 + H2O
(v) H20z reacts with bases to form peroxides (salts) and water
9. (i) D 20 has more molecular mass and greater degree of association 2NaOH + H20 2 ~ NaZ02 + 2HzO
than Hi) and thus shows higher m.pt. and b.pt.
Ba(OH)z + H202 ~ Ba02 + 2HzO
(ii) Water reacts with NaZ02 to produce NaOH which increases 10. (i) On electrical sparking; (ii) At elevated temperature
the decomposition of HzOz. (500-550°C) and high pressure (200 atm.) in presence of a catalyst;
(iii) The reaction is highly exothermic. It brings large increase in (iii) By electrolysis or by the action of some metal like sodium in
the form of amalgam; (iv) Provided the position of the metal is
volume also. above hydrogen in the electrochemical series; (v) In the presence
Nz~ + 2HzOz ~ Nz(g) + 4H20(g) of a catalyst at elevated temperatures.
(iv) This is due to the following reactions.
Answers : Matching lYpe Questions
Oxidising agent:
(a-vi); (b-vii); (c-v); (d-i); (e-viii); (f-ii); (g-iv); (h-ili)
-1ttUSTRATfONS-7"OF" OBJECTIVE QUESTIONS

1. An inorganic substance liberates oxygen on heating and [Hint : The reaction in which hydrogen accepts the electron or
turns an acidic solution of KI brown and reduces acidified its oxidation number changes from 0 to -I, it acts as an
oxidising agent. 2Na + Hz ~ 2Na+ Jr.]
KMn04 solution. The substance is :
(a) HgO (b) H2Ch 5. When H 20 2 is added to ice cold solution of acidified
(c) KN~ (d) Pb(N~h potassium dichromate in ether and the contents are shaken
ADS. (b) and allowed to stand:
(a) a blue colour is obtained in ether due to formation of
[Hint : 2H20z Hea\ 2H20 + O 2 ;
Cr2(S04h·
2KI + HZ0 2 ~ 2KOH + 12 ; (b) a blue colour is obtained in ether due to formation of
Brown 005,
Acidified KMn04 acts as an oxidising agent when it is (c) a blue colour is obtained in ether due to formation of
decolourised, H20 2 + 0 -~ H20 + O2.]
003-
2. The volume strength of 10 N H 202 is : (d) chromyl chloride is formed.
(a) 112 (b) 11.2 ADS. (b) ,
(c) 0.112 (d) 56 [Hint : CrzO~- + 2W + 4Hz0 2 ~ 2CrOs + 5H20]
, Blue colour
ADS. (d) in ether
[Hint : Volume strength = 5.6 x normality] 6. Mass percentage of deuterium in heavy water is :
3. In which of the properties listed below, hydrogen does not (a) same as that of protium in water
show similarity with halogens? (b) 11.1
L Nature of the oxide (c) 20.0 (d) cannot be predicted
n. Electropositive character ADS. (c)
m. Combination with aIkali metals [Hint: The formula of heavy water is DzO, i.e., molecular mass
= 20
N. Atomicity
(a) I and IT (b) III and IV (c) IT only (d) I and III % of deuterium 20 ]
ADS. (a) 7. 2 g of aluminium is treated separately with excess of dilute
[Hint: Hydrogen forms a neutral oxide, i.e., H20 (water) while
H2S04 and excess ofNaOH. The ratio of volumes of hydrogen
the oxides of halogens are acidic. Hydrogen shows
electropositive nature also while halogens are mostly evolved under similar conditions of pressure and temperature
electronegative in nature.] is :
(a) 2: 3 (b) 1: 1 (c) 2: 1 (d) I: 2
4. In which of the following reactions does hydrogen act as an
ADS. (bj
oxidising agent?
(a) H2+F2~ (b) H2+SiC4~
(c) Na+H2~ (d) CuO+H2~
2Al + 2NaOH + 2H20 ~ 2NaAlOz + 3Hz
Ans. (c) Thus, ratio of volumes of hydrogen evolved is I: 1]
8. In which reaction, hydrogen peroxide neither acts as an

oxidising agent nor as a reducing agent? + 2H20 + 02
(a) PbS + H2~ ---:t (b) S03 + H2~---:t Mn(OHh is oxidised by H20 2 in alkaline medium.
(c) Pb02 +H20 2 ---:t (d) Na2C03 + H20 2---:t Mn(OHh + H202 ----7 Mn02 + 2H20]
ADs. (d) 12. When a substance. A reacts with w~er, it produces a
[Hint : Hi02 behaves as an acid when reacts with Na2C03' combustible gas B and a solution of substance C in water. D
Na2C03 + H202 ----7 Na202 + C~ + H20] reacts with this solution of C and produces the same gas B
9. Which one of the following reactions does not form gaseous on warming. D can also produce gas B on reaction with dilute
product? . H2S04. A imparts a deep golden yellow colour to smokeless
(a) Pb02 + H202---:t (b) PbS + H202---:t flame. A, B, C and D respectively are :
(c). Cl2 + H20 2---:t (d) Na2C03 + H20 2---:t (a) Na, H2, NaOH, Zn (b) K, H2, KOH, AI
Ans. (b) (c) Ca, H2, Ca(OH)z, Sn (d) CaC2, CzH2, Ca(OH)z, Fe
[Hint : PbS + 4H202 PbS04 + 4H20] Ans. (a)
(Solid) (Liquid)
[Hint : 2Na + 2H 20 ----72NaOH +
10. What is the degree of hardness of a sample of water (A) (C)
Gives golden yellow
containing 24 mg of MgS04 (molecular mass 120) per kg of colour to flame
water?
Zn + H 2S0 4 ----7 ZnS04 + H2 ]
(a) lOppm (b) 15ppm (c) 20ppm (d) 25ppm (D) Dilute (B)
Ans. (c)
[Hint : 24 mg of MgS04 present in 103g of water 13. Polyphosphates are used as water softening agents because
they:
106g water will contain = 24000 mg of MgS04 = 24 g of
MgS04 (a) form soluble complexes with anionic species
120 g of MgS04 = 100 g of CaC03 (b) precipitate anionic species
(c) form soluble complexes with cationic species
So, 24 g of MgS04 = 100
120 X24 = 20 gof CaC03 (d) precipitate cationic species
Hardness of water = 20 ppm] Ans. (c)
11. In alkaline medium, H20 2 reacts with Fe3+ and Mn2+ 14. What is false about H20 2?
separately to give: [J,E.E. (Orissa) 2006] (a) Acts both as oxidising and reducing agent
(a) Fe4+ and Mn4+ (b) Fe2+ and Mn2+ (b) Two OH bonds lie in the same plane
(c) Pale blue liquid
(c) Fe2+ and Mn4+ (d) Fe4+ and Mn2+
(d) Can be oxidised by 0 3.
Ans. (c)
Ans. (b)
[Hint: K3Fe(CN)6 is reduced by H202 in alkaline medium.
[Hint: Two OH bonds lie in the different planes.]
... -
I OBJECTIVE......QUESTIONS -
Set I: This set contains questions with one correct answer.
1. Hydrogen has the tendency to gain one electron to acquire 14. Heavy water is qualified as heavy because it is: '
helium configuration, in this respect it resembles: (a) a heavy liquid 0
(a)a1kalimetals 0 (b) carbon 0 . (b) an oxide of a heavier isotope of oxygen 0
(c) a1kaIine earth metals 0 (d) halogens 0 (c) an oxide of deuterium 0
2 Pure hydrogen is obtaitied by carrying electrolysis of: (d) denser than water 0
(a) water containing H2S04 0 15. Both temporary and permanent hardness in water is removed
(b) water containing NaOH 0 by:
(c) Ba(OH)z solution 0 (a) boiling 0 . (b) filtrationd'~:>~ ~ ....
(d) KOH solution 0 (c) distillation 0 (d) decantation O..
3. In Bos~h's proc~s which gas is uti'ised for the production 16. Both temporary and permanent hardness is removed on
of hydtogen? : . I . boiling water with:
(a) Producer gas· 0 (b) Water gas ..' 0 (a) Ca(OHh 0 (b) Na2C03 0
(c) Coal gas 0 (d) Natural gas 0 (c) CaCo3 0 (d) Cao 0
4. In which property listed below hydrogen does not resemble 17. Temporary hardness is caused due to th~presence of:
a1kali metals? (a) CaS04 0 (b) CaCl2 0
(a) Nature of oxide 0 (c) CaCo3 0 (d) Ca(HC~h 0
(b) Reducing nature . 0 18. Permutit is:
(c) Tendency to form cation 0 (a) hydrated sodium aluminium silicate 0
(d) Presence of one electron in valence shell 0 (b) sodium hexametaphosphate 0
5. Adsorbed hydrogen by palladium is known as: (c) sodium silicate 0
(a) atomic 0 (b) nascent 0 (d) sodium meta-aluminate 0
(c) occluded 0 (d) heavy 0 19. Calgon is an industrial name given to:
6. The conversion of atomic hydrogen into ordinary hydrogen (a) normal sodium phosphate 0
is: (b) sodium meta-aluminate 0
(a) exothermic change 0 (b) endothermic change 0 (c) sodium hexametaphosphate 0
(c) nuclear change 0 (d) photochemical change 0 (d) hydrated sodium aluminium silicate 0
7. The gas used in the hydrogenation of oils in presence of 20. Which of the following is not a water softener?
nickel as a catalyst is: (a) . Calgon 0 (b) Permutit 0
(a) methane 0 (b) ethane 0 (c) Na2C03 0 (d) NaZS04 0
(c) ozone 0 (d) hydrogen 0 21. When the same amount of zinc is treated separately with
8. The isotopes of hydrogen known is/are: excess of sulphuric acid and excess of sodium hydroxide, the
(a) 4 0 (b) 3 0 ratio of volumes of hydrogen evolved is:
(c) 2 0 (d)l 0 (a) 1: 1 0 (b) 1 : 2 [l
9. Tritium contains...... neutron/neutrons. (c) 2: I 0 (d) 9: 4 0
(a) 4 0 (b) 3 o ~. The temporary hardness of water due to calcium bicarbonate
(c) 2 0 (d) 1 o can be removed by adding:
10. Tritium undergoes radioactive decay giving: (a) Caco3 0 (b) CaClz 0
(a) IX-particles 0 (b) ~-particles o (c) HCl. 0 (d) Ca(OH)z 0
(c) neutrons 0 (d) y-rays o 23. Which elements out of the following do not produce
1L The decay product of tritium is: hydrogen on treatment with caustic soda?
(a) iH' 0 (b) 1H o (i) Zn (ii) Sn (iii) Cu (iv) Ca (v)A1
(c) ~He 0 (d) 1He o (a) (i) and (v) 0 (b) (iii) and (iv) 0
12. Deuterium differs from hydrogen in: (c) (ii) and (iv) 0 (d) (iv) and (v) 0
(a) chemical properties 0 (b) physical properties 0 24. The exhausted permutit is generally regenerated by perco-
(c) both physical and chemical properties 0 lating through it a solution of:
(d) radioactive properties 0 (a) sodium chloride 0 (b) calci.umchloride 0
13. In which of the following reactions does hydrogen act as (c) magnesium chloride 0 (d) barium chloride 0
an oxidising agent? 25. The oxide that gives H202 on treatment with a dilute acid is:
(a)· Hz + F2---7 o (b) CHz=CHz + H Z---7 0 (a) PbOz 0 (b) MnO" 0
(c) PbO + Hz ---7 o (d) Ca + H2---7 0 (c) NazOz 0 (d) TiOz 0
'2fi Hydrogen gas will not reduce: (c) reducing agent 0

(a) heated cupric oxide 0 (b) heated feme oxide 0 (d) none of the above 0
(c) heated stannic oxide 0 (d) heated aluminium oxide 0 41. Which hydride is called alanate ?
27. Heavy water is: (a) CaH2 0 (b)LiAll:4 0
(a) Hz{) 0 (b) DzO 0 (c) NaB~ 0 (d) AlH3 0
(c) water at 4°C 0 42 The volume of '10 vol.' of H202 required to liberate 500 mL
(d) water obtained by repeated distillation 0 02 at NTP is:
28. The sum number of neutrons and protons in one of the (a) SOmL 0 (b) 25mL 0
isotopes of hydrogen is: (c) l00mL 0 (d) 125mL 0
(a) 3 0 (b) 4 0 43. Hydrogen peroxide has a:
(c) 5 0 (d) 6 0 (a) linear structure 0
29. A commercial sample ofH202 is labelled as '15 volume'. Its (b) closed chain structure 0
percentage strength is nearly: (c) closed book type structure 0
(a) 1% 0 (b) 4.5% 0 (d) half open book type structure 0
(c) 10% 0 (d) 90% 0 44. Hydrogen peroxide does not:
30. The decomposition of H202 can be slowed down by the (a) liberate iodine from KI 0
addition of small amount of phosphoric acid which acts as: (b) turn the titanium salt yellow 0
(a) stopper 0 (b) detainer 0 (c) give silver peroxide with moist silver oxide 0
(c) inhibitor 0 (d) promoter 0 (d) tum the mixture of aniline, KCI03 and dil. H2S04 violet
3l. The colour of hydrogen is: 0
(a) yellow 0 (b) orange 0 45. Hydrogen peroxide was for the ftrst time prepared by:
(c) red 0 (d) none 0 (a) Priestley 0 (b) Thenard 0
32. Hydrogen is evolved by the action of cold dilute HN03 on: (c) Gay-Lussac 0 (d) Bernard 0
(a) Fe 0 (b) Cu 0 46. Hydrogen peroxide is a:
(c) Mg 0 (d) AI 0 (a) liquid 0 (b) gas 0
33. Hard water is not fit for washing clothes because: (c) solid 0 (d) semi-solid 0
(a) it contains Na2S04 and KCl 0 47. Hydrogen peroxide is:
(b) it gives precipitate with soap 0 (a) in the form of a dilute solution 0
(c) it contains impurities 0 (b) in pure form 0
(d) it is acidic in nature 0 (c) in impure form 0
34. Hydrogen peroxide is not: (d) in gaseous state 0
(a) a reducing agent 0 (b) an oxidising agent 0 48. When 50% solution of H2S04 is electrolysed by passing a
(c) a dehydrating agent 0 (d) a bleaching agent 0 current of high density at low temperature the main products
35. In the laboratory H202 is prepared by the action of : of electrolysis are:
(a) cold dilute H2S04 on hydrated Ba02 0 (a) oxygen and hydrogen 0
(b) dil. HCI on Mn02 0 (b) H2 and peroxy disulphuric acid 0
(c) cold H2S04 on Mn02 0 (c) H2 and S02 0
(d) aqueous alkali on Na20z 0 (d) 02 and peroxy disulphuric acid 0
36. Which of the following hydride is most 'volatile? 49. Which one of the following reactions shows oxidising
(a) Hydrolith 0 (b) Oxidane 0 nature of H20 2?
(c) Sodium hydride 0 (d) Azane 0 (a) H20 2 + 2KI ---7 2KOH + 12 0
37. The bleaching properties of H20 2 are due to its: (b) CI 2 + H20 2---7 2HCI + O2 0
(a) reducing properties 0 (b) oxidising properties 0 (c) H202 + Ag 20 ---7 2Ag + H20 + 02 0
(c) unstah!e nature 0 (d) acidic nature 0 (d) NaCIO + H20 2---7 NaCI + H20 + 02 0
38. For the bleRching of hair, the substance used is: ~. Ortho and Para hydrogen differ:
(a) SOz 0 (b) bleaching powder 0 (a) in the number of protons 0
(c) H20z 0 (d) 0 3 0 (b) in the molecular mass 0
39. The reaction, H2S + H202 -? S + 2H20 manifests: (c) in the nature of spins of protons· 0
(a) acidic nature of H202 0 . (d) in the nature of spins of electrons 0
(b) alkaline nature of H202 0 51. Decolourisation of acidifted potassium permanganate occurs
(c) oxidising action of H202 0 when H202 is added to it. This is due to:
(d) reducing nature of H 20 2 0 (a) oxidation of KMn04 0
40. H20 2is: (b) reduction of KMn04 0
(a) an oxidising agent 0 (c) both oxidation and reduction of KMn04 0
(b) both oxidising and reducing agent 0 ~d) none of the above 0
52. Which of the following metals adsorbs hydrogen? 66. Hydrogen directly combines with:
(a) Zn 0 (b) Pd 0 (a) Ca 0 (b) Mg 0
(c) AI 0 (d) K 0 (c) AI 0 (d) Cu 0
53. The permanent hardness of water can be removed by boiling 67. The metal which displaces hydrogen from a boiling caustic
the water with: soda solution is:
(a) NaOH 0 (b) Na2C03 o (a) Ag 0 (b) Zn o
(c) Na3P04 0 (d) all the three o (c) Mg 0 (d) Fe o
54. Hydrogen reacts with the following in the dark: 68. Hydrogen peroxide is used as:
(a) Br2 0 (b) F2 o (a) oxidising agent 0
(c) 12 0 (d) Cl2 o . (b) reducing agent 0
55. H20 2 reduces K~e(CN)6 in: (c) both as oxidising and reducing agent 0
(a) neutral solution 0 (b) acidic solution 0 (d) drying agent 0
(c) alkaline medium 0 (d) non-polar medium 0 69. The melting points of most of the solid substances increase
56. In which of the following reactions does water act as an with an increase of pressure acting on them. However, ice
oxidising agent? melts at a temperature lower than its usual melting point when
(a) 3F2 + 3H20 ~ 6HF + 03 o the pressure is' increased. This is because:
(b) CaC 2 +2H 20 ~Ca(OHh+C2H2 o (a) ice is less densethan water o
(c) C+H20~CO+H2 o (b) it generates heat o
(d) AlN+ 3H20 ~ AI(OHh + NH3 o (c) -chemical bonds break under pressure Q-
57. The species that do not contain per<lXide ions are: (d) none of the above o
(a) PbOz 0 (b) H20z o 70. A mixture of hydrazine and H20 2 is:
(c) SrOz 0 (d) BaOz o (a) antiseptic 0 (b) rocket fuel o
58. The 'volume strength' of 1.5 N H 20z solution is: (c) germicide 0 (d) insecticide o
(a) 4.8 0 (b) 8.4 0 71. Decomposition of H 20 2 is accelerated by :
(c) 3.0 0 (d) 8.0 0 (a) traces of acids 0 (b) acetanilide o
59. When zeolite, which is hydrated sodium aluminium silicate, (c) finely divided metals 0 (d) alcohol o
is treated with hard water the sodium ions are exchanged with:. 72. The shape of water molecule is same as that of:
(a) H+ ions 0 (b) Ca++ ions 0 (a) C2H2 0 (b) COz 0
(c) SO"4 ions 0 (d) OH- ions 0 (c) NH3 0 (d) Cl20 0
60. Which of the following statements is incorrect?[BHU 2008J 73. 20 mL of a sample of H20 2 gives 400 mL of oxygen
(a) H 20 2 can act as an oxidising agent 0 measured at NTP. The sample should be labelled as:
(b) H 20 2 can act as a reducing agent 0 (a) 5 vol. H 20 2 D (b) dil. H20 2 0
(c) H20 2 has acidic properties 0 (c) anhydrous H20z 0 (d) 20 vol. H 20 2 0
(d) H20 2 has basic properties 0 74. An orange coloured solution acidified with H2S04 and treated
61. The hybrid state and oxidation state of two oxygen atoms in with a substance 'X' gives a blue colourerl ,solution of crOs.
H202 are respectively : The substance 'X' is:
(a) si, -1 0 (b) sp2, +1 0 (a) H20 0 (b) dil. HCI o
(c)sl, -1 0 (d) sl, +1 0 (c) H20z 0 (d) COllC. HCI
62. Given colourless liquid will be determined whether it is water 75. Consider the two reactions:
or not? (x) H20 2 + H 2S ~ S + 2H20
(a) By smelling o (y) H20 2 + 03 ~ 202 + H 20
(b) By tasting o H 20 2 acts as:
(c) By phenolphthalein o
(d) By adding a pinch of anhydrous CUS04 o (a) oxidising agent in both (x) and (y) 0
63. Heavy water is used in atomic reactor as: (b) oxidising in (x) and reducing in (y) 0
(a) coolant o .....
(c) rcl!Wcing in (x) and oxidising in (y) 0
(b) moderator o (d) reducing in both (x) and (y) 0
(c) both coolant and moderator o 76. Hydrogen can be placed in VIlA (or 17th group) of periodic
(d) neither coolant nor moderator o table because:
64. Heavy water freezes at: (a) hydrogen forms hydrides like NaH 0
(a) O°C o (b) 3.8°C o (b) hydrogen has isotopes D and T 0
(c) 38"C o (d) -3.8°C o (c) it is light 0
65. Hydrogen does not combine with: (d) hydrogen combines with halogens 0
(a) He 0 (b) Na o T7. H202~ 2H+ + 02 + 2e-, EO = 0.68 V
(c) Sb 0 (d) Bi o The above equation represents which of the following
behaviour of H202?
(a) Reducing 0 (b) Oxidising 0 84. The H-O--H angle in water molecule is about:
(c) Acidic 0 (d) Catalytic 0 [A.F.M.C. 2001]
78. Which of the following is a true structure of H20 2? (a) 90° o(b) 1800 o
1800
H~ (c) 102° o(d) 105 0 o
(a) H~-H 0 0 85. When two ice cubes are pressed over each other, they unite
H H (b) "'" to form one cube. Which of the following forces is respon-
~°
sible to hold them together? [A.F.M.C. 2001]
H" (a) Hydrogen bond formation 0
(c) 0 (d) /0=0 0
(b) van der Waals' forces 0
H
79. Hydrolysis of one mole of peroxydisulphuric acid produces: (c) Covalent attraction 0
(a) two moles of sulphuric acid 0 (d) Ionic interaction 0
(b) two moles of peroxymonosulphuric acid 0 86. The process used for the removal of hardness of water is:
.[E.A.~.C.E.T. 2001]
(c) one mole of sulphuric acid and one mole of peroxy-
monosulphuric acid 0 (a) Calgon 0 (b) Baeyer 0
(d) one mole of sulphuric acid, one mole of peroxymonos- (c) Serpeck 0 (d) Hoope . 0
ulphuric acid and one mole of hydrogen peroxide 0 87. In which of the following reactions, H202 acts as a reducing
[Hint: H 2S20 g + H 20 - - ? H2S04 + H 2SOs] agent? [E.A.M.C.E.T.'20011
SO. Which of the following is correct for hydrogen? (a) Pb02(s) + H202(aq.)~ PbO(s) + H20(1) + 02 (g) 0
(a) It can form bonds in+l as wellas·-l oxidation state 0 ,(b) Na2S03(aq.)+ H 20 2(aq.).--? Na2S04(aq·) + H:P(lJD
(b) It is collected at cathoC!e. 0 .(c) 2KI(aq.) + H 20 2(aq.)---'---t 2KOH(aq.) + 12(S) 0
(c) It has a very high ionis'ation potential 0 (d) KN02(aq.) + H202(aq.)~ KN0 3(aq.) + H 20(1) 0
(d) All of the above :. .0 88. Action of water or dilute mineral acids on metals can give:
81. Which of the following stateinents is correct? [M.E.E. (Kerala) 2002]
(a) Hydrogen has same ioni;ation potential as sodium 0 (a) Monohydrogen o (b) Tritium 0
(b) H has same electronegativity as halogens 0 (c) Dihydrogen o (d) Trihydrogen 0
(c) It will not be liberated at anode 0 (e) Dz o
(d) H has oxidation state + 1 and -1 0 89. H20 2 is "5.6 volume", then:
82. Consider the following statements: (a) it is 1.7% weight by volume 0
I. Atomic hydrogen is oburlned by passing hydrogen (b) it is I N 0
through an electric arc. (c) both is true 0
II. Hydrogen gas will not reduce heated aluminium oxide. (d) none is true 0
III. Finely divided palladium absorbs large volume of 90. H2 can be obtained from:
hydrogen gas. (a) water gas (CO + H2) by liquefaction of CO at low
N. Pure nascent hydrogen is best obtained by reacting Na temperature under pressure 0
with C2HSOH. (b) water gas by oxidation of CO into CO 2 (by steam) which
Which of the above statements is/are correct? can be easily removed by dissolving in H20 0
[S.C.R.A. 2001]
(c) electrolysis of water or NaOH 0
(a) I alone 0 (b) II alone 0 (d) alI'are correct 0
(c) I, II and III 0 (d) II, III and IV 0 91. Out of the following metals which will give H2 on reaction
83. Match List I with List II and select the correct answer using with NaOH?
the codes given below in the lists: [S.C.R.A. 2001] I : Zn, n : Mg, III : AI, IV: Be
List I Listll (a) I,n,Ill,IV 0 (b) I,Ill,IV 0
1. Heavy water A. Bicarbonates of Mg and (c) n,IV 0 (d)I,Ill 0
Ca in water 92. Out of LiH, MgH2 and CuH:
2. Temporary hard water B. No foreign ions in water (a) all are ionic hydrides 0
3. Soft water C D20 (b) LiH, MgH2 are ionic and CuH is covalent 0
4. Permanent hard water D. Sulphates and chlorides (c) all are covalent 0
of Mg and Ca in water (d) LiH is ionic, MgH2 and CuH are intermediate 0
Codes: 93. Which of the following metals will give H2 on reaction with
(a) I-C, 2-D, 3-B, 4-A o NaOH? [p.E.T. (Raj.) 2003]
(b) I-B, 2-A, 3-C,4-D o (a) Be 0 (b) Ba 0
(c) I-B, 2-D, 3-C, 4-A o (c) ('..a 0 (d) Sr 0
(d) I-C, 2-A, 3-B,4-D o
94. Which of the following is used as rocket fuel ? (c) NaH and NH3 0 (d) CaH2 and B2Hti D
[P.E.T. (Raj.) 2003] . I~. Hydrogen is not obtained when zinc reacts with:
(a) Liquid0 2 0 (b)LiquidN2 0 [C.E.T. (J & K) 200S]
(c) LiquidNH3 0 (d) Liquid H2 0 (a) steam 0 (b) hot NaOH solution. D
95. Water is considered to be polluted if the dissolved oxygen (c) conc. H2S04 0 (d) dilute HCI D
(DO) content is less than ............. ppm. lE.A.M.C.E.T.2003] 107. The hardness of water sample containing 0.002 mole of mag-
(a) 5 0 (b) 10 0 nesium sulphate dissolved in a litre is expressed as:
~15 0 ~IOO 0 [p.E.T. (Kerala) 2007]
96. Which of the following could act as propellant for rockets? (a) 20ppm o (b) 200ppm D
[A.I.E.E.E.2oo3] (c) 2000ppm o (d) 120ppm D
(a) Liquid oxygen + liquid argon o (e) 240ppm o
(b) Liquid nitrogen + liquid oxygen o [Hint : 0.002 mol = 240 x 10-3 g == 200 x 10-3
(c) Liquid hydrogen + liquid oxygen o MgS04 CaC03
(d) Liquid hydrogen + liquid nitrogen o 108. Match list I with list n. Choose the correct matching codes
ff7. On burning hydrogen in air the colour offlame is: from the choices given: [p.E.T. (Kerala) 2007]
[A.F.M.C. 2003]
List I Listll
(a) green 0 (b) light bluish 0
(c) yellow 0 (d) none of these 0 A. BeH2 1, Complex
98. Surface water contains: . [A,F.M.C. 2003] B. AsH3 2. Lewis acid
(a) suspended impurities 0 C. B2Hti 3. Interstitial
(b) organic impurities 0 D. LaH3 4. Covalent
(c) salt 0 E LiAlH4 5. Intermediate
(d) salt and organic compound 0 6. Ionic
99. Water is oxidised to oxygen by: [p.E.T. (Kerala) 2003] (a) A - 6, B 2,C "- 4, D - 5, E - 1 D
(a) Ozone 0 (b) KMn04 0 (b) A-6,B':"'2,C 4,D-3,E-l D
(c) H2~ 0 (d) F2 0 (c) A 6,B-4,C-2,D 3,E 5 D
(e) a~ 0 (d)A-6,B-4,C 2,D-3,E 1 D
100. Number of H-bonds formed by a water molecule is: (e) A-5,B-4,C-2,D 6,E-I D
[M.GI.M.S. (Wardha) 2003] 100. When hydrogen peroxide is added to acidified potassium
(a) 2 0(b) 8 0 dichromate, a blue colour is produced due to the formation
(c) 1 0 (d) 4 0 of: [P.E.T. (Kerala) 2007]
101. Water softening by Clarke's process uses: (a) ct03 0 (b) Cr2O:3 C~
[p.M.T. (Kerala) 2003] (c) CtOs 0 (d) CtO~- C

(a) calcium bicarbonate 0 (e) Cr20~- 0
(b) sodium bicarbonate 0 110. The hybridization of oxygen atom in H202 is :
(c) potash alum 0 [P.M.T. (Kerala) 2007; C.M.C. (VeUore) 2008]
(d) calcium hydroxide 0 (a) sp3 d 0 (b) sp D
(e) sodium aluminate 0 (c) si 0 (d) sp3 D
102. The H--O--O bond angle in H 20 2 is : [C.E.E. (Kerala) 2004]
(e) sp3d 2 0
(a) 107.28° 0 (b) 109.28° 0 111. Hydrogen can be prepared by the action of dilute H2S04 on:
(c) 104,50 0 (d) 97° 0 [A.I.I.M.8. 2007]
103. Which is false about H202? [D.C.E. 2005] (a) copper o (b) iron D
(a) Acts both as oxidising and reducing agent 0 (c) lead D (d) mercury D
(b) Two OH bonds lie in the same plane 0 112. Match the following:
(c) Pale blue liquid 0 Set I Set IT
(d) Can ~ oxidised by 03 0 A. 10 vol. H 20 2 1. Perhydrol
104. When electric current is passed through an ionic hydride in B. 20 vol. H 20 2 2 5.358N
molten state: [p.KT. (Kerala) 2005] C 30 vol. H 20 2 3. 1.785M
(a) hydrogen is liberated at anode 0 D. 100 vol. H202 4. 3.03%
(b) hydrogen is liberated at cathode 0 The correct match is: [E.A.M.C.E.T. (l\ied.) .2007]
(c) hydride ion migrates towards cathode 0 (a) A-4,B-3,C 2,D-l D
(d) hydride ion remains in solution 0 (b)A 1,B-2,C-3,D 4 D
105. Among CaH2, NH3, NaH and B2Hti. which are covalent (c) A 1, B 3, C - 2, D - 4 D
hydrides? [J.E.E. (Orissa) 2005] (d) A-4,B-2,C 3,D-l D
(a) NH3 and B2H6 0 (b) NaH and CaH2 0
113. The alkali metals form salt like hydrides by direct synthesis (ii) Heavy water is more associated than ordinary water.
at elevated temperatures. The thermal stability of these (iii) Heavy water is more effective solvent than ordinary water.
hydrides decreases in which of the following orders? Which of the above statements are correct? [C.B.S.E. 2010]
[C.B.S.E. 2008] (a) (i) and (ii) D (b) (i), (ii) and (iii) D
(a) NaH>LiH>KH>RbH>CsH D (c) (ii) and (iii) D (d) (i) and (iii) D
(b) LiH>NaH>KH>RbH>CsH D 120. The following can convert hard water into soft water:
(c) CsH>RbH>KH>NaH>LiH D [C.E.C.E. (Bihar) 2010]
(d) KH<NaH<LiH>CsH>RbH D (a) Sodium palmitate D
114. In context with the industrial preparation of hydrogen from (b) H202 D
water gas (CO + H2) which of the following is the correct (c) Lead nitrate D
statement? [A.I.E.E.E. 2008] (d)' Sodium aluminium silicate D
(a) CO is oxidised to C02 with steam in the presence of a 121. H202 is a : [C.E.c.E. (Bihar) 2010]
catalyst followed by absorption of C02 in alkali D (a) monobasic acid D (b) dibasic acid D
(b) CO and H2 are fractionally separated using difference in (c) neutral compound D (d) weakalkali D
their densities D 122. Which one of the following compounds is a peroxide?
(c) CO is removed by absorption in aqueous CU2Cl2 D [C.B.S.E. (P.M.T.) Pre. 201V]
(d) H2 is removed through occlusion with Pd D (a) K02 D (b) Ba02 D
115. The bond angle and dipole moment of water respectively are: (c) Mn02 D (d) N02 [J
[J.E.E. (Orissa) 2008] 123. Ortho and para hydrogen have: [J.E.E. (W.B.)2010J-
(a) 109.so,1.84D D (b) 107.so,1.56D D (a) identical chemical properties but different physical
(c) 104.so,1.84D D (d) 102.5°,1.56D D properties D
116. Which one of the following is used for reviving the exhaust (b) identical physical and chemical properties [J
permutit? [D.C.E.· 2008] (c) identical physical properties but different chemical
(a) HCI solution [J (b) 10% CaCl2 solution D properties [J
(c) 10% MgCl 2 solution D (d) 10% NaCl solution D (d) different physical and chemical properties D
117. Which of the following is not correct regarding the
124. CO + H2 300°C/300atm) CH OH
electrolytic preparation of H202? [D.C.E. 2008] x (catalyst) 3
(a) Lead is used as cathode D The catalyst X is : [J.E.E. (Orissa) 2010]
(b) 50% H2S04 is used D (a) Fe D (b) Cr203/ZnO D
(c) Hydrogen is liberated at anode D (c) V20S D (d) AI203 D
(d) sulphuric acid undergoes oxidation D 125. Which one of the following undergoes reduction with H202
118. Blackened oil painting can be restored into original form by in an alkaline medium? [P.E.T. (Kerala) 2010]
the action of : [J.E.E. (W.B.) 2009] (a) Mn2+ [J (b) HOCI D
(a) Chlorine D (b) Ba02 D (c) PbS D (d) Fe2+ D
(c) H2~ D (d) Mn02 D (d) 12 []
119. Some statements about heavy water are given below: [Hint : HOCl + H 20 2 ~ HCI + H 20 + O2]
(i) Heavy water is used as a moderator in nuclear reactors.
Set II : The following questions may have more than one correct answer.·
126. Which of the following metals on treatment with NaOH will (c) Sodium and ethyl alcohol D
liberate H2 gas? (d) Iron and steam D
(a) Zn D (b) Sn D 130. The oxides which give H202 on treatment with dilute acid
(c) AI 0 (d) Mg D are:
127. When zeolite, which is hydrated sodium aluminium silicate, (a) Pb02 0 (b) Mn02 D
is treated with hard water, the- sodium ions are exchanged (c) Na202 [J (d) Ba02 D
with: 131. The oxidation states of the most electronegative element in
(a) H+ ions D (b) SO~- ions D the products of the reaction between Ba02 with dilute H2S04
(c) C~+ ions D (d) Mg + ions D are :
128. Hydrogen will reduce: (a) -1 D (b) + 1 D
(a) heated cupric oxide D (b) heated ferric oxide D (c) - 2 D (d) 0 D
(c) heated zinc oxide D (d) sodium oxide D [Hint: Ba02 + H2S04 ~ BaS04 + H20 2. The most electro-
129. Which of the following pairs of substances on reaction will negative element in products is oxygen. The oxidation state
evolve H2 gas? of oxygen in H20 2 is -1 and in BaS04 is -2.]
(a) Iron and dilute H2S04 D 132. In which of the following hydrides, hydrogen exists in
(b) Copper and dilute HCI D negative oxidation state?
(a) Hel 0 (b) NaH 0 134. Which of the following heated qx,ides are reduced by
(c) CaH2 0 (d) HI 0 hydrogen? ,~ ,
133. An acidified solution of KMn04 undergoes reduction with: (a) Sn02 0 (b) Al20 3 0
(a) H2 0 (c) Fe203 0 (d) CuO 0
(b) ZnJCu couple and H20 0 135. The reagent(s) used for softening the temporary hardness
(c) Na + absolute alcohol 0 of water is (are) : [LI.T.2010]
(d) ZnlH 2S0 4 0 (a) Ca3(P04n 0 (b) Ca(0H)2 0
(c) Na2C03 0 (d) NaOCl 0
1. (d) 2. (c) 3. (b) 4. (a) 5. (c) 6. (a) 7. (d) 8. (b) 9. (c) 10. (b)
11. (c) 12. (b) 13. (d) 14. (c) 15. (c) 16. (b) 17. (d) 18. (a) 19. (c) 20. (d)
21. (a) 22. (d) 23. (a) 24. (a) 25. (c) 26. (d) 27. (b) 28. (a) 29. (b) 30. (c)
31. (d) 32. (c) 33. (b) 34. (c) 35. (a) 36. (d) 37. (b) 38. (c) 39. (c) 40. (b)
41. (b) 42. (a) 43. (d) 44. (c) 45. (b) 46. (a) 47. (a) 48. (b) 49. (a) 50. (c)
51. (b) 52. (b) 53. (d) 54. (b) 55. (c) 56. (c) 57. (a) 58. (b) 59. (b) 60. (d)
61. (c) 62. (d) 63. (c) 64. (b) 65. (a) 66. (a) 67. (b) 68. (c) ~. (a) 70. (b)
71. (c) 72. (d) 73. (d) 74. (c) 75. (b) 76. (a) 77. (a) 78. (b) 79. (c) SO. (d)
81. (d) 82. (c) 83. (d) 84. (d) 85. (a) 86. (a) 87. (a) 88. (c) 89. (c) 90. (d)
91. (b) 92. (d) 93. (a) 94. (d) 95. (a) 96. (c) 97. (b) 98. (a) 99. (d) 100. (d)
101. (d) 102. (d) 103. (b) 104. (a) 105. (a) 106. (c) 107. (b) 108. (e) 109. (c) 110. (d)
111. (b) 112. (a) 113. (b) 114. (a) 115. (c) 116. (d) 117. (c) 118. (c) 119. (a) 120. (d)
121. (b) 122. (b) 123. (a) 124. (b) 125. (b) 126. (a,b,c) 127. (c,d) 128. (a,b,c) 129. (a,c,d) 130.lc,d)
131. (a,c) 132. (b,c) 133. (b,c,d) 134. (a,c,d) 135. (b,c)
- "._~ Objective Questions for liT ASPIRANTS' ' . "

1. Hydrogen behaves as an oxidising agent in its reaction with: 4. Which of the following hydrides conducts electricity?
, (a) chlorine 0 (b) potassium 0 (a) Sif4 0 (b) B2~ 0
(c) nitrogen 0 (d) sulphur 0 (c) CH4 0 (d) KH 0
[BiDt : An oxidising agent is a species which accepts an electron [Hint : KH is a crystalline solid, in molten state it conducts
or electrons. Hydrogen accepts an electron from potassium electricity as it possesses K+ and Jr i~ns.]
when it forms KH 5. The correct increasing order of the acidity of CO2, H20 and
H2 + 2K ~ 2KH (K+W)] H20 2 is:
2. Hydrogen cannot be obtained by: (a) CO2 < H20 2 < H20 0 (b) H 20 < H202 > CO2 0
(a) Zn + dil. H 2S04 0 (b) Zn + dil. HN0 3 0 (c) H20 < H;02 < C02 0 (d) H202 < H20 <C02 0
(c) Mg + H20 IJ (d) Mg + diI. H 2S04 0 6. Hydrogen combines with other elements by:
[Hint : Zn reacts to form hydrogen with dilute HN03' Before the (a) losing an electron 0
hydrogen is r~leased, it reduce HN03 into an oxide of (b) gaining an electron 0
nitrogen.] (c) sharing an electron 0
3. Hydrogen peroxide ionises as : H20z :;:=:::: H+ + HOi. If pH (d) (a), (b), (c) all are correct 0
Q
of H 20z is 5.91 at 25 C, the ionic product of H 20 2 is: 7. Metallic hydride is formed by:
(a) 1.51 x 10- 12
0 (b) 1.15 x 10-12 0 (a) iron 0 (b) manganese
(c) 1 X 10- 14
0 (d) 1'.1 x 10-12 0 (c) palladium 0 (d) molybdenum 0
[Wmt: [Hi at 25°C = 10- . = 1.23 x 10-6 M;
5 91
[HOz] = 1.23 x 10-6 M

K = [Hi [HO}] = [1.23 x 1O-6 f
1.51 x 10-12]
1. (a) 2. (b) 3. (a) 4. (d) 5. (c) 6. (d) 7. (c)
Matrix Matching Questions for liT A§pirants

1. Match List-I with List-II: (c) Fe304 + 4H2 (r) Uyeno's method
List·! List·II .. - 3Fe + 4H20
(a) Hard water '(p) Ca(HC0 3h (d) C + H20(g) (s) Bosch process
(b) Temporary hardness (q) MgS04 CO(g) + H2t
(c) Sodium ion in zeolite gets (r) Ca2+ 3. Match List-I with List-II:
exchanged with List·! List·II
(d) Permanent hardness (8) Mg2+ (a) LiAlH4 (p) Binary hydride
2. Match List-I with List-II: (b) NaBH4 (q) Used as reducing agent for
List·! List·II organic compounds
(a) 2Al + 2KOH +2H20 ~ (p) Vivification (c) CaH2 (r) Complex hydride
2KAIOz + 3H2 (d) LiH (s) Alanate
(b) Fe304 + 4CO ~ (q) Involved in Lane's process
3Fe + 4C02
(b-p) (c-r, s) (d-q) 3. (a-q, r, s) (b-q, r) (c-p) (d-p)

, (b-p, q) (c-p, q)" (d-s)
I Assertion-Reason Type QuesJions

The following questions consist of two statements each, 4. (A) The process of adsorption of hydrogen on palladium is
Assertion (A) and Reason (R). You are required to choose any known as occlusion.
one of the following responses for each question. (R) The adsorbed hydrogen is more active than ordinary
(a) If both (A) and (R) are true and the (R) is a correct expla- hydrogen.
nation of the (A). . 5. (A) Hydrogen is prepared in the laboratory by the action of
(b) If both (A) and (R) are true but (R) is not the correct cO.!,lc. H2S04 on zinc metal.
explanation of (A). (R) Pure hydrogen can be obtained by the action of water
(c) If (A) is true but (R) is false. on sodium hydride.
(d) If (A) is false but (R) is true. 6., (A) Hard water is used in a nuclear reactor.
(e) If both (A) and (R) are false. (R) Dilute solution of H20 2 under the name of perhydrol is
1. (A) Alkali metals form ionic hydrides. used in medicines as antiseptic for washing wounds,
(R) Alkali metals lose their valency electron which is accepted teeth, ears, etc.
by hydrogen to form a negative ion. 7. (A) Normal hydrogen consists of a mixture of two forms:
2., (A) When blood is added to a solution of H202,the solution ortho-(75%) and para (25%).'
bubbles furiously. (R) Pure ortho form can be obtained at low temperature but
(R) Catalase (an enzyme) present in blood decomposes H 20 2 pure para form cannot be obtained.
and produces bubbles of 02' 8. (A) H20 2 is a linear molecule.
3. (A) Old lead paintings regain their original colour by washing (R) Each oxygen is sp-hybridized.
with hydrogen peroxide solution. 9. (A) NaCl is less soluble in heavy water than in ordinary water.
(R) Hydrogen peroxide dissolves the blackened layer by (R) Dielectric constant of ordinary water is more than that of
virtue of its acidic nature. heavy water. .. IE.A.M.C.E.T. (Engg.) 2007]
1. (a) 2. (a) 3. (c) 4. (b) S. (d) 6. (d) 7. (j 8. (e) 9. (a)
11111111 , .
THOUGHT TYPE QUESTIONS
.
11111111
THOUGHT· 1,~",_,~...",,..;.,.___, .,,__ ~..~.. ~ .•_""~•.. "",".._••_,=..,..,,.~.~,~ The reaction of hydrogen and oxygen is highly exothermic, and
Hydrogen is thought to account for approximately 75% of the gas mixtures that contain as little as 4% by volume hydrogen in
mass· of the universe. Our sun and other stars, for instance, are oxygen (or in air) are highly flammable and potentially explosive.
composed mainly of hydrogen, which serves as their nuclear fuel. 2H2(g) + 02(g) ~ 2H20(g) !ili" = -484 kJ
On earth, though hydrogen is rarely found in its uncombined state Hydrogen is an enormously attractive fuel because it is
because earth's gravity is too weak to hold such light molecules. environmentally clean. 'Hydrogen economy' is a new field in which
Nearly all the H2 originally present in the earth's atmosphere has it is thought that our energy needs can be meet by gaseous, liquid
been lost to space. In the earth's crust and oceans, hydrogen is and solid hydrogen. Since hydrogen is not a naturally occurring
found in water, petroleum, proteins, carbohydrates, fats and substance like coal, oil or natural gas, energy must be expended
literally millions of other compounds and is ninth most abundant to produce hydrogen before it can be used. Current research
element on a mass basis. therefore focuses on finding cheaper methods for extracting
There are three isotopes of hydrogen : protium or ordinary hydrogen.
hydrogen dB); deuterium or heavy hydrogen dH or D) and tritium 1. Which fuel does produce least environmental pollution ?
(fH or T). The chemical properties of the three isotopes are similar (a) Gasoline (b) Hydrogen
because they have same electron configuration. The. physical (c) Wood (d) Coal
properties of three isotopes are different due to difference in their 2. If an isotope of hydrogen has two neutrons in its atom, its
masses, i.e., isotope effects. atomic number and atomic mass number will respectively be :
(a) 2 and I (b) 3 and I In alkaline medium, however, its reducing nature is more
(c) I and I (d) I and 3 effective.
3. Which of the following gas is lightest? H2~ +20H- ---7 2H 20 + O 2 + 2e
(a) Oxygen (b) Nitrogen 1. In which of the following reactions, H20 2 acts as a reducing
(c) Hydrogen (d) Helium agent?
4. Which isotope of hydrogen is radioactive in nature?
(a) Pb0 2 + H202 ---7 PbO + H20 + O2
(a) Protium only (b) Deuterium only
(c) Deuterium and tritium (d) Tritium only (b) Na2S03 + H20 2---7 Na2S04 + H20
5. Abundance of H2 in the earth's atmosphere is very small. (c) 2KI + H20 2---7 2KOH + 12
This is because : (d) KN02 + H20 2---7 KN0 3 + H20
(a) the earth's gravity is weak to hold light molecules 2. In which of the following reactions, H20 2 acts as an oxidising
(b) the hydrogen is inflammable agent?
(c) the hydrogen readily combined with oxygen of (a) 104" + H202 ---7 103+ H20 + O2
atmosphere
(b) 2r + H202 + 2H+ ---712 + 2H20
(d) the hydrogen is diatomic in nature
6. Liquid H2 has been used as a rocket fuel because of : (c) Ag20 + H20 2 ---7 2Ag + H20 + O2
(a) high thrust (d) 2Mn04" + 6W + 5H20 2 ---7 2Mn2+ + 8H20 + 502
(b) its reaction with oxygen is highly exothermic 3. In the reaction, H202 + 0 3 ---7 H20 + 202, H202 acts as :
(c) small space it occupies (a) an acid
(d) all these are correct (b) an oxidising agent
(c) a reducing agent
(d) both as a reducing agent and an oxidising agent
[Hint : 0 3 acts as an oxidising agent as it gives oxygen which
Red Hot COke] oxidised HzOz.
[
+ lOOO'C ) I X'
i
500"C) • A'
Catalyst
+H
2
°
HzOz + ---7 HzO + Oz]
4. The bleaching properties of H20 2 are due to its :
Steam Steam (Y)
(a) unstable nature (b) acidic nature
1. The above sequence refers to : (c) reducing nature (d) oxidising nature
(a) Lane's process (b) Bosch's process 5. Decolourisation of acidified KMn04 occurs when H20 2 is
(c) Haber's process (d) Ostwald's process added to it. This is due to :
2. 'X' is: (a) oxidation of KMn04
(a) water gas (b) producer gas (b) reduction of KMn04
(c) coal gas (d) oil gas (c) both oxidation and reduction of KMn04
3. 'A' is :
(a) carbon monoxide
(c) carbon dioxide
4. The catalyst 'Y' is :
(a) V 20 5
(b) oxygen
(d) water
(b) Ni
THOUGHT 4 ~ __,_ _ _ ___

'"~" ~~~~m_~
On large scale, H2~ is prepared by hydrolysis of peroxy-

disulphuric acid obtained by electrolysis of 50% H2S04. The
(c) Fe (d) Cr203 + Fe203
strength of H 20 2 is expressed in number of ways namely
5. 'A' is removed by passing the gaseous mixture:
normality, molarity, percentage strength and volume strength.
(a) through water under high pressure of 25 atmospheres
Volume strength refers to the volume of ~ obtained at NTP by
(b) through acidic solution
decomposition of ImL of H2~ solution.
(c) through alkaline solution
(d) through an organic solvent 1. The volume of 20 volume H20 2 solution that decolourises
200 mL of 2 N KMn04 solution in acidic medium is:
(a) 112mL (b) 336mL
(c) 200mL (d) 224mL
Hydrogen peroxide is a powerful oxidising agent. It is an . . 20
[Hint: Nonnality of 20 volume H20 2 = 5.6 N
electron acceptor in acidic and alkaline mediums.
20
H2~ + 2Jr + 2e ---72H20 (in acidic medium) :. 5.6xV,=2X200 or V=112mL
H202 + 2e ---720H- (in alkaline medium) 2. Hydrolysis of one mole of peroxydisulphuric acid gives:
It can also act as a reducing agent towards powerful oxidising (a) two moles of H2S04
agents; (b) two moles of Cam's acid
(c) one mole of H2S04 and one mole of H2S05
(d) one mole of H2S04, one mole of H2S05 and one mole of
H2~
3. The volume strength of 1.S N H 20 2 solution is: 5. What is the volume of O2 liberated at NTP by complete
(a) 4.8 (b) S.2 decomposition of 100 mL of 2 M solution of H20 2?
(c) 8.8 (d) 8.4 (a) 22.4 L (b) 2.24 L
[Hint: Volume strength ;;. 5.6 x normality] (c) 0.224L (d) 224L
4. Commercial 11.2 volume H20 2 solution has molarity of: [Hint: Volume strength ;;. 11.2 x Molarity 22.4
(a) l.0 (b) O.S 100 mL = 0.1 L, i.e., 22.4 x 0.1
(c) 112 (d) 1.12 ;;. 2.24 L O2 released ]
[Hint : Molarity ]
Thought 1 1. (b) 2. (d) 3. (c) 4. (d) 5. (a) 6. (d)

Thought 2 1. (b) 2. (a) 3. (c) 4. (d) 5. (a)
Thought 3 1. (a) 2. (b) 3. (c) 4. (d) 5. (b)
Thought 4 1. (a) 2. (c) 3. (d) 4. (a) 5. (b)
I. What is the oxidation state of hydrogen in N3H and NH3? [Hint: N,V, (H2OV ;; N2V2 (hypo)
Indicate_ ~e,nature of these compounds. N, x 50 ;;. 0.1 x 20
[Hint :N3H (Hydrogen in +1 state; acidic) 1
-3+3 N, ~ 25
NH3 (Hydrogen in +1 state; basic)] gllitre strength ;;.N x Eq. mass
2. Write two examples of bridging hydrogens. ; . is x 17 ;;. 0.68 gIlitre J
H H . CO
t t
co 1 6. What is Fenton's reagent?
Ans. )B<\ )B< OC 9'" /9 ~ co

l··\ J.J 2
[Hint: Fe +1H20z used as oxidising agent or dehydrogenating
-7 agent for organic compound.J
[
H H H co H co
7. In some tooth pastes hydrogen peroxide is used. What is role
3. Write down hydrogen bonded coordinated water in hydrates. of H20 2 in it?
[Ans. Hydrogen peroxide is used as antiseptic.]
[mnt':>~M; :>I-M; :)o<:j

8. Hydrogen peroxide acts as oxidising agent in acidic as well
as basic mediums. Substantiate this fact by electrode poten-
tial data.
[Ans.H20 2 + 2H+ + 2e- ;;. 2H 20; EO 1.77 V
4. What is mass in grams of available O2 per litre from a solution Oz + 2W + 2e- = H20 2 ; EO;;. 0.68 V
of H 20 2, 10 mL of which when titrated with N/20 KMn04 HOl + H20 + 2e- ;;. 30Ir ; EO 0.87 VJ
solution, required 2S mL for the reaction? 9. There are three samples of H 20 2 labelled as 10 vol; IS vol;
2KMn04 + SH2~ + 4H2S04- - 7 20 vol. Half litre of each sample are mixed and then diluted
S02 + 8H20 + 2KHS04 + 2MnS04 with equal volume of water. Calculate volume strength of
resultant solution.
[Hint: N, V, (KMn04) ;;. NZV2 (H2OV
[Hir.t : We know, V;;. 5.6 x N
1 10
x25 N2 x 10
20 N, =5.6; N2 = 5.6' N3
2~=~ N1V1 + N2V2 +N3V3 NRVR

1
w Nx Eq. mass;;. 8 x 16;;. 2 g] 10 1 15 I 20 1
-x-+-x-+-x- = NR X 3
5.6 2 5.6 2 5.6 2
5. Excess of KI and dil. H2S04 were mixed in SO mL H202. The NR 1.339
liberated 12 requires 20 mL of 0.1 N Na2S203. Find out the Vo]un,c strength = NR x 5.6 = 1.339 x 5.6 = 7.5J
strength of H20 2 in gllitre.
\
264. GR.B. Inorganic Chemistry for Competitions
10. Answer the following questions: (li) Hydrogen peroxide is used to wash old oil paintings.Write
(a) Indicate whether ortho or para hydrogen has zero down the reaction involved in this process.
nuclear spin. (iii) H202 on reaction with ethene gives a commercially
(b) Indicate whether ortho or para hydrogen can be obtained important compound. Write down name of this compound
in pure form. and its use. .
[Ans. (a) Para hydrogen (iv) Arrange C~, H 20 and H202 in decreasing order of acidic
(b) At OK 100% para hydrogen can be obtained.] • nature.
11. Predict whether H 20 2 acts as oxidising or reducing agent in (v) Give the pH of D 20 and H 20 at 298 K.
. following reactions: [Ans. (i)· 0 3 (ii) PbS + 4H20 2 ~ PbS0 4 + 4H20
(i) 104+ H 20 2 ~ 103 + O 2 + H 20 CH 20H
(li) PbS + 4H202 ~ PbS04 + 4H20 (iii) I It is used as antifreeze in the radiator of car.
CH 20H
(ill) Ag20 + H2~ ~ 2Ag + H 20 + O 2
(Ethylene glycol)
(iv) AU20 + H 20 2 ~ 2Au + H20 + O 2
(iv) C02> H202 > H20
(v) 2r +H2~ +2H+ ~h +2H20 (v) 7.35 arid 7.0 ]
[Ans. (i), (iii), (iv) Reducing agent; (H), (v) Oxidising agent] H 20 2 H 2S04
18. [A] + Na[Cr(OH)4] ~ [B] -------t [C]
12. AS mLofH20 2 solution liberates 0.508 gI2 from an acidified
Yellow Orange coloured
KI solution. Calculate strength of H 20 2 solution in terms of coloured solution compound
volume strength at STP.
What are [AJ, [B] and [C]? Give the reactions involved.
[Ans.4.48]
[Hint : 2NaCr(OH)4 + 2NaOH + 3H 2Ch ~ 2Na2Cr04 + 8H20
[Hint : 2KI + H20 2 ~ 2KOH + 12
I mole I mole [Al [Bl
.: 254 g 12 is produced by I mole H202 2Na2Cr04 + H2S04 ~ Na2Cr2~ + Na2S04 + H20]

[Bl [c]
:. 0.508 g 12 is produced by 2!4 x 0.508 mole H202 = 2 X 10-3
19.· Two liquids (A) and (B) are made of same elements and are
number of moles diamagnetic. Liquid (A) on treatment with KI and starch gives
Molarity of H20 2 = volume in mL x 1000 blue coloured solution, however, liquid (B) is neutral to lit-
mus and does not give any response to starch iodide paper.
= 2X~0-3 x 1000 =0.4 [Ans. (A) ~ H20]
H 20z ; (B) ~
Volume strength = Molarity x 11.2 = 0.4 x 11.2 = 4.48] 20. Volume strength of H202 is 22.4. What volume of it is
13. How many types of !teavy water- are possible? Write down required to oxidise 3.4 gH2S gas?
formulae of all possible heavy water molecules. [Ans. 100 mL]
[Ans. There are six possible heavy water molecules
21. 25 mL H202 on treatment with excess of acidified KI solution
18 17 16 liberates iodine. Liberated iodine requires 20 mL of 0.3 N
H-O-D, H-O-D, H-O-D,
Na2S203 solution. Calculate volume strength of H 20 Z
16 17 18 solution.
D-O-D, D-O-D, D-O-D]
[Ans. 1.334]
14. What is perhydrol? Give its composition and use. [Hint : NI V1(H z0 2 ) = N2V2(Na2S2~)
[Ans. 30% H20 2 is called perbydro1 which is used as an antiseptic Nl x 25 = 0.3 x 20
and germicide for washing wounds, teeth and ears.] Nl = 0.24
15. Give an example in which H 20 acts as reducing agent. Volume strength of H20 2 = Normality x 5.6
[Ans. 2F2 + 2H20 ~ O2 + 4HF =0.24 x 5.6 = 1.344]
In above reaction, H20 acts as reducing agent.] 22. Naturally hard water is usually preferred in drinking and soft
water in working why?
16. How the active hydrogen can be obtained?
[Ans. Soft water is usually acidic and contains Na+ ions in place
[Ans. Active hydrogen can be obtained by subjecting fll .....lecular of di- and trivalent metal ions. An increased in take of Na+ is
hydrogen to silent electric discharge at ordinary temperature known to be related to heart disease and moreover the acidic
and 0.5 mm pressure. This hydrogen has great chemical soft water is more likely to attack metallic pipes, resulting
activity. The half-life period of active hydrogen is similar to in the solution of dangerous ions such as Pbz+. One way to
that of atomic hydrogen (0.3 sec).] avoid sodium ions in drinking water and to use less soap
when washing would be to drink naturally hard water and
17. Answer the following questions:
work in soft water.]
(i) Which of the following cannot be oxidised by H202?
KI ; 0 3 ; PbS; Na2S03
The answer to each of the following questions is a single 4. A commercial sample ofH20 2 is labelled as 'lO volume' . what .
'digit integer, ranging from 0 to 9. is its percentage strength?
1. What is the sum of protons, electrons and neutrons in the 5. What is the degree of hardness of a sample of water
heaviest isotope of hydrogen? containing 6 mg of MgS04 (molecular mass 120) per kg of
2. How much volume of lO volume H20 2 is required to liberate water?
50 cm3 of oxygen at STP? 6. What is the molarity of a commercial sample of 33.6 volume
3. One mole of calcium phosphide on reaction with excess of hydrogen peroxide solution?
water gives .... mole/s of phosphine.
1. (4) In tritium atom one proton, one electron and two neutrons are 5. (5) 6 mg of MgS04 present in 103 g of water.
present. 106 g water will contain = 6000 mg of MgS04 = 6g of MgS04
2. (5) 10 mL of O 2 iSdbtaiiled at STP from H20 2 == 1 mL 120 g of MgS04 100 g of CaC0 3
3. (2) Ca3P2 + 6H20 ~ 3Ca(OHh + 2PH3 100
So, 6 g of MgS04 = 120 x6= 5 g of CaC03
4. (3) 2H202~2H20+ O2 i.e., Hardness = 5 ppm
68 g 22400 mI
6. (3) Molarity = Volume strength 33.6 =3
10 mL of oxygen is obtained from = ~ x 10 = 0.03 g HZ0 2 11.2 11.2
22400
1 mL of H202 solution contains 0.03 g H20 2
100 mL of H202 solution contains = 3.0 g H20Z
Group
IAor 1 CHAPTER 6
Li
Lithium
Alkali Metals and
11
Na their Compounds
(Group IA or 1, nsl)
37
Rb
Rubidium
6." POSITION OF ALKALI METALS IN PERIODIC TAB':
The members of Group IA or I, except hydrogen are called the alkali metals,
because they react with water to fonn alkaline solutions. All the group lA elements
are soft silvery-grey metals. Their valence electron configurations are nsl, where
n is the period number, and their physical and chemical properties are dominated
Fr
Francium
by the ease with which the single valence electron can be removed. The group
1
IA of the periodic table consists of six elements-lithium, sodium, potassium,
Contents: rubidium, caesium and francium besides hydrogen. These elements are collectively
called as alkali metals and group IA is known as alkali group as the hydroxides
6.1 Position of Alkali Metals in Periodic Table
of these metals are soluble in water and these solutions are highly alkaline in
6.2 Abnonnal Behaviour of Lithium
nature. The word alkali has been derived from Arabic word 'Alquili' meaning the
6.2.1 Diagonal Relationship:
ashes of plants from which compounds of sodium and potassium were first
Similarities with Magnesium
isolated. They are soft enough to cut with a knife (Fig. 6.4). The alkali metals are
6.3 Lithium
the most reactive of all metals, reacting readily with water and air. The alkali
6A Sodium
metals, being reactive in nature, are never found free in nature but always found
. 6.5 Compounds of Sodium
in combined state. The alkali metals are so reactive that, they must be stored under
6.6 Potassium oil. This prevents the reaction of alkali metals with oxygen and water vapour in
the air.
Of all the alkali metals, only sodium and potassium are found in abundance in
nature, i.e., they are seventh and eighth most abundant elements by weight in
I::S::
Period
2
Zero
He
IA
1
[j
HA
1
Be
earth's crust. Their compounds are very common and have been known and used
from very early times. The last member, francium, occurs only in traceS as a
radioactive decay product because its half life period is very small, i.e., 21
(2) (3) (4)
minutes. Thus, not much is known about this element. The following table shows
3 Ne Na Mg the percentage and relative abundance of alkali metals in earth's crust by weight.
(10) (11) (12)
4 Ar K Ca Element Relative abundance
(18) (19) (20) Li 0.0018 35
5 Kr Rb Sr Na 2.27 7
(36) (37) (38) K 1.84 8
6 Xe Cs Ba Rb 0.0078 23
(54) (55) (56) Cs 0.00026 46
7 Rn Fr Ra Each alkali metal occupies a place just after a member of Zero group. Except
(86) (87) (88)
I first period, rest of the six periods of the periodic table start with a member of
Alkali Metals and their Compounds 267
alkali group. Next to the elements of Zero group, alkali metals form the most homogeneous of all the groups of the periodic table.
The members of this group show a marked resemblance in their properties and possess the same electronic configuration. There
is gradual gradation in the properties with the increase of atomic number. This justifies their inclusion in the same group of the
periodic table. The main properties of alkali metals are discussed below for this justification.
ill 1. Electronic Configuration

The arrangement or the distribution of electrons on various subshells in the atoms of alkali metals is given below :
Element At. No. Electronicoonfiguration I Configuration of the
valency sheD
Ii 3 2, 1 IS2, 2s1
Na 11 2,8, I Is2, 2s2 2p6, 3s 1
K 19 2,8,8,1 Ii, 2s2 2p6, 3; 3p6, 4s1
Rb 37 2, 8, 18, 8, I Ii, 2s2 2p6, 3s2 3p6 3dlO, 4s 2 4p6, 5s 1
Cs 55 2, 8, 18, 18, 8, I Ii, 2s2 2p6, 3s2 3p6 3dlO , 4s2 4p6 4d 1O, 5s2 5p6, 6s i
Fr 87 2, 8, 18, 32, 18, 8, 1 Is2, 2s2 2p6, 3; 3p6 3d lO , 4s2 4p6 4d lO 4f14, 5? 5p6 5d
The outermost shells of these elements have one electron Li Na h Rb Cs

and the penultimate(nextto outermost) shells containS electrons Metallic radii .(pm) 152 186 227 1,48 265
except in the first member, lithium, which contains 2 electrons, Ionic radii (pm) 76 102 138 152 167
which is the atomic number of helium. Since, the last electron Atomic volume also increases as the atomic number increases.
enters ns-orbital, these are called s-block elements. Li Na K Rb CS
Lithium shows somewhat abnormal properties as its At. volume (roL) 13.0 23.7 44.4 55.8 69.3
electronic configuration is slightly different than the rest of the
(c) Density.= All are light metals. The densities are low.
members. Because of their similarity in electronic configuration,
Lithium, sodium and potassium are lighter than water, for this
[noble gas] nsl, they are placed in the same sub group, i.e., IA
very reason they float on water. Density gradually increases in
of the periodic table and closely resemble in their physical and
moving down from Li to Cs. Potassium is, however, lighter
chemical properties.
than sodium.
1m 2. Physical Properties Li Na K Rb Cs
Density (g/roL) 0.54 0.97 0.86 1.53 1.87
(a) All the alkali elements are silvery white solids. These are The reason for the low values is that these metals have high
soft in nature and can be cut with the help of knife except the
atomic volumes. The abnormal value of potassium is due to
lithium. When freshly cut, they have a bright lustre which
unusual increase in atomic size, i.e., atomic volume.
quickly fades due to surface oxidation.
(d) Melting and boiling points: The energy binding the
The silvery lustre of alkali metals is due to the presence of
atoms in the crystal lattices of these metals is relatively low on
highly mobile electrons of the metallic lattice. There being only
account of a single electron in the valency shell. Consequently,
a single electron per atom, the metallic bonding is not so
the metals have low melting and boiling points. These decrease
strong. As a result of this, these metals are soft in nature.
However, the softness increases with increase of atomic number in moving down from Li to Cs as the metallic bond strength
because there is continuous decrease of metallic bond strength· decreases or cohesive force decreases.
on account of an increase in atomic size. Bigger is the size of Ii Na K Rb Cs
metal kernel weaker is the metallic bonding. Melting point (K) 454 371 336 312 302
(b) Atomic and ionic radii: Group IA atoms are the Boiling point (K) 1615 1156 1032 961 944
largest in their horizontal periods in the periodic table. When (e) Ionisation energies and electropositive character:
the outermost electron is removed to give a positive ion, the Due to their large size, the outermost electron is far from the
size decreases considerably. There are two reasons for this : nucleus and can easily be removed. Their ionisation energies
(i) The outermost shell of electron has been completely or ionisation enthalpies are relatively low. Thus, the metals
removed. have a great tendency to lose the ns 1 electron to change into
(ii) The positive charge on the nucleus is now acting on W ions. These metals are highly electropositive in nature. As
lesser number of electrons, i.e., attraction increases which the ionisation enthalpy decreases from Li to Cs, the electropositive
brings contraction in size. character increases, i.e., metallic character increases. The
Atomic as well as ionic size increases from Li to Fr due to reactivity of these metals increases from Li to Cs. *
the presence of one extra shell of electrons.
*(i) In gaseous state covalent molecules of M2 type are also known.
(ii) Cs metal has golden yellow appearance.
li . Na K Rb Cs of hydration decreases from U+ to Cs+, the hydration energy

Ionisation entrnUPY 520 496 419 403 376 of alkali metal ion also decreases from Li+ to Cs+.
(k1 mol-I) .. Alkali metal ion Li+ Na+ K+ Rb+ Cs+
Decreases
Electropositive or . Increases • Hydration energy (kJ mor l ) -506 -406 -330 -310 -276
metallic nature (h) Electronegativity: The tendency to attract electrons
Reactivity Increases is low as the alkali metals are electropositive. The electro-
The ns 1 electron is
so loosely held that even the low energy· negativity, thus, decreases from Li to Cs as the electropositive
photons (light) can eject this electron from the metal surface. character increases.
This property is termed as photoelectric effect. K and Cs are (i) Conductivity: The alkali metals are good conductors
used in photoelectric cells which are sensitive to blue light. of heat and electricity. This is due to the presence of loosely
(f) Oxidation states: The alkali metals can lose their held valency electrons which are free to move throughout the
ns l electron quite easily to form univalent positive ion, M+. metal structure.
The ion has a stable configuration of an inert gas. (j) Specific heats: The specific heat values decrease
from Li to Cs.
U+ He-configuration
Li Na K Rb Cs
Na+ Ne-configuratio~
Specific heat at O"C 0.94 0.29 0.17 0.08 0.05
K+ Ar-configuration
Rb+ Kr-configliration (k) Heat of atomisation: Heat of atomisation decreases---
Cs+ Xe-configuration fromU to Cs.
Li Na K Rb· Cs
The energy required to pull out another electron from M+
Heat of atomisation(kJ mbr-1) 163.6 104.2 83.2 79.5 75.7
ion is very high, i.e., the second ionisation enthalpy values are
high. This is due to the decrease in the metallic bond strength
U Na K Rb Cs from Li to Cs.
12 (k1 mor l ) 7298 4562 3051 2633·· 2230 0) Flame colouration: The alkali metals and their salts
Consequently, it· is not possible for alkali metals to form impart a characteristic colour to flame (Fig. 6.1).
M2+ ions under ordinary conditions. These metals, thus show U Na K Rb Cs
Crimson red Golden yellow Pale violet Red violet Violet
only one oxidation state, i.e., +1 oxidation state. These metals
are univalent in nature and show electrovalency, i.e., form
electrovalent compounds.
Since the electronic configuration of M+ ions are similar to
those of inert gases, these ions have no unpaired electrons and
consequently are colourless and diamagnetic in nature.
(g) Hydration of ions, hydrated radii and hydration
energy: The salts of alkali metals are ionic and soluble in
water. The solubility is due to the fact that cations get hydrated
by water molecules. .
M+ + aq. ~ [M(aq.)]+ Fig. 6.1 Colour of flames of some alkali metals :
.• Hydrated cation (a) Lithium (Crimson red); (b) Sodium (Golden yellow);
The smaller the cation, the greater is the degree of its. _ (c) Potassium (Pale viol~); (d) Rubidium (Red violet)
hydration. Thus, the degree of hydration of M+ ions decreases
The reason for flame colouration is that the energy of the
from U+ to Cs+. Consequently the radii of the hydrated ion
flame causes an excitation of the outermost electrons which
decreases from Li~ to Cs+.
on return to their original position give out the energy so
[U(aq.W [Na(aq.W [K(aq·W [Rb(aq.W [Cs(aq.W
absorbed in the visible region. The energy released is minimum
Hydrated 3.40 2.76 2.32 2.28 2.27
in the case ofLi+ and increases in order Li+, Na+, K+, Rb+,Cs+.
radii (A)
Thus, the frequency of the light emitted increases in accordance
The ionic conductance of these hydrated ions increases
with the formula E = hv. The frequency of light in lithium is
from [Li(aq.W to [Cs(aq.)]+.
minimum which corresponds to red region of the spectra.
[Li(aq.)t < [Na(aq.W < [K(aq.W < [Rb(aq.>t < [Cs(aq.)t
(m) Reducing nature: An element, which acts as a
Ionic 33.5 43.5 64.5 67.5 68
.mobility at infinite dilution reducing agent, must have low ionisation energy. Alkali metals
act as strong reducing agents as their ionisation energy values
Hydration of ions is an exothermic process. The energy
are low. Since ionisation energy decreases on moving down
released when one gram mole of an ion is dissolved in water
from Li to Cs, the reducing property increases in the same
to get it hydrated is called hydration energy. Since the degree
order. Thus, Li is weakest reducing agent while Cs is the (ii) They have low heat of atomisation and easily come into
strongest reducing agent amongst alkali metals in free state. vaporised form.
The tendency of an element to lose an electron in solution (iii) They have high heats of hydration.
is measured by its standard oxidation potential value (Egx). (a) Reactivity towards air : On exposure to moist air,
Since alkali metals have high Egx values, these are strong redu- all alkali metals except lithium tarnish quickly. The effect of
cing agents.·Because their standard oxidation potentials are so atmosphere increases from Li to Cs. These are, therefore,
strongly positive, the alkali metals can even reduce water. always kept under kerosene to protect them from air.
2Na(s) + 2H20(l) ~ 2NaOH(aq:) +·H2(g) M ~ M 20 H 20 )MOH ~ M 2C0 3
.However, it is observed that Li is the strongest reducing Alkali metal Oxide Hydroxide Carbonate
agent amongst alkali metals in solution as Egx value of Li is
maximum. 1 02
Li Na K Rb Cs M 20 2
Peroxide·
Oxidation potential (V) • +3.05 +2.71 .+2.925 +2.93 +2.927
Lithium when heated in air combines with nitrogen to form
It looks surprising at fITst sight that lithium having high nitride, it is due to diagonal relationship with magnesium.
value of ionisation energy amongst alkali metals acts as All alkali metals react directly with most nonmetals (other
strongest reducing agent in solution. This can be explained if than the noble gases). However, only lithium react with nitrogen,
we understand the fact that ionisation energy is the property which it reduces to the nitride ion.
of an isolated atom in gaseous state while oxidation potential A
is concerned when the metal atom goes into the solution. 6Li(s) + N2(g) ~
2Li3N(S)
The ionisation energy involves the change of gaseOus· atom (b) Reactivity towards water: Alkali metals decompose
to gaseous ion, water with the evolution of hydrogen.
M(g) ~ M\g) + e 2M + 2H20~ 2MOH + H2i
while oxidation potential involves the following change: Lithium decomposes water slowly. Sodium reacts with
M(s) ~ M+(aq.) + e water quickly. K, Rb and Cs react with water vigorously. The
The above change occurs in three steps : decomposition is highly exothermic and the evolved hydrogen
sometimes ~nflames. Thus, the reactivity towards water
(i) M(s) ~ M(g) sublimation energy
increases from Li to Cs. This is due to increase of electropositive
(ii) M(g) ~ M+(g) + e-ionisation energy character in the same order.
(iii) M+(g) + H20 ~ M+(aq.) + hydration energy [The oxidation potential of lithium is highest amongst alkali
Sublimation energy is nearly same for all the alkali metals. metals, Le., free energy released in the case of lithium is
The energy required in (ii) step is the ionisation. energy maximum (!3.G =nFEgx)' l:l view of this, it looks rather
which is highest for lithium. U+ ion is smallest in size, hence surprising that lithium reacts gently with water whereas
it has maximum degree of hydration. Thus, in (iii) step, potassium which liberates less energy, reacts violently and
maximum hydration energy is released in lithium. catches fire. The explanation lies in the kinetics (the rate at
which reaction proceeds) rather than in the thermodynamics
Li Na K (that is total amount of energy released). Potassium has a low
. Step (i) +122 kJ +78 kJ +61 kJ melting point and heat of reaction is sufficient to make it melt
Step (ii) +520 kJ +496 kJ +419 kJ or even vaporise. The molten metal spreads out and exposes
Step (iii) 506 kJ - 406 kJ - 330 kJ a larger surface to the water, so it reacts even faster, gets even
overall 136 kJ 168 kJ 150 kJ hotter and catches fITe.]
Thus, with greater ease the following overall change occurs The alkali metals also react with alcohols fonning alkoxides
in lithium and it acts as a strongest reducing agent : with the evolution of hydrogen. This reaction is used in
M(s) ~ M+(aq.) + e preliminary test of alcoholic group.
It is, therefore, concluded that highest reducing power 2Ll + 2C2H sOH ~ 2C 2H s OLi + H2 i
of lithiuni in solution is due to its large heat of hydration. Ethyl alcohol Lithium ethoxide
(C) Affinity for non-metals: Alkali metals have great
?i': 3. Chemical Properties affinity for non-metals.
Alkali metals are highly reactive metals and the reasons for (i) Reactivity towards hydrogen: The alkali metals
high reactivity are : combine directly with hydrogen to form crystalline hydrides of
(i) They have low values of ionisation energies and readily . the formula MH. These hydrides are ionic and contain the
lose their valence electron to form M+ ion. hydride ion, H-.
2M + H2~ 2MH
The electrolysis of the fused hydride (LiH) yields hydrogen electron bond is present between two oxygen atoms. Yellow
at anode [other hydrides decompose before melting.] The colour of Na2~ is probably due to the presence of small
hydrides react with water liberating hydrogen. amount of superoxide. Superoxides are even stronger oxidising
MH + H20~ MOH + H2t agents than peroxides.
The ionic character of the bonds in these hydrides increases.
from LiH to CsH and their stability decreases in the same order.
They are powerful reducing agents especially at high
temperatures.
SiCl4 + 4NaH ~ Si~ + 4NaCI
(ii) Reactivity towards oxygen (oxides and hydroxides):
Affmity towards oxygen increases. When heated in atmosphere
of oxygen, the alkali metals ignite and form oxides. On
combustion Li forms Li20; sodium gives the peroxide, Na202;
and potassium, rubidium and caesium give superoxides, M~.
Nonnal oxide Peroxide Superoxide

(LizO) (NaZ02) (K02• RbOz. CsOz)
Fig. 6.2 When alkali metals react with oxygen gives
The normal oxides contain 0 2- ion, the peroxides contain different colour oxides : (a) lithium gives light colour oxides
O~- ion and superoxides contain 02" ion. The peroxides and (b) sodium gives very pale yellow peroxide and (c) potassium
superoxides become more stable with increase in atomic number gives yellow coloured superoxide
of the alkali metal. The formation and stability of these oxides
(iii) Reactivity .towards haJogens: The alkali metals
can be explained on the basis of lattice energy effects. Li+ ion
directly react with halogens forming the halides of the type MX.
being a small ion has a strong positive field around it and can
stabilise only a small anion, 0 2- whereas Na+ being a large 2M + X2~ 2MX
cation can stabilise a large ion and so on. The reactivity of alkali metals towards a particular halogen
increases from Li to Cs. On the other hand, reactivity of halogens
0 2-
Oxide ion
[-O-O-f-
Peroxide ion
[:0 ~ 0:]
Superoxide
towards a particular alkali metal decreases from F2 to 12 i.e.,
F2 > Cl 2 > Br2 > 12
The normal oxides 'M20' react with water to form With the exception of certain lithium halides, the alkali metal
hydroxides. halides are ionic compounds (M"'X-). The halides are crystalline
M 20 + H 2 0 ~ 2MOH and have high melting and boiling points. The fused halides are
good conductors of electricity and are used for the preparation
The basic nature of the oxides (M20) increases gradually
of alkali metals. All halides except LiF dissolve in water.
on moving down in the group. The hydroXIdes (MOH) are
Alkali metal halides are colourless but on heating they turn
colourless, strong alkaline and corrosive compounds. These
yellow, blue, etc., owing to non-stoichiometry and crystal
are soluble in water and dissolve with the evolution of heat.
defects.
The hydroxides are thermally stable except LiOH. The relative
Halides of potassium, rubidium and caesium have a property
strength of the hydroxides increases from LiOH to CsOH.
of combining with extra halogen atoms forming polyhalides.
CsOH > RbOH > KOH > NaOH > LiOH
KI + I2~ KI3
The crystal structures of Li 20, Na20, K20 and Rb20 are
[The insolubility of LiF in water can be explained in the
antifluorite structures. Cs20 has an anti-CdCl2 layer structure.
following manner. The lithium ion has the highest energy of
The higher oxides, viz., peroxides and superoxides are strong hydration as it is small in size in comparison to other alkali
oxidising agents. They react with dilute acids forming hydrogen metal ions and thus it should have high solubility. However, the
peroxide and oxygen respectively. small Li+ and P- ions interact very strongly resulting in high
Na202 + H 2S0 4 ~ Na2S04 + H20 2 lattice energy of LiF which is responsible for its insolubility
4K0 2 + 2H 2S04 2K2S04 + 2H20 + 302
~ (the ionic compounds, which possess low value of lattice
energy, are freely soluble in water).]
2K02. + 2H20 ~ 2KOH + H202 + 0,
(iv) Action with snlphur and phosphorus: Alkali metals
The peroxides are diamagnetic in nature (all the electron;., '1irectly combine with sulphur and phosphorus when heat~
are paired) and are regarded as the salts of the dibasic acid, wiU~ them. The monosulphides, M2S, cannot be obtained by
H2~' The superoxides are paramagnetic and coloured as odd
passing H2S through their salt solutions as sulphides get (iii) Nature of sulpbates: Sulphates of the type M2S04
hydrolysed. are known. With the exception of Li2S04, other sulphates are
M2S + H20 ~ MOH + MHS soluble in water. The sulphates when fused with carbon form
Phosphides on hydrolysis evolve phosphine. sulphides.
3M + P ---t M3P M 2S0 4 + 4C ---7 M2S + 4CO
M3P + 3H20 ---t 3MOH + PH3 The sulphates of alkali metals form double salts with the
(d) Nature of oxysalts: Alkali metals readily react with sulphates of the trivalent metals like Fe, AI, Cr, etc. The double
oxyacids forming corresponding salts with evolution of sulphates crystallise with large number of water molecules as
hydrogen. Lithium salts behave abnormally due.to polarising potash alum, K2S04·AI2(S04h·24H20 consists of 24 water
power ofLi+ ion (small size) and lattice energy effects. However, mole(:ules. Sulphate of lithium is not known to form alum.
the salts of rest of the alkali metals behave similarly and there (tv) Nature of perchlorates: Perchlorates of the type
is a gradual gradation in their properties with the increase of MCl04 are known. The stability increases gradually as larger
atomic number. M+ ion form more stable lattice with large CI0 4 ion. The
(i) Nature of carbonates and bicarbonates: All the alkali solubility of perchlorates decreases.
metals form carbonates of the type M2C03' Since the alkali LiCI04 > NaCl04 > KCI04 > RbCI04 > CSCI04
metals are highly electropositive, their carbonates are highly
LiCI04 is ten times more soluble than NaCI04. It is mainly
stable towards heat and readily soluble in water. As the
due to extensive solvation of smaller Li+.
electropositive character increasesfrom-Li to Cs, the stability .. (c) SOlubility iniiqUid ammonia:· The -alkali ~~tals
of the carbonates increases in the same order. dissolve in liquid ammonia without the evolution of hydrogen.
CS2C03 > Rb2C03 > K2C03 > Na2C03 > Li2C03 The colour of the dilute solutions is blue. The metal atom loses
LizC03 decomposes on heating and is insoluble in water. electron and it combines with ammonia molecule.
The aqueous solutions of carbonates are alkaline. This is M ---7 M+ (in liquid ammonia) + e (ammoniat~)
due to hydrolysis as carbonates are salts of strong bases and M + (x + y)NH3 ---7 [M(NH3U+ + e (NH 3)y
weak acid (H2C03 carbonic acid). Solvated electron
M2C03 + 2H20 ~ 2MOH + H2C03 On heating its blue colour changes to bronze.
Strong alkali Weak acid It is ammoniated electron which is responsible for colour.
The bicarbonates, MHC0 3, of the alkali metals, with the The solutions are good conductors of electricity and have strong
exception of lithium, are known in solid state. The bicarbonates reducing properties. The solutions are paramagnetic in nature.
are soluble in water. On heating, bicarbonates decompose into When dry ammonia is passed over hot metal, amides are
carbonates with evolution of C02. formed.
2MHC0 3 ~ M2C03 + H 20 + C02 2M + 2NH3 ---7 2MNH2 + H2 i
Amide .
The abnormal behaviour of Li2C03 towards heat can be The amides are decomposed by cold water with evolution
explained in the following manner.
of NH3 •
The Li+ ion exerts a strong polarising action and distorts the
electron cloud of the nearby oxygen atom of the large CO§- MNH2 + H 20 ---7 MOH + NH3
ion. This results in the weakening of the C--O bond and Recent studies proved the existence of Li(NH 3)4, a
strengthening of the Li--O bond. This ultimately facilitates the golden yellow solid.
decomposition of Li2C03 into Li20 and C02. The lattice energy (f) Formation of alloys: The alkali metals form alloys
of Li20 is higher than the lattice energy of carbonate. This also· amongst themselves and with other metals. These combine
favours the decomposition of Li2C03' with mercury readily forming amalgams.
Lithium due to its less electropositive nature, does not form (g) Complex formation: Alkali metals have a very little
solid bicarbonate. tendency to form complexes. Lithium being small in size forms
(ii) Nature of nitrates: Nitrates of the type, MN0 3, are certain complexes but this tendency decreases as the size
. known. These are colourless, soluble in water and electrovalent increases .
in nature. The nitrates do not undergo hydrolysis. With theexcep- (Ie j Extraction of alkali metals: Alkali metals cannot
tion ofLiN03, the other nitrates decompose to nitrites and oxygen. be extracted by the application of common processes used for
the extraction of metals due to following reasons:
2MN03 ---t 2MN02 + O2
(i) Alkali metals are strong reducing agents, hence cannot
Lithium nitrate decompose to oxide on heating, it is due to
be extracted by reduction of their oxides and other compounds.
diagonal relationship with magnesium.
(ii) Being highly electropositive in nature, it is not possible
2LiN03 ---7 Li 20 + 2N02 + ~ O 2 to apply the method of displacing them from their salt solutions
by any other element.
(iii) The aqueous solutions of their salts cannot be used for (xi) Lithium reacts with bromine very slowly. Other alkali
extraction by electrolytic method because hydrogen is discharged metals react violently.
at cathode instead of an alkali metal as the discharge potentials of (xii) Lithium fluoride (LiP), lithium phosphate (Li3P0 4),
alkali metals are high. However, by using Hg as cathode,alkali lithium oxalate (Li 2C 20 4), lithium carbonate (Li2C03), etc.,
metal can be deposited. The alkali metal readily combines with are sparingly soluble in water. The corresponding salts of other
Hg to form an amalgam from which its recovery is very difficult. alkali metals are freely soluble in water.
The only successful method, therefore, is the electrolysis (xiii) LiCl is highly deliquescent and soluble in alcohol and
of their fused salts, usuaJly chlorides. Generally, another pyridine. LiCI separates out from aqueous solution as hydrated
metal chloride is' added to lower its fusion temperature. crystals LiCI·2H20 whereas chlorides of other alkali metals are
~";:!;l insoluble in organic solvents and do not form hydrated crystals
6..;~ ABNORMAL BEHAVIOUR OF LITHIUM under ordinary temperatures.
The lithium, beingthe first member of alkali group, exhibits the (xiv) Li when heated in NH3 forms imide Li2NH while other
characteristic properties of alkali metals but it differs at the alkali metals form arnides, MNH 2 .
same time in many respects from them. Reasons for its (xv) LiOH is much weaker base than NaOH or KOH.
6;~1 DIAGONAL RELA'"IONSHIP :

abnormal behaviour are mainly due to the following
reasons:
(i) Lithium atom and its ion has very small size. Lithium ion SIMILARITIES WITH MAGNESIUM
(Li+) on account of its small size exerts high polarising effect Lithium shows resemblance with magnesium, an element of-.
on anions in its compounds resulting in increased covalent group IIA. This resemblance is termed as diagonaJ relation-
character. ship.
(ii) Lithium atom has highest ionisation enthalpy and low Group I Group IT
electropositive character as compared to other alkali metals.
(iii) Nonavailability of d-orbitals in its valence shell. Li_______ ... Be .
~Mg
(iv) Lithium has strong metallic bonding which is responsible
for its low reactivity to some extent. Na
Lithium differs from alkali metals in the following Reasons for the diagonal relationship are the following:
respects: (i) Electronegativities of Li and Mg are quite comparable.
(i) It is more harder and lighter than other alkali metals. (Li = 1.00, Mg = 1.20)
(ii) It is not affected by air easily and does not lose its lustre (ii) Atomic radii and ionic radii of Li and Mg are not very
even on melting. much different.
(iii) It reacts slowly with water to liberate hydrogen. Atomic radii (pm) . Li 152 Mg 160
(iv) It does not react with oxygen below O°e. When burnt "Ionic radii (pm) Li+ 76 Mg2+ 72
in air or oxygen, it forms only monoxide, Li 20. However, the (iii) Atomic volumes of Li arid Mg are quite similar.
rest of the alkali metals give peroxides or superoxides. Li 20 is
Li 12.97 rnL, Mg 13.97 rnL
much less basic than oxides of other alkali metals.
(v) Lithium is the only alkali metal which directly reacts (iv) Both have high polarising power (ionic potential)
with nitrogen to form Li3N. . . Ionic charge
(vi) Lithium hydroxide decomposes at red heat to form Polansmg power (el» = (I . d·)2
ornc ra IUS
Li20. Hydroxides of other alkali metals donot decompose. Cations with large ionic potentials have a tendency to polarise
2LiOH ~ Li20 + H 20 the anions and to give partial covalent character to compounds.
(vii) Lithium bicarbonate, LiHC03 is known in solution but Lithium resembles magnesium in the following
not in solid state while the bicarbonates of other alkali metals respects:
are known in solid state. (a) Both Li and Mg are harder and have higher melting
(viii) Li2C03 is less stable, as it decomposes on heating. points than the other metals in their respective groups.
Li2C03 ~ Li20 + CO2 (b) Li like Mg decomposes water slowly to liberate hydrogen.
The other carbonates are stable. . 2Li + 2H20 ~ 2LiOH + H2
(ix) LiN03, on heating gives a mixture of N02 and 02 Mg + 2H20 ~ Mg(OHh + H2
while nitrates of rest of alkali metals yield only oxygen, (c) Both the elements combine with nitrogen on heating.
4LiN03 ~ 2Li20 + 4N0 2 + O 2 6Li + N2 ~ 2Li3N
2NaN03 ~ 2NaN02 + O 2 3Mg + N2 ~ Mg3N2
Both the nitrides are decomposed by water with evolution
(x) Li 2S04 is the only alkali metal sulphate which docs n0t
of ammonia (NH3).
form double salts, e.g., alums.
Li3N + 3H20 ~ 3LiOH + NH3 atom is available. Thus, alkali metals are soft in nature. However,
Mg3N2 + 6H20 ~ 3Mg(OHh + 2NH3 the size of the metal ion increases with increasing atomic
number, the metallic bond strength decreases and, therefore,
(d) Both Li and Mg combine with carbon on heating.
softness increases.
2Li + 2C ~ Li2C2 (b) The small size of Li+ gives it a huge polarising power.
Mg+2C~ MgC2 The electron cloud of larger halide ion gets distorted and this
Both the carbides yield' C2H2 with water. leads to covalency.
(e) Lithium forms only monoxide when heated in oxygen. (c) The dense charge of Li+ attracts several layers of water
Mg also forms the monoxide. mol~ules around it, i.e., Li+ has maximum degree of hydration.
4Li + 2Li20 Thus, the size of the hydrated lithium ion is largest in comparison
to the size of the other hydrated metal ions which affects its
2Mg -+ O2 ---:--t 2MgO
movement in solution ...
Both the oxides are less soluble in water. (d) The small size of both the Li+ and P- ions leads to a
(f) Hydroxides ofLi and Mg are weak bases and are slightly
very large lattice energy and thus, the crystal is very hard to
soluble in water. Both decompose on heating. break apart.
lliOH ~ Li20 + H2 0 (e) The salts of Li+ with small anions have high lattice
Mg(OHh ~ MgO + H20 energy and thus very stable while with large anion, the lattice
(g) Lithium fluoride, phosphate, oxalate and carbonate, like energy-decreases aria""the salts~~become less stable~ ~~-:;."-C~--~---~-
the corresponding salts of Mg, are sparingly soluble in water. . Example 2. Explain the following:
. (h) Carbonates of Li and Mg decompose on heating. (a) Alkali metals do not occur free in nature.
Li2C03 ~ Li 20 + CO2 (b) Alkali metals are good reducing agents.
(c) Alkali metal salts impart colour to the flame.
MgC0 3 ~ MgO + C02
[Roorkee 1986]
(i) Nitrates of Li and Mg decompose on heating giving (d) Sodium is kept under kerosene,
mixture of nitrogen dioxide and oxygen. .' (e) Potassium and caesium are used in photoelectric cells.
4LiN03 ~ 2Li20 + 4N02• + O2 Solution: (a) Since the ionisation potential values of (llkali
2Mg(N0 3h ~ 2MgO + 4N02 + O2 metals are low, they are very reactive in nature. They readily
(j)Chlorides of both Li and Mg are deliquescent and soluble combine with oxygen, moisture and CO2 of the atmosphere
in alcohol and pyridine. Lithium chloride like magnesium and many other substances. Hence, they do not occur free in
chloride, (MgCI2·6H20) separates out from solutions as nature.
hydrated crystals, LiCI·2H20. (b) Alkali metals act as strong reducing agents because they
(k) Li2S04 like MgS04 does not form double sulphates, can lose valency electrons easily on account of low ionisation
i.e., alums. potential values and high values of oxidation potentials.
(1) The bicarbonates of Li and Mg dO not exist in solid state,
(c) The energy of the flame causes an excitation of the
they exist in solutions only. outermost electron which on return to its original position
gives out energy so absorbed in the visible region. The amount
(m) Lithium salts. like magnesium salts undergo hydrolysis.
of energy released increases' from Li+ to Cs+. Thus, the
(n) Alkyls of Li and Mg are soluble in organic solvents. frequency of light emitted increases in accordance with the
Example 1. Explain the following: formula E = hv. The frequency of light is minimum in lithium
(a) The softness of group fA metals increases down the which corresponds to red light.
group with increasing atomic number. tHT 1986] (d) Sodium is highly electropositive and hence is very reactive.
(b) Lithium salts have a greater degree of covalent character It readily combines with oxygen, moisture and CO 2 of the
than other halides of the group. atmosphere. Hence, it is always kept in kerosene as to prevent
(c) Li+ ion is far smaller than the other alkali metal ions the action of atmosphere.
but it moves through a solution less rapidly than the others. (e) Because of low ionisation potentials, potassium and
(d) Lithium fluoride has the lowest solubility of the group caesium are used in photoelectric cells. The low energy photons
fA metal halides. (light) can eject electrons from their metal surface.
(e) Salts of lithium having small anions are more stable
than the salts having larger anions. 6.~~ LITHIUM
Solution : (a) The metallic bond strength is low in the Occurrence: Lithium is rare but is widely distributed in
case of alkali metals as only one electron per large sized metal the earth's crust. Its amount present in any mineral is generally
274 ORB. Inorganic Chemistry for Competitions
low and, thus, its extraction is somewhat difficult. Important H3P04 + FeCl 3 ~ FeP04 + 3HCI
minerals of lithium are: . The filtrate is evaporated to dryness and the solid residue is
(a) . Aluminosilicates : These include the following extracted with hot water. Mn is removed as MnS by the addition
minerals. of BaS.
(i) Ltlpidolite or lithiamica, (Li, Na, Kh-AI2(Si0 3h(F, OHh. MnCl2 + BaS ~ MnS + BaCl2
It contains 2-6% lithium. ppt.
(ii) Si>odumene, LiAI(Si03h. It contains 3.8 to 5.6% lithium. The filtrate is now treated with H 2S04 to remove barium as
(iii) Petalite, LiAI(Si 20sh It contains 2 to 3% lithium. barlUJ.Tt sulphate.
(b) Phosphates: These include the following minerals: .. \ BaCl2 + H2S04 BaS04 + 2HC}
(i) Triphylite, (Li, NahP04·(Fe, Mnh(P04h It is a double
BaS + H2S04 ~ BaS04 + H2S
phosphate and contains about 1.5 to 3.5% lithium.
The filtrate containing Li2S04 and Na2S04 is evaporated
(ii) Amblygonite, Li(AlF)P04. It contains 7 to 10% lithium.
with oxalic acid. The oxalates of lithium and sodium formed,
Lithil,lm occurs in traces in soils, sea water, certain spring
on ignition give corresponding carbonates.
waters, blood, muscular tissues and ashes of some plants such
as sugar cane, beat, tobacco, coffee, etc. Li2S04 + H2C204 ~ Li2C204 + H 2S04
Lithium occurs in India mainly as lepidolite in Bihar, Kashmir, Li 2C20 4 ---? Li 2C03 + CO
Karnataka and Rajasthan.
Na2C204 ~ Na2C03 + CO
Extraction: The extraction of lithium from anyone of
The carbonates on treatment with HC} give their chlondes.
the minerals involves two steps:
LiC} is extracted .from the mixture with pyridine.
(i) Preparation of lithium chloride from the mineral.
(ii) Electrolysis of lithium chloride.
• (ii) Electrolysis of LiCI
~ (i) Preparation of Lithium Chloride, LiCI Lithium is obtained by the electrolysis of a fused mixture of
lithium chloride and potassium chloride in equal amounts. The
(a) From lepidolite: The powdered mineral is fused
addition of potassium chloride serves the following purposes:
with a mixture of barium carbonate, barium sulphate and
(i) It increases the conductivity of the fused maSs.
potassium sulphate. In fused state, two layers are separated.
(ii) It lowers the fusion temperature of lithium chloride.
The upper layer contains sulphates of lithium, sodium and
The electrolysis is carried out in a steel vessel with refractory
potassium while the lower layer contains heavier materials
lim~g inside. The cell is fitted with a graphite anode and a steel
such as silicateS, barium sulphate, aluminium sulphate, alumina,
cathode which is surrounded by cast iron enclosure so that
silica, etc.
lithium and chlorine formed during electrolysis may not come
The upper layer is dissolved in minimum quantity of in contact with each other (Fig. 6.3).
water and then the solution is treated with barium chloride.
The sulphates of Li, Na and K react and form corresponding
soluble chlorides and insoluble barium sulphate with barium
chloride.
Steel vessel
.Li2S04 + BaCl2 ~ 2LiCI + BaS04 Cast iron --!l~---I
enclosure Brickwork
Na2S04 + BaCl2 ~ 2NaCI + BaS04 (Refractory
Fused lining)
K2S04 + BaCl2 ~ 2KCI+ BaS04
LiCI + KCI
The insoluble barium sulphate is removed by filtration. The
solution containing chlorides of Li, Na and K is evaporated to
dryness. LiCI is extracted from the solid residue with the help
of pyridine. LiCI dissolves in pyridine while other chlorides
remain insoluble. From the pyridine solution, LiCI is recovered
by distillation. . _ - - - - - Steel cathode
(b) Fromtriphylite ore (phosphate ore) : The
powdered ore is digested with conc. HCl. H 3P04 comes into
the solution along with chlorides of Li, Na,'Mn'and Fe. The Fig . .6.3 Electrolysis of lithium chloride
phosphate is removed from the solution in the same manner as
it is done in qualitative analysis. The solution is neutralised with The cell is operated at a voltage of 8-9 volt at 400-450°C
NH40H and then a buffer solution containing CH3COOHand temperature. When electric current is passed, lithium ions, in
CH3COONa is added. Now neutral FeCl3 solution is added preference to potassium ions, get discharged at cathode while
when FeP04 gets precipitated. It is filtered off. chloride ions are discharged at anode.
40 ~ Li++ CI- Except LiF, all other halides show somewhat covalent nature
as the small Li+ cation brings more and more' polarisation
At cathode, Li+ f.l e ~ Li (distortion) in the molecule as the size of the halide ion, X-,
At anode, 2Cr ~ Cl2 + 2e- ; increases.
The molten lithium containing about 1.3% of potassium, (v) Reactivity towards adds: Lithium, bei!1g strongly
being lighter, rises to the surface of the fused electrolyte in the electropositive, reacts with dilute and conc. HOI and dilute
cast iron enclosure. The metal is removed intermittently and H2S04 (non-oxidising acids) liberating hydrogen.
stored either in well stoppered bottles or in liquids like ether,
2Li + 2HCI ~ 2LiCI + H2i
petrol, etc.
2Li + H2S04 ~ Li 2S04 + H2i
• Properties However, the reaction with cone. H2S04 is slow. HN03
Physical : (i) It is a silvery white metal. It is harder than attacks lithium violently. The metal melts and catches rrre.
sodium and potassium. It has two naturally occurring isotopes 2Li + 2HN03 ~ 2LiN03 + H2i
~Li and ~Li. ~Li is most stable isotope. ~Li is used as tritium The oxy-salts are not stable towards heat and decompose
source in thermonuclear reactions. on heating forming stable monoxide, Li 20.
~Li + 6n~ 1H + iHe
(ii) It is very light. _It's density is 0.534 at 20°C which is the
2LiN03 ~ Li20 + 2N02 + G) 02
lowest of all metals. Li 2C0 3 ~ Li20 + CO2 ''

(iii) It melts at 180SC. When volatilized it imparts red (vi) Reactivity towards alkalies: Alkalies have no action
colour to flame. Its boiling point is 1347°C. on lithium.
(iv) It is a good conductor of heat and electricity. It has the (vii) Reactivity towards ammonia: Lithium reacts with
highest specific heat (0.96). ammonia when passed over hot metal to yield H2.
(v) It forms ap. amalgam and alloys with a number of other 2Li + NH3 ~ Li2NH + H2
metals. An alloy of composition, Li = 1.1%,' Cu =4.5%, (Lithium imide)
=
Mn 0.5%, Cd =0.2% and rest Al is used in aircraft construction. However, lithium dissolves in liquid ammonia and forms
Chemical: (i) Reactivity towards air: . Litilium is not blue coloured solution.
affected by dry air but i"s oxidised when moisture is present. (viii) Lithium forms a number of alkyls and aryls. These
When heated in air above 180°C, it burns with brilliant light compounds are formed from the alkyl or aryl halides, usually the
forming lithium oxide and lithium' nitride. chloride, in the solvent such as ether, cyclohexane or toluene.
4Li + O2 ~ 2Li20 (Lithium oxide) RCI + 2Li ~. LiR + LiCI
6Li + N2 ~ 2Li3N (Lithium nitride) These compounds are usually tetrameric, (LiCH3)4, or
(ii) Reactivity towards water: Lithium reacts with water hexameric, (LiC2Hs)6' These lithium alkyls or aryls are used
forming lithium hydroxide and liberating hydrogen. However, in the preparation of organometallic and organic compounds.
the reaction is not vigorous due to high melting point. LiR + CO2 ~ RCOOH + LiOH (carboxylic acids)
2Li + 2H20 ~ 2LiOH + H2i LiR + Clz ~ R-CI + LiCI (alkyl/aryl halide)
(iii) The oxidation potential of lithium is high, i.e., + 3.04 2LiR + 3CO ~ R2CO + 2LiCO (ketones)
volt. Thus, it acts as a strong reducing agent in solution. 3LiR + BCI3 ~ BR3. + 3LiCI (organoboron compound)
(iv) Reactivity towards non-metals: Lithium combines 4LiR + SnCl4 ~ SnR4 + 4LiCl (organotin compound)
with a number of non-metals and form stable compounds. The 2LiR + HgI2 ~ HgR2 + 2LiI (organomercury
reaction usually occurs when lithium is ·heated above its fusion compound)
point. These compounds are ionic in nature and their stability is
due to the fact that a small lithium cation is held by a small anion. • Uses
2Li + H2 ~ 2LiH(Lithium hydride) (1) In the refining of metals : Lithium is used as
6Li + N2 ~ 2Li3N (Lithium nitride) deoxidiser in the purification. of nickel and copper. It removes
4Li + O2 ~ 2Li20 (Lithium oxide) the last traces of oxygen and nitrogen.
2Li + S ~ Li 2S . (LithiuPl sulphide)
. (ii) In the preparation ,Of useful alloys: Lithium is used
3Li + P ~ Li 3P (Lithium phosphide)
in the manufacture of a nurri~~r:of alloys. It increases tensile
2Li + 2C'~ Li2C2 (Lithium carbide)
strength and resistance to cQITosion.
2Li + X2 ~ 2LiX (Lithium halide)
(a) Lead-lithium alloy is used fcir making bearings for motor
(X :::: F, Cl, Br or I)
engines.
(b) Aluminium-lithium alloy is used to make aircraft parts

which are light. and strong. .
(c) MagIlesium-lithium alloy is.used to make armour-plate.
(iii) Thermonuclear purposes: There is a great interest
in lithium for thermonuclear purposes, since when bombarded
with neutrons, it produces tritium.
63 L1· + 0In 3 H + 4He'
I 2
~ Li + bn----7 fH + iHe + 1tz
It is also used in the production of thermonuclear energy
required for propelling rockets and missiles. Fig. 6.4 Elemental sqdium is a soft metal that can be
(iv) Lithium batteries :. Lithium batteries are used' cut easily with a knife.
wherever a reliable current is required for a lengthy period.
Pacemaker battery is a type of lithium battery. Lithium is u~d never found free in namre. The most impdrtant compound of
to make both primary and secondary batteries. Primary batteries sodium found in nature is the common Sallt (NaCl). It is also
known as lake salt, rock salt, sea salt, connmon salt or table
have Li-anodes, carbon cathodes and SOCl2 as an electrolyte.
salt. Sea water contains 2.0--2.9% sodium chloride. Sodium
It is strongly favoured to replace the lead-acid battery for
metal as well as other sodium compounds are produced from
electric vehicle propulsion.
sodium chlclride. Other important compoun(fs of sodium found
(v) Lithium compounds have .a'Qum.ber of applications:
in nature are:
(a) Lithium hydroxide is used i~' the production 6nithl~m
soaps, which are used in makirlg lubricating greases frop1 oil (i) Chile saltpetre, NaN0 3
(lithium soap thickens the oil). More"than 60 per centofau (ii) Glauber's salt, Na2S04·lOH20
automotive greases contain lithium. The compound used is (iii) Trona, Na2C03·2NaHC03·3H20
lithium stearate, C 17H 3S COOLi, which is mixed with oil to give (iv) Natron, Na2CO:rH20
a water resistant grease-like material that does not harden at (v) Tincal (Borax), Na2B4~·lOH20
cold temperatures and also stable at high temperatures. (vi) Cryolite, Na3AlF6
(b) Lithium aluminium hydride, LiAl~, is used as a reducing (vii) Soda feldspar, NaAlSi30 s .
agent in organic chemistry.
(c) Lithium carbonate (Li'lC03), which is obtained from • Preparation
lithium ore, is the primary source of other lithium compounds.
Sodium is obtained on large scale by two processes :
Lithium carbonate is also used in the preparation of special
(i) Castner's process
type of glass. It increases the strength and resistance ,of glass.
(ii) Down's process
Significant quantities of lithium carbonate are also used in the
(i) Castner's process: In this process, electrolysis
preparation of porcelairI, enamels and glazes.
of fused sodium hydroxide is carried out at 33(fC using iron
(d) Lithium chloride is used in air-conditioning plants.
as cathode and nickel as anode.
(e) Lithium bicarbonate, lithium salicylate, lithium acetyl
2NaOH ~ 2Na+ + 20H-
salicylate, etc., are used in medicines.
(f) Litlllum alkyls/aryls are used in the preparation of At cathode: 2Na+ + 2e ----7 2Na
organometallic compounds. Butyllithium, LiC4H9, is a useful At anode: 40H- ----7 2H20,+ O 2 + 4e
reagent in organic chemistry. During electrolysis, oxygen and water are produced. Water
(g) Lithium compounds have been used in the synthesis of formed at the anode gets partlyevaporatep and is partly broken
vitamin-A and some pharmaceuticals. down and hydrogen is discharged at cathode.
(h) Lithium salts are used in ceramics to prevent surface . H20 ~ H+ + OH-
cracking of pottery.
At cathode: 2iit+ + 2e ~ 2H ~ H2 t
(i) Lithium hydroxide is used to remove carbon dioxide 7" .~,,:.
from air in spacecraft and submarine. eii) Down's' i Qcess: Now-a-days sodiuni metal is
manufactured by this process. It involves the electrolysis of
6.4 SODIUM fused .sodium chloride containing calciu~ chloride and
potassium fluoride using iron as cathode and graphite as anode
Sodium is soft, silvery-grey, most abundant alkali metal. It can
at about 600"C, the melting point of the mixture.
be cut easily with a sharp knife (Fig. 6.4). It forms 2.27% of
Sodium chloride, obtained from rock salt or sea water, is
the earth's crust. It was isolated by Sir Humphry Davy in 1807
mixed with calcium chloride and melted. The calcium chloride
by the electrolysis of fused caustic soda. Being reactive, it is
is added to'the sodium chloride electrolyte to reduce the working
temperature of the cell from SO 1°C (the melting point of sodium • Properties
chloride) to 600°C (the melting point of the mixture). This
Physi II Properties: (a) It is a silvery white metal
saves electrical energy and, therefore, makes the process more
when freshly cut but the surface is readily tarnished on exposure.
economical.
The most stable isotope of sodium is tiNa. Many radioactive
Chlorine NaCI . . . 20 21 22 24 2S
Isotopes of sodmm such as llNa, llNa, llNa, llNa, llNa are
Steel gauze t 24
known. Among these ]]Na has shortest halflife (0.02 seconds).
-
(b) It is soft in nature and lighter than water.
(c) It is malleable and ductile in nature.
Molten sodium
(d) It is good conductor of heat and electricity.
collects in _ . •_ _ _ II1II. (e) It has low melting point. It melts at a temperature of
storage tank only 371 K or 97.SoC (Just below the normal boiling point of
water) and its boiling point is 1156 K.
(f) With mercury, it forms an amalgam.
(g) It dissolves in liquid ammonia forming intense blue
coloured solution.
(h) It gives two bright -lines D 1' (5S9.2 nm) and D2
Molten sqdium
chloride -+- upto (590.4 nm) in the yellow region of spectrum.
60% CaCr 2 Chemical Properties: (a) Reactivity towards air:
On keeping it in the moist atmosphere, it loses its lustre on
Graphite anode account of the formation of oxide, hydroxide and carbonate.
4Na + O 2 -----t 2Na20 2H 20 ) 4NaOH IlC0 2
Fig. 6.5 The Down's cell used for the electrolysis Moisture In atmosphere
of sodium .chloride 2Na2C03 + 2H 20
The cathode is a circle of steel around the· graphite It is always-,therefore;,_kept under kerosene because it
cffiode. At 600°C sodium and chlorine would react violently corrodes rapidly by reacting with water vapour in. the air. On
t.ogether to re-form sodium chloride. To prevent this from heating in air or oxygen, it fOmls'a"imlxtlite: 6fNa:;0 and
happening, the Down's cell contains a steel gauze around the Na202' Na202 is industrially known as oxone.
graphite anode to keep it and the'dathode apart. The molten 4Na + O 2 -----t 2Na20
\
:sodium float on the electrolyte and,i~ run off for storage. A 4Na + 20 2 -----t 2Na202
Sodium peroxide
problem arises, however, is that the\,calcium ions are also
attracted to the cathode, where they'. form calcium metal. The peroxide ion, b~- acts as an oxidizing agent.
Therefore, the sodium which is run off contains a significant (b) RoeadiYity towants water: It decomposes water
amount of calcium. Fortunately, the calcium crystallises out vigorously with evolution of heat _and liber~ting hydrogen.
when the mixture cools and relatively pure sodium metal Sometimes the hydrogen catches fire. '., -
remains. 2Na + 2H 20 -----t - 2NaOH + H2
The worldwide production of sodium metal each year is (e) Readirity towards acids: It is strongly .electro-
about 60,000 to SO,OOO tonnes.- positive in nature, easily loses electron and converted into
The overall reaction which takes place in the cell is, monovalent ion, Na+. On account of this, it readily displaces
NaCI ~ Na+ +!CI- hydrogen from acids and forms corresponding salts.
At cathode: Na+ + e -----t Na 2Na + 2HCI -----t 2NaCI + H2
At anode: 2CI- -----t Cl 2 + 2e (II) AfIioiIy for .......... : It has high affinity for
non-metals. Except carbon and nitrogen, it directly reacts with
Thle electrolysis of pure NaCl presents the following
hydrogen, halogens, sulphur, phosphorus, etc., to form
difficulties:
corresponding compounds on heating.
(a) The fusion temperature of NaCl is hig\h, i.e., SOl°C. At
this temperature both sodium and chlorine are corrosive. 300°C
(b) Sodium forms a metallic fog at this tdmperature. 2Na + H2 -----7 2NaH
To remove above difficulties, the fusion temperature is 2Na + Cl 2 -----t 2NaCI
reduced from SOl°C to 600°C by adding CaCl2 and KF. This 2Na + S -----t Na2S
is a cheaper method and chlorine is obtained as a byproduct. 3Na + P -----t Na3P
Sodium thiocyanate
NaCNS+H2S
NaCN + H20
Sodium cyanide ~ .
'j cs
NaCN + H2 .. NaNH2
ylit. NaH + NH3 .
~SQdamid~
NaOH + NH /y..1! '. NaN3 + H~O
3 Sodium azide
IH S0
2 4
Dry •
ammonia N3 H"(Hydrazoic acid)
Oxidising agent
Electrolysis
of fused NaCI Heated in
" Na20
O2
.
.
II
/1,
Na2~i(Yellow)
containing. air/oxygen. Sodium peroxide~ .
CliCI2 and KF
. OC\ (Oxone)
(C6H5C~)202 .~. \~"":

Benzoyl peroxide -(-!? ~o ~
(Bleaching agent) cF:I Na2COS + O2
". 8
Flowsheet diagram of properties of sodium and preparation of some important compounds
(e) Reducing agent: On account of low valQe of (iv) in molten state in nuclear reactors as heat transfer
ionisation potential and high value of oxidation potential, it acts medium.
as a strong reducing agent. (v) in sodium vapour lamps which emit yellow light.
Si02 +4Na '---7 Si + 2Na20 (vi) as a laboratory reagent for organic analysis.
3C02 + 4Na ~ C + 2Na2C03 (vii) in high temperature thermometers in the form of sodium
Al20 3 + 6Na ~ 2Al + 3Na20 potassium alloy.
(viii) for the extraction of C. Be, Mg and Si.
BeCl2 + 2Na ~ Be + 2NaCI
(ix) largely as a reducing agent in industry for the production
(f) Reactivity towards ammonia: When dry ammonia
of artificial rubber, dyes,' pharmaceutical drugs, etc.
is passed over sodium at 300-400°C in absence of air, sodamide
(x) for mling exhaust valves of aeroplane engines on account
is formed with liberation of hydrogen.
of its lightness and high thermal conductivity.
2Na + 2NH3~ 2NaNH2 + H2 (xi) as a liquid coolant in nuclear power stations.
Sodamide is a waxy solid and is used for making a number (xii) molten sodium metal is used to produce zirconium and
of sodium compounds . titanium from their chloride.
• Uses TiCI 4(g) + 4Na 4NaCI(s) + Ti(s)

Sodium is used :
(i) in the manufacture of various chemicals like sodium . : _ COMPoUNDS OF SODIUM
peroxide (Na2~), sodamide (NaNH2), sodium cyanide
(NaCN), etc. • 1. Sodium Oxide, N~O
. '
(li) for making lead tetraethyl (used as antiknock' in PreparatiOn: It is prepared by heating sodium nitrate or
petrol). sodium nitrite with sodium.
4C2HsCI + 4Na-Pb ~ (C2Hs)4Pb + 3Pb + 4NaCI 2NaN03 + lONa ~ 6Na20 + N2
(iii) in the preparation of sodium amalgam (used as a reducing
2NaN02 + 6Na ~ 4Na20 + N2
agent).
Pure sodium oxide is formed when the mixture of sodium Uses: It is used :
azide and sodium nitrite is heated. (i) as an oxidising agent in laboratory.
3NaN3 + NaN02 ~ 2Na20 + 5N 2 (ii) for theproduction of oxygen under the name oxone.
Properties: It is a white amorphous substance. It reacts (iii) for the purification of air.
with water violently forming sodium hydroxide and evolving a (iv) as a bleaching agent for delicate fibres like wool, silk,
large amount of heat energy. . etc.
(v) for the preparation of benzoyL peroxide.
Na20 + H20 ~ 2NaOH + Heat
(vi) for the preparation of H202.
On heating at 400°C, it disproportionates forming sodium
peroxide and metallic sodium vapour. III 3. Sodium Hydroxide (Caustic Soda), NaOH
400°C
2Na20 ~ Na202 + 2Na Sodium hydroxide, NaOH, is a soft, waxy, white, corrosive
Sodamide is formed when it reacts with liquid ammonia. solid. It is commonly known as lye or caustic soda. It is one
of the important chemicals and is manufactured on a very large
Na20 + NH3 ~ NaNH2 + NaOH scale forming an important chemical industry. It is most
Uses : It is used as dehydrating and polymerising agent in conveniently manufactured by one of the following processes:
organic chemistry.
(a) Methods involving sodium carbonate as a
• 2. Sodium Peroxide, Na202 starting material
Preparation: It is formed by heating sodium in excess Two methods are used. These are:
of air free from moisture and carbon dioxide or in excess of (i) Csusticisation process (Gossage process) :This
pure oxygen. process depends on the reaction between suspension ·of lime
2Na + 02(excess)
3S0°C
~ Na202 (milk of lime, calcium hydroxide) and sodium carbonate. This
reaction is reversible.
Properties: It is a pale yellow powder. On exposure, it ....
becomes white as it reacts with moisture and carbon dioxide. Na2C03 + Ca(OHh ~ CaC03 + 2NaOH
. .......
2Na202 + 2H20 ~ 4NaOH + O2 Calcium carbonate being only slightly soluble separates out
2Na202 + 2C02 ~ 2Na2C03 + O2 as a mud. The temperature is maintained 80-90°C by blowing
At low temperature, it forms H202 with water and acids. steam. Caustic soda solution is drained out and evaporated to
Na202· + 2H20 ~ 2NaOH + H20 2 dryness when flakes of caustic soda are obtained.
The most suitable concentration of sodium carbonate taken
Na20z + H2S04 ~ Na2S04 + H20 2
in this process is 15-20%. The caustic soda produced by this
It combines with CO and CO2,
. method is not pure and contains some calcium carbonate,
Na202 + CO ~ Na2C03 sodium carbonate and calcium hydroxide as impurities.
2Na202 + 2C02 ~ 2Na2C03 + O2 (ii) Lowig's process: In this process, a mixture of
It acts as a powerful oxidising agent. sodium carbonate and ferric oxide is heated to redness in a
(a) Chromic compounds are oxidised to chromates. revolving furnace. Sodium ferrite is thus formed with evolution
[Na202 + H20 ~ 2NaOH .+ 0] x 3 of carbon dioxide.
2Cr(OH)3 + 4NaOH+ 30 ~2Na2Cr04 5H20 + Na2C03 + Fe203 --7 2NaFeOz + C02
Sodium ferrite
2Cr(OHh + 3Na202 ~.2Na2Cr04 + 2NaOH + 2H20
(b) Manganous salt is oxidised to sodium manganate. The sodium ferrite is cooled and thrown into hot water. The
[Na202 + H20 ~ 2NaOH + 0] x 2 hydrolysis of sodium ferrite occurs forming a solution of sodium
hydroxide and insoluble ferric oxide (Fe203).
MnS04 + 4NaOH + 20 ~ Na2Mn04 + Na2S04 + 2H20
2NaFe02 + H 20 2NaOH + Fe203
MnS04 + 2Na202 ~ Na2Mn04 + Na2S04
The solution is filtered and evaporated to dryness to get
(c) Sulphides are oxidised to corresponding sulphates.
flakes of sodium hydroxide.
Na2S + 40 ~ Na2S04
Benzoyl peroxide (bleaching agent) is formed when (b) Methods involving sodium chloride as
C6HsCOCI reacts with Na202' starting material
.. 1:C6HsCOCI + Na202 ~ (C6HSCOh02 + 2NaCI Methods used are electrolytic as the electrolysis of sodium
Benzoyl peroxide
chloride solution is carried out in an electrolytic cell.
280 GR.B. Inorganic Chern:istry for Competitions
Principle: A sodium chloride solution contains Na+, H+, chlorine is liberated at the anode and let out through the
Cl- and OH- ions. outlet. 'Sodium ions penetrate through the asbestos and reach
NaCI ~ Na+ + CI- the cathode where hydrogen and OH- ions are formed by
reduction of water. Sodium ions combine with 0 H- ions to form
H20 ~ H++OH-
NaOH which is collected in the outer tank while hydrogen is
On passing electricity, Na+ and H+ ions move towards drawn off through the outlet. The steam blown during the
cathode and Cl- and OH- ions move towards' anode. The process keeps the electrolyte warm and helps to keep perforation
discharge potential of H+ ions is less than Na+ ions, thus clear.
hydrogen ions get discharged easily and hydrogen.is liberated. NaCI ~ Na+ + cr (in solution)
'Similarly, at anode Cl-ions are easily discharged as their
At cathode: 2H20 + 2e ~ H2 + 20H-
discharge potential is less than that of OH- ions. Cl2 gas is,
Na+ + OH- ~ NaOH
therefore, liberated at anode.
The solution on electrolysis becomes richer in Na+ and OH- At anode : 2CI- ~ Cl2 + 2e
ions. The solution containing NaOH and NaCI as impurity is taken
Since, chlorine reacts with sodium hydroxide solution even out and evaporated to dryness.
in the cold forming sodium chloride and sodium hypochlorite, (ii) Castner-Kellner cell: This is, the common cell in
it is neGessm:y that chlorine should not .come in contact with which mercury is used as cathode. The advantage of using Hg
sodium hydroxide during electrolys!s: _, ______ _ as a cathode is that the discharge potential of Na+ ions is less
2NaOH + Cl2 ---t NaCI + NaCIO + H20 than that of H+ ions.Na+ iOIlS get dis~harged on ~ercury and
sodium so deposited combines with mercury to form sodium
To overcome thi,s probletp, the, anode is separated from the amalgam. The cell consists of a large rectangular trough divided
cathode in the electrolytic cell either by using a porous into three compartments by slate partitions which do not touch
diaphragm or by using a mercury cathode. the bottom of the cell but dipping in mercury as shown in the
Four methods are used, these are: (Fig. 6.7).
(i) Porous diaphragm process (Nelson cell process)
(ii) Castner-Kellner c e l l ' ,
(iii) Solvay-Kellner cell
(iv) Diaphragm cell
(i) Porous diaphragm process (Nelson cell pro-
cess): Nelson cell consists of a perforated steel tube
Graphite anode
<"r;::=...~ Fresh brine

r = : -.... H2
Spenl--:;::=:!===:~ Asbestos
brine lining Fig. 6.7 Castner-Kellner cell
=+--t- NaCI Solution The mercury can flow from one compartment into other
(Brine)
;,t--+- Perforated but the solution kept in one compartment cannot flow into
cathode other. Sodium chloride solution is placed in the two outer
a
-Steam compartments and dilute solution of sodium hydroxide in the
inner compartment. 'Two graphite electrodes which act as
anodes are fixed in the outer compartments and a series of iron
rods fitted in the inner compartment act as cathode. Mercury
in the outer compartments acts as cathode while in the inner
compartment it acts as anode by induction. The cell is kept
Fig. 6.6 Nelson cell rocking with the help of an eccentric wheel.
When electricity is circulated, sodium chloride in the outer
lined inside wi~ ,asbestos. The tube acts as a cathode compartments is electrolysed. Chlorine is evolved at the graphite
(Fig. 6.6).
anode while Na+ ions are discharged at the Hg cathode. The
It is suspended in a steel tank. A graphite rod dipped in sodium liberated sodium forms amalgam with mercury.
chloride solution serves as anode. On passing electric current,
NaCI ~ Na+ + Cl- chloride solution) uses a diaphragm cell, containing steel and
At anode: 2Cl- ~ 2Cl + 2e~ Cl 2 titanium electrodes which are separated by porous diaphragms .
At cathode : . Na+ + e~ Na to isolate the products. The process produces chlorine and
Na + Hg ~ Amalgam _ hydrogen as well as sodium hydroxide.
The sodium amalgam thus fonned comes in the inner 2NaCl + 2H20 ~ 2NaOH + Cl2 + H2
compartment due to rocking. Here, the sodium amalgam acts The porous diaphragm prevents the chlorine -from mixing
as the anode and Iron rods act as cathode. - with the hydrogen and sodium hydroxide. The liquid is drawn
At anode: Na-amalgam ~ Na+ + Hg + e off and the water is partially evaporated. The unconverted
At cathode: 2H20 + 2e ~ 20H- + H2 i sodium chloride crystallizes, leaving the sodium hydroxide in
The concentrated solution of sodium hydroxide (about 20%) solution.
is taken out from inner compartment and evaporated to dryness
to get solid NaOH. • Preparation of pure sodium h.ydroxide
(iii) Solvay-Kellner cell: This is the modified cell.
Commercial sodium hydroxide is purified with the help of
This cell has no compartments. The flowing mercury as shown
alcohol. Sodium hydroxide dissolves in alcohol while impurities
in Fig. 6.8 acts as cathode. A number of graphite rods dipping
like NaCl, Na2C~, Na2S04. etc;, remain insoluble. The
in sodium chloride solution act as anode. A constant level of
alcoholic filtrate is distilled. The alcohol distills off while pure
sodium chloride solution (brine) is maintained in the cell. On
solid sodium hydroxide:. is left-behind.
electrolysis chlorine gas is liberated at anode and Na± ions are
discharged at cathQde (mercury). Sodium discharged dissolves • Properties
in Hg and fonns sodium amalgam.
Physical Properties: (a) ltis a white crystalline solid.
·2Cl- ~ Cl2 + 21 (anode reaction) It has soapy touch.
2Na + 2Hg + 2e --;7 2Na·Hg (cathode reaction) (b) It is highly deliquescent.
sodium-amalgam
(c) Its density is 2.13 g1mL and melting point 318.4°C.
This amalgam flows out in a vessel containing water. Sodium (d) It is highly soluble in water. It is bitter in taste.
hydroxide is fonned with evolution of hydrogen. (e) It is corrosive in nature.
2Na·Hg + 2H20 ~ 2NaOH + 2Hg + H2i (f) Its solubility is comparatively less in alcohol.
+ve Graphite anode Chemical Properties: (a) Reactivity towards atmos-
Brine in phere: It cannot be kept in atmosphere. It absorbs moisture
and carbon dioxide from atmosphere and converted into sodium
carbonate.
2NaOH + C02 '----7 Na2C03 + H20
(b) Strong alkali: Sodium hydroxide is a strong alkali as
it di~sociates completely in water furnishing Na+ and OH- ions.
Sodium Mercury
amalgam out NaOH ~ Na+ + OH-
cathode
(i) It reacts with acids forming corresponding salts.
Fig. 6.8 Solvay-Kellner cell
NaOH + HCI ~ NaCI + H 20
2NaOH + H 2S04 ~ Na2S04 + 2H20
NaOH + HN03 ~ NaN03 + H20
3NaOH + H3P04 ~ Na3P04 + 3H20
NaOH + CH3COOH ~ CH 3COONa + H20 -
(ii) It combines with acidic oxides to fonn salts.
2NaOH + CO 2~ Na2C03 + H 20
Sodium
carbonate
2NaOH + S02~Na2S03 +H 20
Sodium
sulphite
2NaOH + 2N02~NaN03+NaN02 +H 20
Sodium Sodium
Diaphragm Steel cathode nitrate . nitrite
Fig. 6.9 A diaphragm cell for the electrolytic produ~ion of sodium (iii) Amphoteric oxides of aluminium; zinc, tin and lead
hydroxide from brine (aqueous sodium· chloride solution) dissolve in sodium hydroxide forming corresponding salts.
Ah03 + 2NaOH ---7 2NaAl02 + H20 (d) Reactivity towards metals: Metals like Zn;AI, Sn,
Sodium meta- Pb react with sodium hydroxide solution and evolve hydrogen.
aluminate
Zn + 2NaOH ---7 Na2Zn02 + H2
ZnO + 2NaOH ---7 Na2Zn02 .of: H20
Sodium zineate 2Al + 2NaOH + 2H20 ---7 2NaAI02 + 3H2
SnO + 2NaOH ---7 Na2Sn02 + H 20 Sn + 2NaOH + H20 ---7 Na2Sn03 + 2H2
Sodium stannite Pb + 2NaOH + H 20 ---7 Na2Pb03 + 2H2
Sn02 + 2NaOH ---7 Na2Sn03 + H20 [However, Sn and Pb when fused with NaOH form Na2Sn02
Sodium stannate and Na2Pb02, respectively.
PbO + 2NaOH ---7 . Na2Pb02 + H 20 Sn + 2NaOH --+ Na2Sn02 + H2
Sodium plumbite
Pb + 2NaOH ---7 Na2Pb02 + H2]
Pb0 2 + 2NaOH ---7 Na2Pb03 + H20
Sodium plumbate (e) Action on salts: Sodium hydroxide reacts with
metallic salts to form hydroxides which may be insoluble or
(e) Reactivity towards non-metals: Non-metals like
dissolve in excess of NaOH to form salts of oxyacids. Some
halogens; P (yellow), S, Si, B, etc., are attacked by NaOH.
of the hydroxides decompose into insoluble oxides,
(i) Halogens: Hypohalites and halides are formed by
.(i) Insoluble hydroxides: Salts of nickel, iron, man-
reaction of halogens with cold and dilute solution of NaOH.
ganese, copper,- etc., ·fonn insoluble hydroxides.
Cl2 + 2NaOH ---7 NaCl + NaClO + H20
(cold and Sodium hypo- Ni(N0 3h + 2NaOH ---7 Ni(OH}z + 2NaN03
dilute) chlorite
FeS04 + 2NaOH ---7 Fe(OH}z + Na2S04
Br2 + 2NaOH ---7 NaBr + .NaBrO + H20
(cold and Sodium hypo-
FeCl3 + 3NaOH ---7 Fe(OHh + 3NaCI
dilute) bromite Red ppt;
12 + 2NaOH ---7 NaI + NaIO + H20 CrCl3 + 3NaOH ---7 Cr(OHh + 3NaCI
(cold and Sodium hypo- Green ppt.
dilute) iodite
MnS04 + 2NaOH ---7 Mn(OHh + Na2S04
Halogens form halates and halides with hot and concentrated Buff coloured ppt.
solutiot;l of NaOH. CuS0 4 + 2NaOH ---7 Cu(OHh + Na2S04
':3Ct2 + 6NaOH ~ 5NaCI + NaCI0 3 + 3H20 Blue coloured ppt.
(hot and cone.) Sodium chlorate (U) Insoluble hydroxides which dissolve in excess of
3Br2 + 6NaOH ~ 5NaBr+NaBr03 + 3H20 NaOH:
(hot and cone.) Sodium bromate
ZnS04 + 2NaOH ---7 . Zn(OHh + NaZS04
312 + 6NaOH ---7 5NaI + NaI03 + 3H20 White (insoluble)
(hot and cone.) Sodium iodate Zn(OHh + 2NaOH ---7 Na2Zn02 + 2H20
(U) Yellow phosphorus (white) when heated with NaOH Sodium zincate
(soluble)
solution evolves phosphine gas (PH3) along with the formation
of sodium hypophosphite. AICl 3 + 3NaOH ---7 Al(OHh + 3NaCI
White ppt.
P4 + 3NaOH + 3H20 ---7 3NaH2P02 + PH3
Sodium Phosphine AI(OHh + NaOH ---7 NaAl02 + 2H20
hypophosphite Sodium meta-
aluminate (soluble)
(ill) Sulphur on heating with sodium hydroxide solution
SnC12 + 2NaOH ---7 Sn(OHh + 2NaCl
forms sodium thiosulphate. White ppt.
4S + 6NaOH ---7 Na2S203 + 2Na2S + 3H20 Sn(OHh + 2NaOH ---7 Na2Sn02 + 2H20
Sodium thie- Sodium Sodium stannite
sulphate sulphide (soluble)
(iv) Silicon evolves hydrogen when heated with NaOH (ill) Unstable hydroxides :
solution. 2AgN03 + 2NaOH ---7 2AgOH + 2NaN03
2NaOH + Si + H20 ---7 Na2Si03 + 2Hz 2AgOH ---7 Ag20 + H20
Sodium silicate (Brown)
(v) Boron also evolves hydrogen when fused with NaOH.
HgC12 + 2NaOH ---7 Hg(OHh' + 2NaCl
2B + 6NaOH ---7 2Na3B03 + 3H2
Sodium borate
Hg(OHh ---7. HgO + H20
(Yellow)
(f) Reactivity towards ammonium salts: . Ammonium (a) Le-Blanc process

salts are decomposed on heating with sodium hydroxide solution
The raw materials of this process are cominon salt (NaCl),
with the evolution of ammonia gas.
sulphuric acid, coke and limestone (CaC03)' It involves the
NH4CI + NaOH -----7 NH3 i + NaCI + H20 following steps:
. (NH4hS04 + 2NaOH -----7 Na2S04'+. 2NH3 i + 2H20 (i) Conversion of NaCI into Na2S04: The common
(g) Reactivity towards carbon monoxide: NaOH reacts salt is heated with calculated quantity of sulphuric acid
with carbon monoxide under pressure at 150-200°C to form (concentrated) in the furnace shown in Fig. 6.10.
sodium formate. NaCI + H 2S04 -----7 NaHS0 4 + HCI
Sodium hydrogen
NaOH + CO l50-200°C) HCOONa sulphate
5-,-10 atm. Sodium fonnate
The pasty mass of NaHS0 4 is then raked out on the hearth
(h) Caustic property:Sodium hydroxide breaks down
the proteins of skin to a pasty mass. On account' of this
is
of the furnace with common salt. The paste heated at higher
property, it is commonly called as Caustic soda. r==_- Cold water
• Uses
Sodium hydroxide is among the top ten industrial chemicals.
It is an important ind:ustrial chemical because it is an inexpensive Absorption
tower
base for the production of other sodium salts. It is .a strong
base, and this property is useful in many applications. It is used:
(i) as a reagent in. the laboratory.
(ii) in refining of p~troleum. HCI
(iii) in the manufacture of soap.
(iv) in the manufacture of sodium metal.
Hot gases
(v) in the manufacture of paper and rayon.
(vi) in the manufacture of dyes and drugs. I
(vii) as an absorber of gases. Fig. 6.10 Le-Blanc process
(viii) in the manufacture of sodium hypochlorite, sodium
chlorate and sodium nitrite. temperature when sodium hydrogen sulphate is converted into
sodium sulphate. . I
(ix) for mercerizing cotton.
(x) In large quantities in the production of aluminium which NaHS04 + NaCI ~ Na2S04 + HCI
depends on its reaction with the amphoteric aluminium hydroxide. Sodium sulphate, thus formed is technically called salt cake.
The HCI evolved is dissolved in water to form hydrochloric
/IIi 4. Sodium Carbonate or Washing Soda
acid.
(Na2C03·10H20) (ii) Conversion of salt cake into black ash: The salt
Sodium carbonate (Na2C03) is the most important of all cake formed in the first step is broken into small pieces. These
alkali salts in commercial use. It is one of the world's most pieces are mixed with coke and limestone. The mixture is
important industrial chemicals. It occurs in the ashes of marine introduced into the cylindrical revolving furnace where it is
plants which used to be its only source upto 1790. It is also strongly heated. Sodium sulphate is converted into sodium
found as natural deposits like sajji in India and trona carbonate along with calcium sulphide with evolution of carbon
(Na2C03·NaHC03·2H20) in Egypt. The world production of monoxide according to the following reaction.
sodium carbonate now exceeds 30 million tonnes per year. Na2S04 + CaC0 3 + 4C -----7 Na2C03 + CaS + 4CO
'--------v-----
Black ash
Manufacture
The solid residue is called black ash. This contains about
The ftrst process for the manufacture of Na2C03 was
45% sodium carbonate.
invented by Le-Blanc in 1790. However, this process has become
(iii) Recovery of Na2C03: The black ash is crushed
obsolete and has been replaced by modem ·methods. The most
and extracted with water. The sodium carb.onate dissolves and
i.mportant one is Solvay process. The following are the three
the insoluble impurities mainly consisting CaS are left behind.
main processes for the manufacture of sodium carbonate :
The insoluble material is called sludge or alkali waste. The
(a) Le-Blanc process,
solution consisting sodium carbonate is evaporated to get solid
(b) Solvay ammonia soda process and
sodium carbonate,
(c) Electrolytic process.
(b) Solvay ammonia soda process Ammonia mixed with a little carbon dioxide ,if used,
precipitates calcium and magnesium as carbonates.
This is the modern process used for the manufacture of
sodium carbonate worldwide; a large quanti!)' of sodium carbo- CaClz + 2NH3 + HzO + COz ~ CaC03 + 2NH4CI
ppt.
nate is still produced by the solvay process. It is an industrial The clear liquid is now allowed to go into the carbonation
method for obtaining sodium carbonate from sodium chloride tower.
and limestone (CaC03)' The raw materials required in this (ii) Carbonation: Ammonical brine solution is cooled in
process are the common salt, ammonia and limestone. In the the cooling pipe and then allowed to enter a little above the
main steps of this process, ammonia is 1st dissolved in a middle of the carbonation tower packed with perforated plates.
saturated solution of sodium chloride and then carbon dioxide It flows down slowly in the tower and meets with an upward
is passed in it. The process involves the formation of a sparingly stream of carbon dioxide. The sparingly soluble sodium
soluble sodium bicarbonate (baking soda) by the reaction of bicarbonate (NaHC03) gets precipitated. This is taken out
sodium chloride and ammonium bicarbonate in aqueous solution. from the tower.
The reactions taking place in the process are:
NaCl + NH3 + HzO + COz = NaHC03 + NH4CI
NH3 + HzO + CO z ~ Nl4HC03
Ammonium
(iii) Filtration: The solution obtained from carbonation
bicarbonate tower is filtered with the help of rotatory vacuum filter. The
NaCI + NH4HC03 ~ NaHC03 ,:. Nl4CI filtrate is pumped to the top of recovery tower.
Sodium . (iv) ADunollla recovery: The filtrate from the vacullm
bicarbonate filter contains ammonium chloride and· a little ammonium
NH3 + HzO + CO Z + NaCI ~ NaHC03 + NH4CI bicarbonate. Ammonia is recovered from this filtrate by passing
Sodium bicarbonate on heating decomposes into sodium steam and adding Ca(OHh- This ammonia is again used.
carbonate, Heat
~C03 ~ NH3 + HzO + CO Z
2NaHC03 ~ NaZC03 + HzO + C~ 2NH4CI + Ca(OHh ~ 2NH3 + CaClz + 2HZO
The various steps involved in the process are: (V) Calcination: Sodium bicarbonate obtained in step
(i) Saturation of brine with ammonia: This step is (ii) is strongly heated in especially designed cylindrical vessels
done in ammonia absorber (Fig. 6.11). Ammonia from the when sodium carbonate is obtained.
ammonia· generator is circulated through· the solution, The Z50°C
ammonical brine solution i~ allowed to·stand for some time as 2NaHC0 3 ~ Na2C03 + H20 + COz
to allow any precipitate formed to settle down. Ammonia Carbon dioxide used in the carbonating tower is produced
precipitates, the hydroxides of magnesium, iron,calcium, etc.; by heating limestone, CaC0 3.
if present as impurity in the common salt. .CaC03 ~ CaO + COz
Calcium oxide
NH3 + HzO ~ Nl40H
MgClz + 2NH40H ~ Mg(OHh + 2NH4CI The calcium oxide (CaO) produced from this process is
ppt. known as quicklime or lime. It is dissolved in water to form
calcium hydroxide which is used for the recovery of
Brine ammonia.
CO2+ NH3 Limestone
+ Coke The byproduct of this process is calcium chloride. The
Carbonation process on the whole is cheap, self~contained and self-sufficient
I
tower and the product formed, NaZC03, is of high purity.
~
~
l-
~as
'c
E
E
0 ~::'----------CaQt
~ Heat
~ <:
E NaCI- , + NH 4 CI II NH4CI
J
•I ·1
Fig. 6.11 Solvay ammonia soda process Flow Sheet of Solvay Process
(c) Electrolytic process (d) Reaction with slaked lime: Sodium hydroxide
is formed when the solution of sodium carbonate and slaked
In this process sodium chloride is fIrst converted into sodium
lime, Ca(OHh, is heated.
hydroxide by electrolysis. In the Nelson cell used. for _the
manufacture of sodium hydroxide, carbon dioxide under Na2C03 + Ca(OHh --:--1- 2NaOH + CaC03
pressure is blown along with steam. The sodium hydroxide (e) Reaction with sulphur and sulphur dioxide: When
produced will then react with carbon dioxide to form sodium aqueous solution of. sodium carbonate containing sulphur is
carbonate. The solution is concentrated and crystallised. treated with sulphur dioxide, sodium thiosulphate (Na2S203)
is formed. .
. 2NaOH + CO2 --:--1- Na2C03 + H20
H20 ~
Sodium carbonate can also be made in the laboratory by Na2C03 + S02 ----7 Na2S03 + CO2 I
nel.ltralising sodium hydroxide solution with carbon dioxide.
Na2S03 + S --:--1- Na2S203
The solution on concentration and cooling deposits crystals of
(f) Action on salts of non-alkali metals: Sodium
the decahydrate; Na2C03·lOH20.
carbonate reacts with metal salts (except alkali metal salts) to
• Properties form insoluble normal or basic carbonates.
CaCl2 + Na2C03 --:--1- CaC03 + 2NaCI
Physical Properties: (a) S~dium carbonate is a white
crystalline solid. It is known in several hydrated forms. The BaCl2 + Na2C03 --:--1- BaC03 + 2NaCI
common form is decahydrate, Na2C03:10H20. This form is 2MgCl2 + 2Na2C03 + H20 ·:-:-:::-:.:nVlgc03~Mg(OHh+ 4NilCI
called washing soda. The decahydrate form on standing Basic magnesium + CO2
carbonate
in air effloresces and crumbles to powder. It is the mono-
hydrate form,Na2C03·H20. It also forms a heptahydrate, 5ZnS04 + 5Na2C03 + 4H20 --:--1-
Na2C03·7H20. [2ZnC03·3Zn(OHh}H20 + 5Na2S04 + 3C02
Basic zinc carbonate
(b) On heating, the monohydrate changes into the anhydrous
form which does not decompose on further heating even to CUS04 + Na2C03 --:--1- CuC03 + Na2S04
redness. It is the amorphous powder and called soda ash. It 2CUS04 + 2Na2C03 + H20 --:--1-
melts at 852°C. Cu(OHh·CuC03 + CO2 + Na2S04
below 373K Basic copper carbonate . -
Na2C03 . lOH 20 , ' Na2C03 . H 20 + 9H 20
3(CH3COOhPb + 3Na2C03 + H20 --:--1-
above 373K
Na2C03 . H 20, ' Na2C03 + H 20 2PbC03Pb(OHh + CO2 + 6CH 3COONa
Soda ash Basic lead carbonate
(c) It is soluble in water with evolution of considerable 2AgN03 + Na2C03 --:--1- Ag2C03 + 2NaN03
amount of heat. The solution is alkaline in nature due to Carbonates of metals like Fe, AI, Sn, etc., when formed are
hydrolysis. immediately hydrolysed to hydroxides.
Na2C03+ 2H 20 ~ 2NaOH + H2C03
Fe2(S04h + 3Na2C03 --:--1- F~(C03h + 3Na2S04
When the hot solution of sodium carbonate is concentrated
Fe2(C03h + 3H20 --:--1- 2Fe(OHh + 3C02
and cooled, crystals of decahydrate form are obtained.
Chemical Properties: (a) Reaction with acids: It
is readily decomposed by acids with evolution of carbon dioxide. • Uses
The reaction occurs in two steps. Sodium carbonate is used:
Na2C03 + HCI ~ NaHC03 + NaCI (i) in the manufacture of soaps, detergents, dyes, drugs and
other chemicals. .
NaHC03 + HCI --:--1- NaCI + H20 + CO2
(ii) in laundries and in softening of water as washing soda.
(b) Reaction with C02: On passing CO 2 through the
(iii) in the manufacture of glass, sodium silicate, paper,
concentrated solution of sodium carbonate, sodium bicarbonate borax, soap powders, caustic soda, etc.
gets precipitated. (iv) as a laboratory reagent. The mixture of Na2C03 and
Na2C03 .+ H20 + CO2 --:--1- 2NaHC03 .K2C03 is used as a fusion mixture. It is used in quantitative
(c) Reaction with silica: When the mixture of sodium analysis to standardise acid solutions. In qualitative analysis, it
carbonate and silica is fused, sodium silicate is formed. is used in the detection of acidic radicals especially of insoluble
Na2C03 + Si02 --:--1- Na2Si03 + C02 I salts.
(v) in textile, petroleum refIning, paints and dyes.
Sodium silicate is called soluble glass or water glass as it
(vi) for the preparation of various carbonates of metals.
is soluble in water.
2.86 GR.B. Inorganic Chemistry for Competitions
II 5. Sodium bicarbonate (Baking soda), NaHC03 The resulting solution is concentrated and allowed to
crystallise when crystals of sodium thiosulphate being less
Preparation : Sodium hydrogen carbonate, NaHC03
soluble separate out first.
(Sodium bicarbonate), is commonly called bicarbonate of
(iii) When the solution containing sodium carbonate and
soda or baking sbda. It is obtained as the intermediate product
sodium sulphide is treated with sulphur dioxide, sodium
in the solvay ammonia soda process. Normal carbonate can be
thiosulphate is formed with evolution of carbon dioxide.
changed to bicarbonate by passing carbon dioxide through its
saturated solution. 2Na2S + Na2C03 + 4S02 ---t 3Na2S203 + CO2 i
(iv) Sodium thiosulphate is formed when sulphur is heated
Na2C03 + C02 + H20 ---t 2NaHC03 with caustic soda solution.
Sparingly soluble
4S + 6NaOH ---t Na2S203 + 2Na2S + 3H20
Properties: It is a white crystalline solid, sparingly soluble
With excess of sulphur, sodium pentasulphide is formed.
in water. The solution is alkaline in nature due to hydrolysis.
The solution is weakly basic. Na2S + 4S ---t Na2SS
(v) On passing S02 gas through the solution of Na2C03 in
NaHC0 3 + H 20 ~ NaOH + H 2C0 3
presence of sulphur we get sodium thiosulphate.
The solution gives yellow colour with methyl orange but no Na2C03 + S02 ---t Na2S03 + C02
colour with phenolphthalein. Na2S03 + S ---t Na2S203
On heating, it loses carbon dioxide and water forming sodium
carbonate. Properties
2NaHC03 ---t Na2C03 + H 20 +
C02 (i) It is a colourless crystalline solid consisting of 5 molecules
of water as water of crystallisation. It has the formula,
The metal salt which forms basic carbonate with sodium
Na2S203·5HiO. It is soluble in water. It melts at 48°C.
carbonate, gives normal carbonate with sodium bicarbonate.
(il) Action of heat: It is efflorescent substance. The
ZnS04 + 2NaHC03 ---t ZnC03+ Na2S04 +H 20 +C02 water molecules are completely lost when heated at 215°C.
215°C
Uses Na2S203·5H20 ~ Na2S203 + 5H20
(i) It is used as a medicine (sodabicarb) to neutralise the When strongly heated above 223°C, it decomposes form-
acidity in the stomach. ing sodium sulphate (salt cake) and sodium pentasulphide.
(ii). It is largely used for making baking powder. Baking 4Na2S203 ---t 3Na2S04 + Na2Ss
powder is a mixture of potassium hydrogen tartrate and sodium (in) Reaction with acids: Dilute acids decompose it with
bicarbonate. Baking powder is also prepared by using NaHC03 evolutIon of S02 and precipitation of sulphur.
(30%), starch (40%), calcium hydrogen phosphate (10%) and Na2S203 + 2HCI ---t 2NaCl + S02 + S + H 20
NaAI(S04h. Na2S203 + H 2S04 ---t Na2S04 + S02 + S + H 20
(iii) It is used in making effervescent drinks.
(iv) O~dation: It is oxidised by iodine quantitatively.
(iv) It is used in fire extinguishers.
(v) It is used for production of carbon dioxide. 2Na2S203 + 2NaI + Na2S406
Sodium
tetrathionate
Ii 6. Sodium Thiosulphate, (Hypo), Na2S203,SH20
In this reaction, colour of iodine disappears:
It is the sodium salt of an unstable acid, thiosulphuric acid (v) Reducing action: It is oxidised by chlorine and
(H2S203)' It is also known as hypo, The following methods bromine water. Sulphur is precipitated.
cari be used for its preparation.· Na2S203 + Cl2 + H 20 ---t Na2S04 + 2HCI + S
(i) It is obtained by boiling sodium sulphite solution with
It reduces FeCl3 to FeCl2
flowers of sulphur..
2Na2S203 + 2FeCl 3 ---t Na2S406 + 2FeC1 2 + 2NaCl
Na2S03 + S ---t Na2S203
(vi) Reaction with AgN03: A white precipitate of silver
Sodium Sulphur Sodium
. sulphite thiosulphate thiosulphate is obtained which changes to yellow, brown and
finally black due to the formation of silver sulphide.
The unreacted sulphur is filtered off and the filtrate is
evaporated to crystallisation. 2AgN03 + Na2S203 ---t Ag2S203 + 2NaN03
(ii) Spring's reaction: The mixture of sodium sulphite Ag2S20 3 + H 20 ---t Ag 2S + H 2S04
and sodium sulphide is treated with calculatel;l quantity of iodine. (vO) Reaction with silver halides: Halides form
Na2S + 12 + Na2S03 ---t Na2S203 + 2NaI complexes with sodium thiosulphate. Silver bromide forms
argentothiosulphate complex.
AgBr + 2Na2S203 Na3[Ag(S203h] + NaBr Uses: It is especially used for testing silica with which a
Sodium argentothiosulphate cloudy bead containing floating properties of silica is obtained.
(colourless)
Similar reactions, 'are observed with AgCl and AgI.
II 8. Sodium Chloride (Common Salt), NaCI
This property is utilised in photography for fIxing the negative
and positive of black and white photography. It removes ! Sodium chloride is the most corrunon of the salts of sodium.
undecomposed AgBr present on the fIlm. It is also called corrunon salt, table salt, rock salt or sea salt.
(viii) Reaction with copper sulphate: Cuprous thio- An aqueous solution of sodium chloride is known as brine.
sulphate is formed which dissolves in excess of sodium Sea water contains about 2.95 per cent sodium chloride. As
thiosulphate to form a complex. a rock salt it is found at several places in England, Australia,
, CUS04 + Na2S203~ CUS203 + Na2S04 'Germany, Canada, Pakistan (Khewra-Punjab) and India (Mandi-
Cupric Himachal Pradesh), It is found in land lakes (e.g., Sambhar
thiosulphate lake in India, lake Elton in Russia).
2CUS203 + Na2S203 ~ CU2S203 + Na2S406
Cuprous Manufacture from sea water
thiosulphate
3CU2S203 + 2Na2S203 ~ Na4[Cu6(S203)S] In tropical countries like India, on the sea coasts, the sea
Sodium cuprothiosulphate water is allowed to dry up under surruner heat in small tanks
or pits. The solid crust so formed is collected.
Uses In very cold countries, the sea water is concentrated by
freezing. The concentrated solution is then evaporated in big
Sodium thiosulphate is used:
iron pans. Sodium chloride thus obtained contains impurities
(i) as an antichlor to rem~)Ve excess of chlorine from
like magnesium chloride, calcium chloride, etc. It is purifIed by
bleached fabrics.
passing hydrogen chloride through a saturated solution of
(ii) in the extraction of silver and gold.
the corrunercial salt. The precipitation of sodium chloride occurs
(iii) in photography as a fixing agent in the name of hypo.
due to corrunon ion effect.
(iv) as a reagent in iodometric and iodimetric titrations for
the estimation ofiodine, CUS04, K2Cr207, KMn04, Na3As03, Properties
etc.
(a) It is a white crystalline solid. It is slightly hygroscopic.
II 7. Microcosmic Salt, Na(NH4)HP04 ·4H20 (b) Its density is 2.17 g/mL when pure. It melts at 800°<;.
It is soluble in water. It dissolves in water with absorption
Preparation: It is prepared by dissolving ammonium
of heat.
chloride and disodium hydrogen phosphate in molecular
(c) It is insoluble in alcohol.
proportion in hot water.
(d) The corrunon salt is the starting material for the
preparation of all the other sodium compounds and extraction
The sparingly soluble microcosmic salt separates out. It is of sodium. Sodium, sodium hydroxide and sodium carbonate
fIltered and purified by recrystallisation. ' are the three main materials obtained from corrunon salt which
are then used to prepare other important compounds of sodium.
Properties
Uses
(i) It is colourless crystalline solid, sparingly soluble in water.
(ii) When heated, it melts to form a clear transparent mass (i) It is an essential constituent of food.
which has the property of combining with metalli~ oxides to (ii) It is used as a preservative of food articles like fIsh,
form coloured orthophosphates. meat, etc.
(iii) It is ,used for making useful sodium compounds.
Na(NH 4)HP0 4 ~ NaP0 3 + NH3 + H20
(iv) It fInds application in salting out of soap, and in making
Sodium
metaphosphate freezing' mixtures.
NaP0 3 + CuO ~ NaCuP04 (v) Impure salt (rock salt) is used to de-ice roads.
Blue mass
II 9. Sodium Cyanide, NaCN
On account of this property, microcosmic salt is used for
the detection of coloured ions. The test is similar to borax bead It is manufactured by the following methods :
test. The salt is heated on a loop of a platinum wire, a transparent (i) From sodium: Sodarnide is fIrst formed by passing
bead is formed., When hot bead is brought in coritact with dry ammonia gas over heated sodium in iron retorts at 300-
coloured substance and strongly heated, a coloured bead is 400°C.
formed if the substance contains Cu2+, Ni 2+, Mn2+: C02+, etc.
~ PHs+NazHP02
NaOH~-~~~"'tl~~ ~
\ ~~. HSP02
.
~ \: NaCIO , NaCIOs Hypophosphorus acid
g ~ NaBrO , NaBrOa
~ !!l NalO , NalOs
a. 0
:k ~ <:T
CO
HCOONa
Under pressure
'"
I '" '0
i .~ AI or Zn or Si
'-----"-~=--=-'--.::.:......::.'---....... Production of hydrogen
"'~
u g
j
UJ
Sodarnide
Electrolysis Sodium hydride

COMMON SALT of fused NaCl
1 - - - - - - - - - - - Sodium """:::::--_~~_
NaCI Containing (See section Sodium peroxide
CaCI2 and KF 6.4)
Sodium sulphide
~ Baking powder
NaHCOa (CaC,:! as by-product)
Washing soda
1
Na2S04+ HCI
C (by-product)
Heat
For the preparation of

various "carbonates
NazS CaS of metals
~ HS
2~
\/$
Na2S0a
Na2S203
(Hypo)
Flowsheet chart for the properties of sodium chloride and preparation of various compounds of sodium
The molten sodamide thus obtained is dropped on red hot (iii) From gas works: Coal gas is always contaminated
charcoal when fIrst sodium cyanamide and then sodium cyanide with some hydrocyanic acid and ammonia. Before it is put into
is formed. use, it is passed through copper sulphate solution when
2NaNH2 + C ----7 Na2CN2 + 2H2 ammonium tricyanocuprate (I) is formed.
Na2CN2 + C ----7" 2NaCN 2CUS04 + 4HCN ----7 2CuCN + (CNh + 2H2S04
NH3 + HCN ----7 NH4CN
2NaNH2 + 2C 2NaCN + 2H2
or 2NH4CN + CuCN ----7 (NH4h[Cu(CNh]
(ll) From calcium cyanamide: NaCN is prepared by The complex is decomposed by the addition of dilute H2S04
fusing a mixture of crude calcium cyanamide (nitrolim) and and the evolved HCN is absorbed in caustic soda.
sodium carbonate in the presence of carbon. (NH4h[Cu(CNhl + H2S04 ----7 (NH4hS04 + CuCN + 2HCN
CaCN2 + C + Na2C03 ----7 2NaCN + CaC03 NaOH + HCN ----7 NaCN + H20
The fused product is extracted with water and the solution
on evaporation-gives NaCN.
Properties of sodium. However, it can also be prepared by carrying
electrolysis of fused potassium hydroxide or by electrolysis of
It is a white crystalline solid. It has a characteristic smell
fused mixture of KCI and CaCI2. Potassium is manufactured
and highly poisonous in nature. It is soluble in water and its
by reducing the fluoride with calcium carbide at 1000°C in
solution is alkaline due to hydrolysis.
steel cylinders.
NaCN + H20 ~ NaOH + HCN IOOO°C
2KF + CaC2 - - ? 2K + CaF2 + 2C
It forms complex cyanides with the salts of copper, silver,
gold, cadmium, zinc, iron, cobalt, nickel, etc. Some examples The metal obtained is 99.7 per cent pure.
are given below: Uses : (i) Potassium is used in photoelectric cells. In the
commercial process, potassium chloride is melted with sodium
(i) AgN03 + NaCN ~ AgCN + NaN0 3
.metal by heating to 870°c'
AgCN + NaCN ~ Na[Ag(CNhl 87(J' C
KCl + Na ) K + NaCI
(ii) CdS04 + 2NaCN ~ Cd(CNh + Na2S04
At this temperature, potassium forms a vapour, which leaves
Cd(CNh + 2NaCN ~ Na2[Cd(CN)41
the reaction chamber and then condensed in photoelectric cells.
(iii) FeS04 + 2NaCN ~ Na2S04 + Fe(CNh (ii) An alloy of potassium and sodium is used in special
Fe(CNh + 4NaCN ~ Na4[Fe(CN)6] thermometers employed for measuring high temperatures.
. '
(iv) CUS04 + 2NaCN ~ Na2S04 + Cu(CNh ""
Compounds of Potassium
2Cu(CNh 2CuCN + (CNh
CuCN + 3NaCN Na3[Cu(CN)41
• 1. Potassium Chloride, KCI
A dilute solution of sodium cyanide dissolves gold and silver
in presence of oxygen. Potassium chloride is the starting material for the preparation
of various potassium compounds. It is obtained from carnallite,
4Au + 8NaCN + 2H20 + O 2 ~ 4Na[Au(CNh] + 4NaOH
KCI·MgCI2·6H20, by fractional crystallisation. The carnallite
Uses is ground and extracted with a 20 percent solution of MgCI2.
The carnallite dissolves while NaCI and MgS04 remain
Sodium cyanide is used: undissolved. The clear solution is put to crystallisation when
(i) in the extraction of Ag and Au. crystals of KCl separate out.
(ii) as germicide in agriculture. More than 90% of the potassium chloride that is mined is
(iii) in electroplating of silver, gold, etc. used directly as a plant fertilizer. The rest is used in the prepara-
(iv) in the preparation of complex .cyanides of transition tion of various potassium compounds.
metals and organic cyanides.
(v) as a laboratory reagent. .~. • 2. Potassium Iodide, KI
,X[;;I
Etf;1 POTASSIUM Preparation

"
Potassium is not found in the native state. In combined state, (i) It is prepared by the action of hydroiodic acid on
potassium compounds are widely distributed in nature almost potassium hydroxide or potassium carbonate.
to the same extent as the sodium compounds. All plants contain KOH + HI ~ KI + H20
considerable amounts of· potassium compounds which they K2C03 + 2HI ~ 2KI + CO2 + H20
recei ve from soil. Its compounds occur as salt beds, in rocks (ii) It may be prepared by heating iodine with hot and
and in sea water. The important minerals of potassium are: concentrated solution of potassium hydroxide. The resulting
Sylvite KCI liquid consisting of KI and KI03 is evaporated to dryness and
the solid residue is then ignited with powdered charcoal to
Carnallite KCI·MgCI 2·6H20
convert iodate also into iodide.
Kainite KCI·MgS0 4:MgCh· 3H20
312 + 6KOH ~ SKI + KI03 + 3H 20
Indian saltpetre KN03
KI0 3 + 3C ~ KI + 3CO
Feldspar K20·Al20 3·6Si02 (clay)
The mass is extracted with water, filtered and the clear
Polyhalite K2S04·MgS04·CaS04·6H20
solution is evaporated to dryness.
Metallic potassium is not of much in demand as cheaper (iii) Potassium iodide is obtained on large scale by the action
sodium can be used for the same purpose. Potassium is prepared of ferroso ferric iodide on potassium carbonate. The solution
by the chemical reduction of potassium chloride, KCI rather is boiled.
than by electrolysis of the molten chloride, as in the preparation 4K2C03+Fe318 + 4H 20---48KI+ 4C02 +Fe(OHh"2Fe(OHh
ppt.
, 290 G.R.B. Inorganic Chemistry for Competitions
[Fe3lg is fonned separately by adding iodine to iron fillings

in water. Yellow
Fe + 12~ Fel2 Pb(CH3COOh + 2KI ~ Pbl2 + 2CH3COOK
Yellow
3Fel2 + 12 Fe31g (ferroso ferric iodide)]
If forms a red precipitate with HgCl2 which dissolves in
The precipitate is filtered off and the clear solution is put to excess of potassium iodide forming potassium mercuric iodide.
crystallisation when crystals of potassium iodide are obtained.
HgCl 2 + 2KI ~ Hgl2 + 2KCI
[Note: KBr, potassium bromide is obtained similarly by the- applica-
Hgl2 + 2KI ~ K2Hgl4
tion of above methods.]
The alkaline solution of K 2HgI4 is called Nessler's reagent
Properties and is used for the detection and estimatio~ of NHt ion.
Uses: It is used:
(a) It is white crystalline solid, highly soluble in water and
(a) as a solvent of iodine.
alcohol. (b) as a reagent in laboratory.
(b) It dissolves in free iodine and forms potassium tri-
(c) in medicine and photography.
iodide.
(d) for making Nessler's reagent in the laboratory.
[The solubility of iodine increases in presence of potassium
iodide.] • 3. Potassium Nitrate, KN03
(
KI3 is unstable and gives up extra iodine readily. Potassium nitrate is prepared by the reaction of potassium
hydroxide and nitric acid.
(c) Sulphuric acid decomposes potassium iodide.
2KI + H 2S04 ~ K 2S04 + 2HI KOH + HN0 3 ~ KN0 3 + H 20
Potassium Nitric acid Potassium
2HI + H2S04 ~ 2H20 + 12 + S02 hydroxide nitrate
Uses : (i) KN0 3 is used in the production of fertilizers and
2KI + 2H 2S04 ~ K2S04 + 12 + S02 + 2H20
for explosives and fireworks.
or 2KI + 3H2S04 ~ 2KHS04 + 12 + S02 + 2H20 (U) Potassium nitrate, KN0 3, releases oxygen when heated,
(d) Chlorine liberates iodine from potassium iodide. i\
2KI + Cl2 ----:--7 2KCI + 12 2KN03(S) ~ 2KN02(s) + °2(g)
(e) It acts as a reducing agent. Oxidising agents like acidified - and is used to facilitate the ignition of matches.
KMn04, acidified K2Cr207, HN0 3, H 20 2, CUS04, etc., liberate (iii) It is less hygroscopic (water absorbing) than the
iodine from KI. corresponding sodium compounds, because the K+ cation is
larger and is less strongly hydrated by H 20 molecule.
(i) 2KMn04 + 3H2S04 --7 K2S04 + 2MnS04 + 3H20 + 50
[2KI + H 2S04 + 0 --7 K 2S04 + H 20 + 12 ] X 5 • 4. Oxides
2KMn0 4 + lOKI + 8H2S04 --7 6K2S04 + 2MnS04 + 512 + Three oxides of potassium are known:
8H20 (a) potassium monoxide, K 2o.
(ii) K2Cr207 + 4H2S04 --7 K 2S04 + Cr2(S04h + 4H20 + 30 (b) potassium dioxide (tetraoxide or superoxide), K02 or
°
[2KI + H2S04 + --7 K2S04 + H20 + 12 ] X 3 K20 4·
(c) potassium sesquioxide, K20 3.
6KI + K2Cr207+ 7H2S04 --7 4K2S04 + Cr2(S04h+ 312+ 7H20 (b) Potassium dioxide; (tetraoxide or snperoxide) K0 2 :
Almost all of the potassium metal produced is used in the
(iii) [CUS04 + 2KI ~ CUl2 + K2S04] x 2
Unstable preparation of potassium superoxide, K02. It is prepared by
burning potassium in excess of oxygen free from moistnre.
K + 02~ K0 2
2CUS04 + 4KI ~ CU212 + 2K2S04 + 12 It is also obtained by reacting dry potassium hydroxide with
Cuprous
iodide
ozone.
2KOH + 0 3 ~ 2K02 + H20
The above three reactions are used in iodometric titrations.
Properties: Potassium superoxide, K0 2, is a chrome
(iv) 2HN03 ~ H20 + 2N02 + 0
°
2KI + 2HN0 3 + ~ 2KN03 + 12 + H 20
yellow powder. It dissolves in water giving H202 and OZ,
2K02 + 2H20 ~ 2KOH + H202 + O 2
2KI + 4HN03 ~ 2KN03 + 2N02 + 12 + 2H20 It reacts directly with CO and CO2,
(f) Potassium iodide forms insoluble iodides with AgN03 2K0 2 + CO ~ K2C03 + 02
and lead salts. 4K02 + 2C02 ~ 2K2C03 + 302
On heating with sulphur, it· forms potassium sulphate. (d) Calcium chloride is added to NaCI in the electrolytic
2K02 + S ~ K2S04 manufacture of sodium.
Uses: K02 is used as an oxidising agent. It is used as air . (e) An aqueous solution of iodine becomes colourless on
purifier in space capsules, submarines and breathing masks as adding excess of sodium hydroxide solution.
in all these it produces oxygen and removes carbon dioxide. Solution:
(c) Potassium sesquioxide; K203.: It is obtained when (a) KHC03, the intermediate, is very soluble in water and
oxygen is passed through liquid ammonia containing potassium. cannot be obtained in solid state as NaHC03 is formed in
Na2C03 manufacture.
4K (dissolved in liquid NH3) ~ 2K20 3 (b) Sodium hydroxide continuously absorbs carbon dioxide
Uses: It is used for the production of self contained and moisture of atmosphere and is converted into sodium
breathing apparatus which is used in the situations such as fire . carbonate solution.
fighting, where toxic fumes may be present. A stage reaches when the solution becomes saturated and
the crystals are formed. These crystals, with the passage of
• 5. Potassium Hydroxide (Caustic Potash), KOH time, lose water of crystallisation (efflorescence) and crumble
to white powder.
It was first prepared from potassium carbonate (K2C03),
(c) The solutions of alkali metal salts contain metal cations,
obtained by leaching plant ashes with water and evaporating
H+, OH- and the anions. The discharge potential of H+ ions is
the solution in large pots (whence the name).
lower than the metal cations and thus, on electrolysis of solutions-
It is manufactured like sodium hydroxide, i.e., by electrolysis
of alkali metal salts, hydrogen is discharged at cathode rather
of aqueous KCl solution.
than· the metal.
Uses: It is an important base and'is used for the absorption
However, on electrolysis of molten salt, the metal cation
of gases like C02, S02, etc: It is often called as caustic only present gets discharged at cathode.
potash and its aqueous solution is known as potash lye. It is (d) Pure sodium chloride melts at about 800°C. At this
used for making soft and liquid soaps. temperature both sodium and chlorine (products of electrolysis)
Alcoholic caustic potash is a useful reagent in organic are corrosive in nature. Sodium also forms a metallic fog at
chemistry as it eliminates hydrogen halides from alkyl halides. this temperature. To remove these difficulties, the fusion
C2HSBr + KOH(alc.) ~ C2~ + KBr + H20 temperature is reduced to 600°C by adding CaCI2.
Like caustic soda, NaOH caustic potash, KOH also is quite (e) Iodine reacts with NaOH forming colourless compounds.
corrosive and destructive to the organic tissue; they convert Thus, the colour of iodine disappears on addition of NaOH.
animal fats to soaps. . 2NaOH + 12 ~ 'NaI + NalO + H20
----,r----'
Colourless products
• 6. Potassium Carbonate, K2C03
Example 4. How would. you prepare the following?
It is also called Potash or Pearl ash. It cannot be made by the
(a) Sodium thiosulphate from sodium carbonate.
use of Solvay process as potassium bicarbonate is more soluble
(b) Microcosmic salt from disodium hydrogen phosphate.
than sodium bicarbonate. However, it can be prepared by
(c) Sodium carbonate from sodium ·chloride.
Le-Blanc process. KCl is fITst converted into K2S04' Potassium (d) Sodium thiosulphate from sodium sulphite.
sulphate (K2S04) is then heated with CaC03 and carbon.
(e) Sodium cyanide from metallic sodium.
KCl + H 2S04 ~ KHS04 + HCI Solution:
KHS04 + KCI ~ K2S04 + HCl (a) Sodium carbonate is first converted into sodium sulphite
K2S04 + CaC03 + 2C ~ K2C03 + CaS + 2C02 by passing sulphur dioxide.
It is a white powder, deliquescent in nature. It is highly Na2C03 + S02 ~ Na2S03 + CO2
soluble in water.
The solution of Na2S03 is then boiled with sulphur for two
Uses: It is used in the manufacture of hard glass. The
hours.
mixture of K2C03 and NaiC03 is used as a fusion mixture
in laboratory. Na2S03 + S ~ Na2S203
Example 3. Explain the following: (b) It is prepared by dissolving ~CI in disodium hydrogen
(a) Sodium carbonate is made by Solvay process but the phosphate in molecular proportion in hot water.
same process is not extended to the manufacture of potassium ~CI + Na2HP04 ~ NaNH4HP0 4 + NaCl
carbonate.
(c) The conversion is made by Solvay process.
(b) On exposure to air, sodium hydroxide becomes liquid
and after sometimes it changes to white powder. CO2 + NH3 + H20 ~ NH4HC03
(c) Alkali metals are obtained by the electrolysis of the NH4HC03 + NaCI ~ NaHC0 3 + NH4CI
molten salts and not by the electrolysis oftheir aqueous solutions. 2NaHC03 ~ Na2C03 + H20 + C02
292 O.R.B. Inorganic Chemistry for Competitions
(d) The solution of sodium sulphite is boiled with sulphur (i) Na2S + Na2S03 + 12 -----t Na2S203 + 2NaI
in an iron retort for two hours. (B) (A)
or 2Na2S + Na2S03 + 3S02 -----t 3Na2S203
Na2S03 + S ~ Na2S203
(n) ·2AgN03 + Na2S203 -----t Ag2S203 + 2NaN03
. (e) Sodium is first converted into sodamide by passing dry (White ppt.)
ammonia gas ov;er heated sodium. Ag 2S20 3 + H20 -----t Ag 2S + H 2S04
(C) Black ppt.
2Na + 2NH3 -----t 2NaNH2 + H2 t
(iii) 2FeCl3 + 3Na2S203 -----t Fe2(S203h + 6NaCI
The liquid sodamlde is then dropped over red hot charcoal. (D) Violet ppt.
2NaNH2 + C -----tNa2CN2 + 2H2 Fe2(S204)3 + Na2S203 -----t 2Fe(S203) + Na2S406

Sod. cyanamide Colourless
Na2CN2 + C -----t 2NaCN (iv) CUCl2 + Na2S203 -----t CUS203 + 2NaCI

2CUS203 + Na2S203 -----t CU2S203 + Na2S406
:Example 5. 'A' is a binary compound ofa univalent metal. (White ppt.)
1.422 g of 'A' reacts completely with 0.321 g of sulphur in an 3CU2S203 + 2Na2S203 -----t Na4[Cu6(S203)5]
evacuated and sealed tube to give 1.743 g of a white crystalline (E) Soluble complex
solid 'B', thatjorms a hydrated double salt 'C' with AI2(S04h. Example 7. A white solid is either Na20 or Na202' A
Identify 'A', 'B' and 'C'. [I.I.T. 1994] piece of red litmus paper turns white when it is dipped into a
Solution: freshly made aqueous solution of the white solid.
Since 'B' forms a hydrated double salt with Al2(S04h 'B' (i) Identify the substance and explain with balanced equation.
should be a sulphate of a monovalent metal, i.e., M2S0 4 . As (ii) Explain what would happen to the red litmus if the
the sulphate (M2S04 ) consists one sulphur atom per molecule, white solid were the other compound. [I.I.T. 1999J
its molecular mass can be determined from the given data. Solution:
0.321 g of sulphur is present in 1.743 g of sulphate (i) A piece of red litmus turns white when dipped into
32.1 g of sulphur is present in ~.~i; x 32.1 = 174.3 g aqueous solution of white solid indicates that the solution has
bleaching action on litmus. This is due to the presence of
Thus, the molecular mass of the sulphate is 174.3. Let the hydrogen peroxide in solution which is formed by action of
atomic mass of the metal be x. water on sodium peroxide. Thus, the white solid is Na202'
So 2x + 32.1 + 64 = 174.3 Na202 + 2H20 -----t 2NaOH + H 20 2
2x = 174.3 96.1 = 78.2 (n) The other compound is Na20 which gives NaOH (sodium
x = 39.1 hydroxide) with water.
Na20 + H 20 -----t 2NaOH
Thus, 'B' is K2S04 and 'C' is K2S04'Al2(S04h'24H20
The solution, thus, turns. red litmus to bh,le.
2 [Oxide] + S -----t K2S04
Example 8. The Solvay process can be represented by the
Thus, the oxide is K0 2 (potassium superoxide).
following scheme:
The given data supports that 'A' is K02.
Example 6. (i) An inorganic compound (A) is formed on
passing a gas (B) through a concentrated liquor containing
sodium sulphide and sodium sulphite.
(ti) On adding (A) into dilute solution of silver 1;litrate, a
white precipitate appears which quickly changes into a black
coloured compound (C) .
. (iii) On adding two or three drops offerric chloride into the
excess of solution of (A), a violet coloured compound (D) is
formed. This colour disappears quickly.
(iv) On adding a solution of (A) into the solution of cupric
chloride, a white precipitate is first formed which dissolves on
adding excess of (A) forming a compound (E). Identify A, B, C, D and E. lU.T.1999]
Identify (A) to (E) and give the chemical equations for the
Solution:
reactions at steps (i) to (iv). [Roorkee' 1996]
Solution: (A) : Ca(OHh
The reactions indicate that the compound (A) is sodium CaO + H 20 -----t Ca(OHh
thiosulphate. It is formed in step (i) by passing gas (B) which (A)
is either 12 or S02'
(B) : NH4HC0 3 (c) Superoxides contain the ion, 02 which has the following
structure:
NH3 + H 20 + CO 2 ~ NH 4HC0 3
.. ]-
(B)
[ ..
:O~O:
..
Ithas a three electron bond, i.e., one unpaired electron is

2NaHC03 ~ Na2C03 + H 20 + CO 2 present and hence, is paramagnetic. Normal oxides contain the
(e) 2
ion, 0 -, which does not has unpaired electron and thus, are
diamagnetic in nature.
(D) : NH4CI
Example--.lO. Comment on each of the following obser-
NH 4HC0 3 + NaCI ~ NaHC0 3 + NH4CI vations:
(D)
(a) Lithium is the only alkali metal which forms nitride
directly.
(E) : CaCl2
(b) LiF is almost insoluble in water while LiCI is soluble in
2NH 4CI + Ca(OHh ~ 2NH3 + 2H20 + CaCl2 water as well as in acetone.
. (E) (c) The mobilities of alkali metal ions in aqueous solutions
are:
,",,-Example 9. (a) .Sodiumfire in the laboratory should not
be extinguished by pouring water. Why?
Solution:
(b) Alkali metals are paramagnetic but their salts are (a) As it shows diagonal relationship with magnesium, it
diamagnetic. Explain. directly combines with nitrogen like magnesium and forms
(c) Why superoxides of alkali metals are paramagnetic while nitride.
normal oxides are diamagnetic? 6Li + N2 ~ 2Li3N
Solution;
(b) Lattice energy of LiF is very large as. both Li+ and F
(a) Sodium being highly electropositive element reacts
ions are small in size. Hence, LiF is almost insoluble in water.
vigorously with water evolving hydrogen which also catches
LiCI is partially covalent in nature due to polarisation of chloride
fIre. As a result, the fIre spreads. Therefore, water should not
ion by Lt. Thus, it is soluhle in water as well as in acetone.
be used to extinguish sodium fIre.
(b) Alkali metals possess ns I configuration, i. e., one unpaired (c) The degree of hydration is more for smaller ions. Thus,
electron is present and hence are paramagnetic. Alkali metals the mass of the hydrated ions follows the following order,
when form salts, the unpaired electron is tr,ansferred to the [Li(aq)t > [Na(aq)t > [K(aq)t > [Rb(aq)t.
nori-metallic atom forming anion. In salts, both cations and
Therefore, the ionic mobility follows the following order:
anions have paired electrons and hence, alkali metal salts are
diamagnetic in nature. [Li(aq)t < [Na(aq)t < [K(aq)t < [Rb(aq)t
SUMMARY AND IMPORTANT POINTS TO REMEMBER

1. The group 1 or IA of the periodic table consists of six ele- 3. The alkali metals, being reactive in nature, are never found
ments-lithium, sodium, potassium, rubidium, caesium and free in nature but always found in combined state. Sodium
francium besides hydrogeri. These elements are called alkali and potassium are found in abundance as they are seventh
metals as the hydroxides of these elements are soluble in and eighth most abundant elements by mass in earth's crust.
water and these solutions are highly aikaline in nature. Alkali The last member, francium, is radioactive and occurs only in
is an Arabic word' Alquili' meaning the ashes of plants from traces- as its half -life is very small, i.e., 21 minutes.
which compounds of sodium -and potassium were fIrst 4. Except fIrst period, rest of the six periods of the periodic table
isolated. start with a member of alkali group. It is a most homogeneou s
2. The alkali metals are s-block elements as .the last electron group. The members of this group show a marked resemblance
enters ns-orbital. They have [noble gas] ns l electronic in their properties. There is a gradual gradation in the
conflguration. The fIrst member lithium, shows somewhat properties with the increase of atomic number.
abnormal properties tb~n rest of the members of the group 5. Physical properties
as the penultimate shell in Li has two electrons while in rest (a) Alkali metals are soft with low melting and boiling points.
of the alkali elements eight electrons are present in the This is due to weak intermetallic bonding. All are light
penultimate shell. metals having low densities. Densities increase from r
to Cs with exception of K.
(b) Alkali metals have the largest size in their respective The peroxides and superoxides become more stable with
periods. Atomic as well as ionic size increases as the at. increase in atomic number of the alkali metal. The basic
no. increases from Li to Cs. At. volume also increases as nature of the normal oxides increases gradually as the
the atomic number increases. atomic number increases. The hydroxides (MOR) are
(c) The ionisation energy decreases from Li to Cs as their thermally stable except LiOH. The relative strength of the
size increases. They are highly electropositive. metallic hydroxides increases from LiOH to CsOH.
innature and reactivity increases from Li to Cs. All except Li20 < Na20 < K20 < Rb20 < Cs 20
. lithium show photoelectric effect. LiOH < NaOH < KOH < RbOH < CsOH
(d) Ail alkali metals are paramagnetic but their salts are Basic nature increases )
diamagnetic in nature. The alkali metals show only one The highe~ oxides. peroxides and superoxides are strong
oxidation state. i.e., +1 in their compounds. oxidising agents. They react with water and dilute acids
(e) Alkali metals and their compounds impart characteristic' forming H 20 2 and 02' .
colour to flame. . (e) The alkali metals directly react with halogens forming
Li Na K Rb Cs hatides (MX). With the exception of lithium halides, the
Crimson red Golden yellow Pale violet Reddish violet Sky blue alkali metal halides are ionic compounds. They are
(f) The salts of alkali metals are ionic and sohible in water. crystalline and have high melting and boiling points. The
The solubility is due to hydration of M+ ions. Smaller fused halides are good conductors of electricity.
the ion, the greater is the degree of hydration. The degree Alkali metal halides are colourless but on heating they
of hydration decreases from Li+ to Cs+. Consequently, turn yellow, b.lne. etc .• due to crystal defects. Except LiP,
the. radii of the hydrated ion decreases from Li+ to Cs+. all halides are soluble in water. The insolubility of LiFi~
(g) Due to large negative electrode potentials, alkali metals due to high lattice energy. Halides of K. Rb and Cs have
are strong reducing agents. The reducing nature a property of combining with extra halogen atoms forming
increases from Na to Cs but Li is the strongest redocing polyhalides.
agent as its reduction potential is highest, i.e, -3.05. This (f) Alkali metals directly combine with P and S when heated
is due to large heat of hydration of Li+ ion. with them. Alkali metals, except lithium, do not combine
(h) The alkali metals are good conductors of heat and directly with nitrogen.
electricity. (g) All the alkali metals form carbonates of type M 2C03 •
6. Chemical properties Carbonates are stable towards heat and readily soluble
The alkali metals are highly reactive elements. The reactivity in water. Li2C03 is an exception.
is due to: The aqueous solutions of carbonates are alkaline due to
(i) low value of ionisation energy hydrolysis.
(ii) low heat of atomisation. The bicarbonates (MHC03) with the exception of
The reactivity ip.creases from Li to Cs. The compounds of l:.iHC0 3, are knQwn in solid state.
alkali metals are electrovalent, colourless and soluble in water. They are soluble in water and decompose on heating into
These are crystalline solids. Lithium compounds show some corresponding carbonate with evolution of CO2,
abnormal properties due to polarisation on account of small (h) Nitrates of the type, MN03, are known. These are colour- .
size of Li+ ion and high lattice energies. less, soluble in water and electrovalent in nature. With
(a)' On exposure to moist air, all alkali metals except lithium the exception of LiN03, the other nitrates decompose to
tarnish quickly. These are, therefore. always kept in nitrites and oxygen on heating. LiN03 decomposes to
kerosene to protect them from air. oxide with evolution of N02 and 02'
(b) Alkali metals decompose water with evolution of (i) Sulphates of the type M2S04 are known with the
hydrogen. The reactivity towards water increases from exception of Li 2S04, other sulphates are soluble in water.
Li to Cs. The decomposition is highly exothermic and the Sulphates are reduced to corresponding sulphides when
evolved hydrogen sometimes catches fire. fused with carbon. Sulphates of alkali metals form double
(c) Alkali metals combine directly with hydrogen to form . salts with the sulphates of trivalent metals like Fe, AI, Cr,
. crystalline solids of formula MH. The hydrides react with etc.
water liberating hydrogen. W The alkali metals dissolve in liquid ammonia without
(d) Affinity towards oxygen increases when heated in atmos- evolution of hydrogen. The colour of dilute solutions is
phere of oxygen, the alkali metals ignite and form oxides. blue. On heating colour changes to bronze. The colour
M ~'_M;O'H02 ) MzOz MOz is due to ammoniated electron.
Normal Peroxide . Superoxide M + (x+y) NH3~ [M(NH3)xt + e(NH3)y
oxide These solutions are good conductors of electricity and
(Li20) (Na20 2) (K0z,Rb02.CS02) have strong reducing properties. The solutions are
.. .. - paramagnetic in nature.
0--
Oxide ion
[-0_0_)2- .
Peroxide ion
,
[ :O~O:
Superoxide ion
] When dry ammonia is passed over hot metal, arnides are
formed.
7. The alkali metals form alloys amongst themselves and with
othermetals. These combine with mercury and form amalgams.
8. Alkali metals have a very little tendency to form complexes. (b) Down's process: Now-a-days, this process is applied..
Lithium being small in size forms certain complexes but this It involves electrolysis of fused N aCI to which CaCl2 and
tendency decreases as the size increases. KF have been added to reduce the melting point of NaCI.
9. Alkali metals cannot be extracted by application of common Iron is used as cathode and graphite as anode.
processes used for the extraction of metals due to following The electrolysis is carried at 600°C. Chlorine is discharged at
reasons: anode.
(i) Cannot be extracted by the reduction of their oxides and 14. Sodium is used in the manufacture of chemicals like Na202
other compounds as being strong reducing agents. (oxone), sodarnide, sodium cyanide, etc. It is used for making
(Ii) Cannot be extracted by displacing them from their salt lead tetraethyl employed as antiknock in petrol. In molten
solutions by any other element as they are highly state, it is used in nuclear reactors as heat transfer medium.
electropositive. For extraction of C, Be, Mg, Si, etc., in sodium lamps and as
(iii) Cannot be extracted by electrolysis of the aqueous a laboratory reagent, sodium metal is also used.
solutions of their salts as hydrogen is discharged at 15. The main source of NaCl is sea water which contains
cathode instead of a1kalj metal. 2.7-2.9 % of the salt. Table salt becomes wet in rainy season
The only successful method, therefore, is the electrolysis due to presence of impurities of MgCl2 and CaCI2.
of their fused salts usually chlorides. Generally, another 16. Sodium carbonate (washing soda), Na2C03·IOH20, is
metal chloride is added to lower its fusion temperature. generally prepared by a process called ammonia-soda
10. Lithium shows abnormal properties due to its sm~ size (atom process or Solvay process. The raw materials are NaCI, NH3
.and ion). Lithium ion on account of its small size exerts polaris- and limestone .
ing effect on negative ions; Consequently, covalent character NH3 + H20 + C02 ~ ~HC03
is developed in Li-salts. Li has highest ionisation energy and NaCI + ~C03 ~ NallC0 3+ NH4CI
electronegativityas compared to other alkali metals. 2NaH~ ~ Na2C03 + H20 + C02
(i) LiCI is more covalent than NaC!.. LiCI is soluble in Solv~rocess cannot be employed for the manufacture of
alcohol, pyridine, etc. Its melting point is lower than that K2C0 3 because KHC0 3 is fairly soluble in water.
of NaCl. A mixture of NaHC03 and potassium hydrogen tartrate is
(n) LiOH, Li2C03, LiN03 behave differently than other called baking powder while sodium bicarbonate alone is called
alkali corresponding salts towards heating. baking soda.
2LiOH ~ Li 20 + H20; Li2~03 ----?Li20 + CO 2; A mixture of Na2C03 and K2C03 is called fusion ririxture.
4LiN03~ 2Li20 + 4N02 + O2 Anhydrous Na2C03 is called soda ash and obtained by·
Hydroxides and carbonates of other alkali metals are heating Na2C03·lOH20 above 100°C. Sodium carbonate is
stable. The nitrates of other alkali metals decompose used in laundries and in softening of water. It is used in the
giving only oxygen. manufacture of glass, sodium silicate, borax, paper, soap
(iii) Lithium directly combines with nitrogen. powders, caustic soda, etc .
.6 Li + N2 ~ 2Li3N NallC0 3 is used for making baking powder, in making
(iv) LiHC0 3 is known only in solution but not in solid state. effervescent drinks, in fire extinguishers and as a medicine.
(v) Li2S04 does not form double sulphates. 17. Sodium hydroxide (caustic soda) is manufactured on a very
(vi) LiF, Li 3P04, Li 2C20 4, Li 2CO} are sparingly soluble in large scale by the following processes: .
water. (i) Gossage process: Sodium carbonate reactSJ with
(vii) LiOH is weaker base in comparison to NaOH or KOH. suspep.sion of lime (milk of lime or calcium hydroxide).
(viii) Although Li has the highest ionisation potential, yet it Na2C03 + Ca(OHh ~ 2NaOH + CaC03
is strongest reducing agent because of its large heat of Calcium carbonate being insoluble separates out and
hydration. the solution on evaporation gives flakes of caustic
11, Lithium shows resemblance with magnesium, an element of soda .
. group II A. This resemblance is termed diagonal relationship. , (ii) Lowig's process: A mixture of sodium carbonate and
The reasons for this resemblance are : (i) nearly same ferric oxide is heated to redness. Sodium ferrite is
electronegativity (ii) not much difference in atomic size and formed. The cooled sodium ferrite is thrown into hot
ionic size (ill) nearly same atomic volumes .(iv) nearly Sanle water when hydrolysis occurs forming a solution of
polarising power. NaOH and insoluble ferric oxide.
12. Important minerals of sodium are: (i) chile saltpetre (NaN03) Na2C03 + Fez03 ~ 2NaFe02 + CO2
(ii) Glauber's salt (Na2S04·lOH20) (ill) trona (Na2C03' 2NaFe02 + H20 ~ 2NaOH + Fe203
2NallC03,3H20) (iv) natron (Na2C03·H20) (v) tincal (iii) Electrolytic process: The electrolysis of sodium
or borax (Na2B40T lOH20) (vi) cryolite (Na3AlF6) chloride is carried out in an electrolytic cell. The
(vii) soda felspar (NaAISi30 g) (viii) common salt or rock salt following electrolytic cells are used:
or sea salt (NaCl). (a) Nelson ceD: It consists a perforated steel tube lined
13. Sodium is obtained on large scale by two processes. inside with asbestos. The tube acts as a cathode. A graphite
(a) CastDer's process: Electrolysis of fused sodium rod dipped in sodium chloride solution serves as anode.
hydroxide is carried at 33O"C using iron as cathode and (b) Castner-KeDnercell: This is a common cell in which
nickel as anode, Hydrogen is discharged at cathode also. mercury is used as cathode. The cell consists of a large
rectangular trough 'divided into three compartments by slate occur as salt beds in rocks and in sea water. The important
partitions. The mercury can flow from one compartment to minerals of potassium are :
other but the solution kept in one compartment cannot flow Carnallite (KCl·MgCI 2·6H20), Indian saltpetre (KN0 3),
into other. Sodium chloride solution is kept in two outer feldspar (K20·Al20 3·6Si02), sylvine (KCI), polyhalite (K2S04·
compartments and a dilute solution' of NaOH .in the inner MgS04· CaS04' 6H20), etc.
compartment. Two graphite electrodes which act as anodes 22. Potassium can-be prepared by electrolysis of fused mixture
are fitted in outer compartments and a senes of iron rods ofKCI and CaCI 2. It is manufactured by reducing fluoride with
fitted in the inner compartment act as cathode. Mercury in calcium carbide at lOOO"C.
the outer compartments acts as cathode while in the inner 2KF + CaC 2 -----7 2K + CaF2 + 2C
compartment it acts as an anode by induction. The cell is , Potassium is used in photoelectric cells. An alloy of potassium
kept rocking with the help of an eccentric wheel. Sodium and sodium is used in special thermometers employed for
discharged at the Hg cathode in the outer compartments forms measuring high temperatures.
amalgam which comes into the inner compartment due to 23. Three oxides of potassium are known : (i) potassium
rocking. Here, NaOH is formed. monoxide, K20 (ii) potassium dioxide, K02 (iii) potassium
(c) Kellner-Solvay cell: This is the modified cell having sesquioxide, K 20 3.
no compartments. Flowing Hg acts as cathode and a number K0 2 is prepared by burning potassium in excess of oxygen
of graphite rods' act as anode in sodium chloride solution. " free from moisture. It is a chrome yellow powder. It dissolves
The sodium amalgam flows out of cell and treated with water in water giving H 20 2 and 02' It is used as an oxidising agent,
to form NaOH. as air purifier in space capsules, submarines and breathing
Commercial NaOH is purified with the help of alcohol. The '" masks as, it produces oxygen ,and removes- C02'~ ,
alcoholic filtrate is rlistillel to get pure NaOH. K0 2 has bond order 1.5 and possesses paramagnetic nature
18. NapH is a white crystalline solid. It has a soapy touch. It is due to the presence of one unpaired electron.
highly deliquescent. It is highly soluble in water. It is a strong 24. K2C03 is called potash or pearl ash. It is prepared by
alkali: It cannot be kept in atmosphere as it absorbs moisture Le-Blanc process,
and COz, It reacts with acids, acidic oxides and amphoteric
oxides to form salts. It attacks non-metals like S, P, Si, B, KCI-----7 K 2S04 CaC03+C) K2C03
halogens, etc. Metals like Zn, AI, Sn, Pb react with NaOH it is used in the manufacture of hard glass.
evolving H2. A number of metallic salts react with NaOH to KHC03 resembles NaHC0 3 in all respects except that it is
form corresponding hydroxides. Ammonium salts evolve more soluble in water. It is used in medicine and in baking
ammonia with NaOH.· NaOH combines, with CO under powders.
pressure to form sodium formate. 25. Caustic potash, KOH, is manufactured like NaOH, i.e., by
19. NaOH is used as a laboratory reagent, in manufacture of soap, 'electrolysis of KCl. It is used for making soft soaps.
in manufacture of paper and rayon, dyes and drugs. It is an 26. Although both NaCN and KCN are poisonous but KCN is
absorber of gases. It is used in petroleum refining and for more poisonous than NaCN.
the manufacture of various useful sodium compounds. 27. Na2S04·lOH20 is called Glauber's salt, anhydrous Na2S04 is
20. Sodium peroxide (oxone), Na202, is formed by heating sodium called salt cake, NaHS04 is called nitre cake.
at about 350"C in excess of air free from moisture. It is a pale 28. Sodium thiosulphate, Na2S203, is used as antichlor in
yellow powder. It is used as an oxidising agent, for purification bleaching.
of air, for production of oxygen' under the name oxone and 2~. Electric eye used in television contains an alloy of caesium
for the preparation of H 20 2 and benzoyl peroxide. and silver.
21. Potassium is not found in the native state. In combined state 30. All alkali metal azides are thermally unstable and liberate
it is widely distributed in nature. All plants contain con- nitrogen and metal on heating. Lithium azide (LiN 3) is an
siderable amourit of potassium compounds. Its compounds exception. It forms stable nitride on heating.
3LiN3 ---:--t Li~ + 4N2
E••• _- PRACTICE PROBLEMS ;.. ••• -

• Subjective Type Questions 2. Give reasons :
(a) LiCI is soluble in alcohol.
1. Answer the following: (b) MgCl 2 is more covalent than NaCl.
(a) Why does table salt get wet in rainy season? (c) LiBr has lower melting point than LiE
(b) Which out of sodium or potassium has higher boiling 3. Answer the following:
point? (a) Name the alkali metals which form superoxides when
~c) Why caesium is used in photoelectric cell while lithium
heated in excess of air.
cannot be? (b) Which one is soluble in water?
(d) What makes lithium to show properties different than other LiForKF
alkali metals?
(c) Which one is soluble in NaOH? (iv) KI + HZS04 + HzO z ---? h + ...... + HzO
Al(OHh or Fe(OHh (v) NaOH + 12 ---? ...... + Nal0 3 + H20
(d) Which alkali metal is radioactive in nature? 9. Write the balanced equations of the reactions of:
(e) Name the alkali metal which shows diagonal relationship? (a) Caustic soda on the following:
(f) Which alkali metal is strongest reducing agent in aqueous (i) zinc, (ii) silver nitrate, (iii) phosphorus,
solution. (iv) arsenious oxide
4. Answer the following: (b) Hypo on the'following:
(a) Which is the most abundant alkali metal in the earth's (i) FeCI3, (li) AgCL (iii) CUS04, (iv) 12
crust? 10. Explain the following:
(b) Which sodium salt is found in plenty in sea water? (i) Sodium is less reactive than p<?tassium.
(c) Name one silicate and one phosphate ore of lithium. [Hint : Ionisation poteniial of potassium is less than
(d) Write the formulae of: sodium, i.e., the tendency to lose valency electron
(i) Caustic potash (ii) Soda ash (iii) Chile saltpetre is more·in potassium than sodium.]
(e) Which compound of sodium is used for making baking (li) Alkali metals are paramagnetic but their salts are
powder? . diamagnetic.
[Hint : In metals, the outennosl energy shell is singly
5. Answer the following:
occupied but in cations, all the orbitals are doubly
(i) What is meant by black ash?
occupied (inert gas configuration).]
(li) What is the action of NaOH on ammonium salts?
(iii) Sodium salts in aqueous solutions are, .either neutraI..or--
.. (iii) Which electrolyte is'used to obtain .sodium in Castner's
alkaline in nature.
process? [Hint : The anions in sodium salts are either from strong
(iv) Waat is washing soda? acids or weak acids. When anions from strong acids,
(v) Which electrolyte is used in Nelson's cell? there is no hydrolysis and aqueous solutions are
(vi) What is the intermediate product in Solvay's process? neutral (NaCI soln.). On the other hand when anions
(vii) Most abundant alkali metal in the earth's crust is : from weak acids, there is hydrolysis of anions and
(viii) Which chloride of an alkali metal is soluble in alcohol? the solutions are alkaline in nature (Na2C03 80ln.).
(ix) Which substance is added to sodium chloride as to C05- + H20 ~ HC0 3 + OW
reduce its fusion temperature during manufacture of
HCO:; + H20 ~ H2C03 + OW]
sodium? .
(x) What product is formed when carbon monoxide is (iv) Standard solution of NaOH cannot be prepared by
passed through sodium hydroxide under high pressure? direct weighing.
6. What happens when following are heated? [Hint : NaOH is affected by atmosphere. It absorbs
moisture. and CO2 from atmosphere. Thus, accurate
(i) Potassium nitrate (li) Sodium carbonate
weighing of NaOH is not possible.]
(iii) Microcosmic salt (iv) Sodium bicarbonate
(v) Commercial common salt becomes slightly damp on
(v) Lithiumhydroxide (vi) Lithiumnitrate keeping.
(vii) Lithium carbonate (viii) Sodium thiosulphate [Hint : Pure NaCI is not hygroscopic. The commercial
7. What happens when? common salt consists small amounts of magnesium
(a) Hot and concentrated caustic soda solution reacts with chloride and calcium chloride which absorb moisture
iodine. from atmosphere making it damp.]
(b) White phosphorus is heated with caustic soda. (vi) Sodium metal can be used for drying dielhyl ether but
(c) Sodium thiosulphate is added to silver nitrate solution. not ethanol.
(d) Iodine is reacted with hypo solution. [Hint : Sodium metal reacts with ethanol,
2C2HsOH + 2Na ----; iC 2HsONa + H2
(e) Excess of caustic soda reacts with zinc sulphate solution.
and thus cannot be used for its drying.]
(f) Excess of NaOH is added to AICl 3 solution.
(vii) A sodium fire. in laboratory is not extinguished by
(g) Anhydrous potassium nitrate is heated with excess of
water.
metallic potassium. [l.I.T.1992] [Hint : Sodium reacts with· water to produce hydrogen
(h) Copper sulphate reacts with potassium iodide. which is also inflanunable. Pyrene (CCL!) can be
(i) Copper sulphate is treated with hypo. used for this purpose.]
(j) Sodium is strongly heated in oxygen and the product is (viii) The hydroxides of aluminium an~ iron are insoluble in
treated with H2S04' . water but NaOH is used to separate one from the
8. Complete and balance the following equations: other. [U.T. 1991]
(i) KO z + HzO ---? ...... + Oz [Hint : AI(OHh dissolves in eXcess of NaOH fonning a
(li) NaNH2 + C ---? ...... + Hz soluble compound, sodium meta aluminate.
Heat Al(OHh + NaOH ----; NaAl02 +. 2H20]
(iii) PbO z + NaOH - - 7 ...... + H 20 (]X) The inside surface of a: glass bottle containing caustic
(Cone.)
soda becomes dull.
[Hint : Silica is present in glass. It dissolves in NaOH (ii) On addition' of Ag+ ion solution, a yellow curdy
slowly and forms soluble sodium silicate and thus precipitate is obtained which is insoluble in ammonium
inside surface becomes dull.] hydroxide.
. (x) Amongst LiF and LiI which has more covalent Identify (X) and give equations for the reactions at steps (i)
character and why? and (ii). [Roorkee 1991]
[Hint : LiI is more covalent. According to Fajan's rule, Li+
17. An unknown. inorganic compound (X) loses its water of
will be able to polarise the bigger ion, r, more than
crystallization on heating and its aqueous solution gives the
the smaller ion, F-. More polarisation brings more
following reactions :
covalent character.]
11. Give one test each to make distinction between the following (a) It gives a white turbidity with dilute HCI solution.
(b) It decolourises a solution of iodine in potassium iodide.
pairs:
(c) It gives a white precipitate with silver nitrate solution
(i) NH4CI and KCI (ii) NazS0:3 and Na2S04
which turns black on standing.
(iii) Na2S03 and Na2S203 (iv) KN0 3 and KI
Identify the compound (X) and give chemical equations for
(v) Na2S03 andNa2C03 (vi) NaCI and KCI the reactions at steps (a), (b) ang(c).
12. Arrange the following as specified : 18. When 20.02 g of a white solid X is heated, 4.4 g of an acid
(i) MgO, SrO, K20, NiO and Cs20 (increasing order of gas (A) and 1.8 g of a neutral gas (B) are evolved, leaving
basic character) [I.l.T. 1991]
behind a solid residue (Y) of weight 13.8 g. (A) turns lime
(li) LiCl, LiBr and LiI (decreasing order of covalent
water milky and (B) condenses into liquid which changes
character) anhydrous copper sulphate blue. The aqueous solution-of
(ill) KCI, KBr and KI (decreasing solubility in water)
(Y) is alkaline to litmus and gives 19.7 g white precipitate (Z)
(iv) NaHC03, KHC0 3, Mg(HC03h and Ca(HC03h with barium chloride solution. (Z) gives carbon dioxide with
(increasing solubility) an acid. Identify A, B, X, Y and Z.
(v) LiF, NaF, KF, RbF and CsF (in order of increasing lattice When 16.78 g of a white solid X were heated, 4.4 g of acid
19.
energy)
gas A that turned lime water milky was driven off together.
(vi) Li, Na and K (in order of decreasing reducing nature in
with 1.8 g of a gas B which condensed to a colourless liquid.
solution) The solid that remained, Y, dissolved in water to give an
13. Identify (A), (B), (C) and (D) and give their chemical formulae. alkaline solution, which with excess of barium chloride solu-
[Roorkee 1986]
tion gave a white precipitate, Z. The precipitate effervesced
Heat with acid giving off carbon dioxide. Identify A, B and Yand
(A) + NaOH ~ NaCI + NH3 + H 20
write down the equation for the thermal decomposition of X.
NH3 + C02 + H20 ~ (B) 20. Gradual addition of potassium iodide solution to Bi(N03h
(B) + NaCI ~ (C)+NH4Cl solution initially produces a dark brown precipitate which
dissolves in excess of KI to give a clear yellow solution. Write.
(C) ~ Na2C03 + H 20 + (D)
the chemical equations for the above reactions. [I.I.T. 1996]
14. From the reactions given below, identify (A), (B), (C) and.(D)
and give their formulae.
(A)(aq.) + Zn ~ (B)gas
. Heat· Match thefoUowing :
(A)(aq.) + (C) ~ PH3
[Al
(A)(aq.) + Nl4CI ~ (D)gas (a) Chile saltpetre (i) NaCN
15. A certain compound (X) imparts a golden yellow flame and (b) Indian saltpetre (li) NazC03'lOH20
shows the following reactions : (c) Gennicide (iii) Na2S04'lOH20
(i) Zinc powder when boiled with a concentrated solution (d) Baking soda (iv) Na2S203
of (X) dissolves and hydrogen is evolved. (e) Washing soda (v) N~HP04'4H20
(li) When an aqueous solution of (X) is added to' an (f) Hypo P (vi) KN~
aqueous solution of stannous chloride, a white (g) Glauber's 'salt (vii) NaHC03
precipitate is obtained frrst which dissolves in excess (h) Microcosmic salt (viii) NaN03
of solution of (X). [B]
Identify (X) and write equations for reactions at steps (a) Castner's process (i) KG
(i) and (ii). [Roorkee 1991) (b) Solvay process (ii) Potassium carbonate
(c) Nelson's cell (iii) Sodium chloride
16. A certain compound (X) is used in the laboratory for analysis,
(d) Oxone (iv) . Mixture (NaOH + CaO)
its aqueous solution gives the following reactions:
(e) Pearl ash (v) Sodium
(i) On addition to copper sulphate, a brown precipitate is
(f) Rock salt (vi) Sodium peroxide
obtained which turns white on addition of excess of
(g) Soda lime (vii) Sodium hydroxide
Na2S203 solution.
~h) Sylvine (viii) Sodium carbonate
Answers : Subjective 'TYpe Questions (i) CUS04 + Na2S203.~ CUSZ03 + NaZS04

1. (a) Table salt contains impurities such as Na2S04. CaS04. MgClz 2CUSZ0 3 + Na2SZ03 ~ CuzSz~ + NaZS406
and CaCI 2. These being hygroscopic absorb moisture from 3CUZSZ03 + 2NazS203 ~ Na4(Cu6(S2~)s]
atmosphere. As a result. table salt gets wet.
Heat
(b) The melting point of sodium is higher as it has greater metallic (j) 2Na + Oz ~ NazOz
bonding than potassium. Na20Z + H ZS0 4 ~ NaZS04 + HzOz
(c) Caesium has low ionisation enthalpy in comparison to lithium.
8. (i) 4KOz + 2HzO ~ 4KOH + 30z
Caesium can lose electrons very easily.
(d) Lithium shows different properties than other alkali metals Heat
(ii) 2NaNH2 + C ~ NazCNz+ 2Hz i
due to following reasons:
(i) small atomic and ionic size NazCN2 + C ~ 2NaCN
(ii) high ionisation potential (ill) . Pb0 2 + 2NaOH ~ Na2Pb03 + HzO
(iii) high polarizing power (iv) 2KI + H2S0 4 + H20 2 ~ 12 + KiS04 + 2H20
2. (a) U" ion. being small in size, has high polarising power and hence (v) 6NaOH + 312 ~ 5NaI + NaI03 + 3HzO
LiCI is a covalent compound and thus. it is soluble in alcohol.
9. (a) See properties of NaOH.
(b) Mg2+ ion, on account of higher charge than Na+ ion, has greater (b) See properties of sodium thiosulphate.
polarising power. Hence, Mg~l2. is more.cov~ent than NaCl.. 11. (a) When heated with NaOH, NH4Cl evolves armnonia gas..~-.
"(efST": ion, on account of bigger size than P- ion, is more
NH4CI + NaOH ~ NH3 + NaCI + H20
polarisabJe than F- ion. Hence, LiBr is more covalent than LiP
and thus, it has lower melting point. (b) On treatment with dil. H2S04• a pungent gas, SOz, is evolved
3. (a) K, Rb, Cs (b) KF (c) Al(OHh (d) Fr (e) Li (f) Li which turns acidified KZCrZ07 green.
4. (a) sodium (b) sodium chloride (c) Lepidolite (silicate ore) • Na2S~ + H 2S04 ~ Na2S04 + H 20 + S02
. Triphylite (phosphate ore) (d) (i) KOH (ii) NazC~ (c) On addition ofAgN03 solution, sodium thiosulphate gives a
(iii) NaN03 (e) NaHC03 white precipitate which turns black.
5. (i) Black ash is impure sodium carbonate produced in Le-Blanc 2AgN03 + Na2S203 ~ Ag2S2~ + 2NaN03
method when salt cake is reduced by coke. (ii) Ammonia is
Ag2Sz0 3 + H20 ~ Ag2S+ H 2S04
liberated: NH4CI + NaOH ~ NH3 + NaCl + H20 (iii) Fused
sodium hydroxide. (iv) Sodium carbonate decahydrate. (v) Sodium (d) On addition of AgN03 solution, KI gives a yellow precipitate
chloride solution. (vi) Sodium bicarbonate. (vii) Sodium. of AgI.
(viii) Lithium chloride. (ix) Calcium chloride. (x) Sodium formate. 2AgN03 + 2KI ~ 2AgI + 2KN03
6. (i) 2KN0 3 ~ 2KN02 + Oz (e) On addition of dil. HC!, NaZS03 gives pungent gas which turns
(ii) Water of crystallisation is lost and the substance becomes acidified K2Cr2~ paper green.
anhydrous. (f) Flame test.
Na2C03'IOH20 ~ Na2C03 + 1OH20 12. (i) NiO < MgO < srO < K20 < Cs20
(ill) NaNH 4HP04 ~ NaP0 3 + NH3 + HzO " (ii) Lil > LiBr > LiCI
Sodium meta- (ill) KI > KBr > KCI, lattice energy of KI is lower than the lattice
phosphate
energy of KCl.
(iv) 2NaHCOj ~ NaZC03 + HzO + COz (iv) NaHC03 < KHC03 < Mg(HC0 3h < Ca(HC03h
(v) 2LiOH ~ LizO + HzO (v) CSfl < RbF < KF < NaF < LiP
(vi) 2LiN03 ~ LizO + 2NOz + ~ Oz (vi) Li > K >Na
(vii) Li zC03 ~ LizO + COz 13. (A) ~Cl, armnonium chloride; (B) ~C03. armnonium bicar-
(vill) 4NazSZ03 ~ 3NazS04 + NazSS bonate; (C) NaHC03• sodium bicarbonate; CD) COz. carbon dioxide.
14. (A) NaOH, sodium hydroxide; (B) H2, hydrogen; (C) P4• phos-
7. (a) 6NaOH + 31z ~ 5NaI + NaI03 + 3HzO
phorus; (D) NH3, ariunonia.
(b) P4 + 3NaOH + 3HzO ~ 3NaHzPOz + PH3 15. (X) NaOH =
(c) 2AgN03 + NaZSZ03 ~ Ag zSz0 3 + 2NaN03 (i) Zn + 2NaOH ~ Na2Zn02 + H2
AgzSz03 + HzO ~ AgzS + HZS04 (li) SnCl 2 + 2NaOH ~ Sn(OHh + 2NaCI
(d) 12 + 2NazSZ03 ~ 2NaI + NaZS406 Sn(OHh + 2NaOH ~ Na2SnOZ + 2H zO
(e)' Zns04 + 2NaOH ~ Zn(OHh + NaZS04 Soluble
. Zn(OHh + 2NaOH ~ NazZnOz + 2HzO
16. X =KI
(i) 2CUS04 + 4KI ~ 2Cul2 + 2KzS04
(f) AlCl 3 + 3NaOH ~ AI(OHh + 3NaCI
2Cul2 ~ CU212 + 12
Al(OHh + NaOH ~ NaAlOz + 2HzO (White)
(g) 2KN0 3 + 10K ~ 6KzO + N2 Iz + 2Na2S203 ~ 2NaI + Na2S406
(h) CuS04 + 2KI ~ Cul2 + K ZS04 (li) Ag++KI ~ AgI + K+
Yellow ppt.
2Cul2 ~ CUz12 + Iz
Insoluble in ~OH
17. X Na2S203'SH20 .
So, X + 61 20.02 or X:::: 39.1 g
(a) Na2S203 + 2HCl ---t 21;laCI + H20 + S + S02 5
(b) KI3 + 2Na2S203 ---t KI + 2NaI + Na2S406 Therefore, the .alkali metal is K.
(c) 2AgN03 + Na2S2~ ----t Ag 2S20 3 + 2NaN03 Thus, X is KHC03
Ag2S20 3 + H 20 ---t Ag 2S + H 2S04 2KHC0 3 ---t K2C0 3 + CO2 + H20
(X) (y) (A) (B)
7
Heat
18. (X) ~ (A) + (B) + (Y) K2C~ + BaCl2 ---t BaC0 3 + 2KCI
White solid . Acid gas Neutral gas' Residue 138.2 (Z)197
20.02 g 1.8 g 13.8 g
138.2 g of K 2C03 forms.197 g BaC03
\:2 0
13.8 g of K2C03 forms ~ x 13.8 g Bae03 or 19.7 g
138.2
Anhydrous Soln.
This confums the given data .
CUS04 . Alkaline to litmus
1 1 BaCI2 soln.
19. X is NaHC0 3.
2NaHC03 ---t Na2C03 + C02 + H20
(~ (y)~)~)
White ppt. (2) 19.7 g
20. At first, Bi(N03h undergoes hydrolysis. Nitric acid is formed.
Acid 1 Which oxidises KI to iodine. The liberated jodine dissolves in KI
C02~
(2 ) is a carbonate as it evolves C~ with acid. (n is also a to form yellow solution of KI3.
lts is
carbonate o{analkali metal because soitition iilIcillineio litmus Bi(N03 h + H20 ~ [Bi(OH)(N03}z] + HN03
and gives a white precipitate of BaC03 with BaCl2 soln. (E) is 2HN0 3 ---t H20 + 2N02 + 0
H20 and (A) is CO 2. Thus, (X) is a bicarbonate, MHC03 •
2KI + H 20 + 0 ---t 2KOH + 12
2MHC0 3 ---t CO2 + H 20 + M 2C03 Dark brown
(X) (A) (B) P')
12 + KI ---t KI3
2[X + 61] Yellow solution
44 g CO2 is obtained from 2(X + 6l)g of X
Answers : Matching TYPe Questions
4.4 g C02 is obtained from 2(X + 61) x 4.4 :::: X + 61 g of X [A] (a-viii); (b-vi); (c-i); (d-vii); (e-ii); (f-iv); (g-iii);
44 . 5 (h-v);
[B] (a-v); (b-viii); (c-vii); (d-vi); (e-ii); (f-iii); (g-iv);
(h-i)
ILLUSTRATIONS ;OF' OBJECTIVE QUESTIONS

\
1. Which one of the following statements is true for aU the alkali increase of the atomic number. However, LiCI has covalent
~~? \ character due to very small size ofU+ ion. Hence, melting
(a) Their nitrates decompose on heating to give N0 2 and O 2, ' \ point of NaCl is highest amongst the above chlorides.]
(b) Their carbonates decompose on heating to give CO 2 and \ 4. Select cOFfect statement :
normal oxide. . (a) Oxides (M20) and peroxides (M202) of alkali metals are
(c) They react with halogens to give the halides of the type, diamagnetic and colourless.
MX. . (b) Superoxides (M0 2 ) of aijcali metals are paramagnetic.
(d) They react with oxygen to give mainly the oxide, M 20. \c) Li and Na do not form superoxides.
Ans. (e) (d) All are correct.
2. The electrolyte used in Castner's process of sodium Ans, (d)
extraction is.: 5. Whi~h of the following salts does not form any precipitate
(a) .anhydrous Na2C03 (b) aqueous NaOH with excess of NaOH ?
(c) NaCI+CaCI 2 (d) fused anhydrous NaOH (a) ZnCl2
Ans. (d) (c) CrCl3 \
Ans. (a) \
3. Based on lattice energy and other considerations which one NaOH.
of the following alkali metal chloride is expected to have [Hint: ZnCI2 + NaOH ---t Zn(OHh ----4 Na2Zn02
. highest melting point ? Soluble
(a) LiO (b) NaCI FeCl 3 + NaOH ---t Fe(OHh (brown ppt.)
(c) KO (d) RbCI CrCl) + NaOH ---t Cr(OHh (green ppt.)
Ans. (b) CuS04 + NaOH---t Cu(OHh (blue ppt.)]
.[Hint : On the basis of lattice energy, the melting point decreases
6. Which of the following is best C02 absorber as well as source
in the alkali group as lattice energy decreases with the
of O2 in space capsule ?
(a) K02 (b) K2~ 12. Which among the following is least soluble in water?
(c) KOH (d) UOH (a) NaF (b) LiF
AIlS. (a) (c) KF (d) RbF
[Hint : 4K02 + 2C0 2 --'--7 2K2C0 3 + 302 ] Ans. (b) .
7. Match the compounds given in (X) with their uses in (Y). [Hint : LiP has maximum lattice energy and hence least soluble.]
(X) {Y) 13. Which of the following metals is used for drying organic
A. NaOH 1. Glass solvents?
B. Na2S2~ 2 Gemricide (a) Magnesium (b) Sodium
C NaCN 3. Antichlor (c) Platinum (d) Nickel
D. Na2C~ 4. Soap AIlS. (b)
Codes: 14. Which of the following does not illustrate the anomalous
ABC D behaviour of lithium ?
(a) 4 3 2 1 (a) Lithium reacts with nitrogen to form a nitride
(b) 3 4 1 2 (b) Lithium is the hardest alkali metal
(c) 2 3 4 1 (c) Lithium reacts with oxygen to form normal oxide only
(d) 1 2 3 4 (d) Lithium carbonate decomposes on heating
AIlS. (a) AIlS. (b)
8. On dissolving moderate amount of sodium metal in liquid 15. The correct order of stability of hydrides of alkali metals is :
ammonia at low temperature, which of the following does not (a) LiH>NaH>KH>RbH (b) NaH>KH>RbH>LiH
occur? (c) RbH > KH>NaH>LiH (d) LiH > RbH> KH>NaH
(a) Blue coloured solution is obtained AIlS: (a)
(b) Na+ ions are formed in solution [Hint: Small anion forms stable compound with small cation.]
(c) Liquid ammonia becomes good conductor of electricity 16. The correct order of mobility of alkali metal ions in aqueous
(d) The liquid ammonia remains diamagnetic solution is: [C.B.S.E. 2006]
Ans. (d) (a) K+ > Rb+ > Na+ > Li+ (b) Rb+ > K+ > Na+ > Li+
9. The aqueous solutions of lithium salts are poor conductor (c) Li+ > Na+ > K+ > Rb+ (d) Na+ > K+ > Rb+ > Li+
Ans: (b)
of electricity rather than other alkali metals because of :
[Hint : Smaller the size of the ion, more is the hydration and
(a) hlgh ionisation energy
therefore lesser is the mobility.]
(b) high electronegativity
(c) lower ability of Li+ ions to polarise water molecules
17. Pick out statement(s) which is(are) not true about diagonal
relationship of Li and Mg:
(d) higher degree of hydration of Li+ ions
AIlS. (d) A Polarising powers of Li+ and Mg2+ ions are almost same
200·e .
B Like Li, Mg decomposes water very 'fast
10. NaOH +CO--::-=..::.,:-~) X. The product X is : C LiCI and MgCl2 are deliquescent
S-lOatm.
'(a) NaHC03 (b) Na2C03 D Like Li, Mg readily reacts with liquid bromine at ordinary
(c) HCOONa (d) H2C03 temperature
AIlS. (c) (a) A and D (b) Band C
11. Which of the property of alkali metals is not listed correctly? (c) Only B (d) Band D
(a) The least electronegative metal : Cs AIlS: (d)
(b) A natural radioactivemeta1: Fr .
(c) The alkali metal with lowest density : K
(d) The most abundant alkali metal in earth's crust: Na
Ans. (c) ,
... -
Set I : Choose the correct answer out of the given alternatives for each question.
1. Electrometallurgical process (electrolysis of fused electrolyte) 13. The colour of iodine solution is discharged by shaking it with
is employed to extract: aqueous solution of:
(a) iron 0 (b) lead 0 (a) H2SO4 0 (b) sodium sulphide 0
(c) silver 0 (d) sodium 0 (c) sodium sulphate 0 (d) sodium thiosulphate 0
2, Molecular formula of Glauber's salt is: 14, Which of the following is not found in solid state?
(a) MgS04'7H2O 0 (b) CuS04'5H2O 0 (a) LiHC0:3 0 (b) NaHC03 0
(c) Na;!S04'lOH2O 0 (d) FeS04'7H20 0 (c) KHC~ 0 (d) NatHC03 0
3. Nitrogen dioxide cannot be obtained by heating: 15. Sodium metal can be stored under:
(a) KN03 0 (b) Pb(N03h 0 (a) benzene 0 (b) kerosene 0
(c) Cu(N03h 0 (d) AgN0 3 0 (c) alcohol 0 (d) water 0
4. An ingredient of baking powder is: 16. A substance X is a compound of an element of group IA.
(a) NaHC03 0 (b) Na2C~ 0 The substance X gives a violet colour in flame test, X is:
(c) Na2S04 0 (d) NaCl 0 (a) NaCl 0 (b) LiO 0
5. Sodium reacts with water more vigorously than lithium (c) KO 0 (d) None of these 0
because: 17. Select the correct statement:
(a) it has higher atomic mass 0 (a) Lithium carbonate is soluble in water 0
(b) it is more electropositive 0 (b) Potassium carbonate is soluble in water 0
(c) it is more electronegative 0 (c) Barium carbonate is soluble in water 0
(d) it is a metal 0 (d) Bicarbonate of lithium is insoluble in water 0
6. Washing soda is: 18. Alkali metals are powerful reducing agents because:
(a) Na2C03 0 (b) Na2C03'lOH20 0 (a) these are metals 0
(c) KHC0:3 0 (d) NaHC03 0 (b) these are monovalent 0
7., On heating sodium carbonate ...... is evolved. (c) their ionic radii are large 0
(a) CO2 0 (b) CO 0 (d) their ionization potentials are low 0
(c) Hz{) 0 (d) NO gas 0 19. Sodium carbonate is prepared by:
8. Sodium carbonate can be manufactured by Solvay process (a) Solvay process 0 (b) Kolbe's process 0
but potassium carbonate cannot be prepared because: (c) Contact process 0 (d) Nessler's process 0
20. Na2S203'5H20 is used in photography to:
(a) K2C03 is more soluble 0
(a) reduce AgBr to metallic Ag 0
(b) K2C03 is less soluble 0
(b) remove reduced Ag 0
(c) KHC0 3 is more soluble than NaHC0 3 0 (c) remove undecomposed AgBr as a soluble complex 0
(d) KHC0 3 is less soluble than NaHC0 3 0 (d) convert metallic Ag to silver salt 0
9, Which of the following represents correct order of decreasing 21. The reaction of sodium thiosulphate with 12 gives:
Eg x or reducing nature? (a) sodium sulphide 0 (b) sodium sulphite 0
(a) Li>Na>K>Rb 0 (b) Rh>K>Na>Li 0 (c) sodium sulphate 0 (d) sodium tetrathionate 0
(c) Rb >Li > Na> K 0 (d) Li>Rb>K>Na 0 22. Electrolysis of fused NaCI will give:
10. The solubility of MCI04 (M =Li, Na, K, Rb) increases in order 0 (b) NaOH
(a) Na 0
of: (c) NaOO 0 (d)" NaOO3 0
(a) LiCI04 < NaCI0 4 < KCI04 < RbCI04 0 23. Tin dissolves in excess of sodium hydroxide solution to
(b) NaCI04 < RbCI0 4 < LiCI04 < KCI04 0 fonn:
(c) RbCI0 4<KCI0 4 <NaCI04 <LiCI04 0 (a) Sn(OH)2 0 (b) Na2Sn03 0
(d) KCI04 < LiCI04 < NaCI04 <RbCI04 0 (c) Na2Sn02 0 (d) Sn02 0
11. Alkali metals are characterised by:
24. The hydroxide of which metal ion is soluble in excess of
(a) good conductors of heat and electricity 0
sodium hydroxide solution:
(b) high melting points 0
(c) low oxidation potentials 0 (a) Fe+++ 0 (b) Cr+++ 0
(d) high ionisation potentials 0 (c) AI+++ 0 (d) Cu++ 0
12 A solution of sodium in liquid ammonia is strongly reducing 25. An element having electronic configuration 1s2, 2i 2p6,
due to the presence of: 3s2 3p6, 4s 1 will fonn:
(a) sodium atoms 0 (b) sodium hydride 0 (a) acidic oxide 0 (b) basic oxide 0
(c) sodium amide 0 (d) solvated electrons 0 (c) amphoteric oxide 0 (d) neutral oxide 0
26. The products of electrolysis of concentrated common salt 38. Na2C03 + Fe203 ---7 A + C02, what is A in the reaction?
solution are: (a) NaFeOz 0 (b) Na3Fe03 0
(a) Na+ O 2 0 (b) H2 + 02 0 (c) Fe304 0 (d) Na2Fe02 0
(c) NaOH + H2 + Cl2 0 (d) NaOH+C1 2 +0 2 0 39. When dry ammonia gas is passed over heated sodium (out
27. Elements in the fIrst column of the periodic table are called of contact of air) the product formed is:
alkali metals. These metals have: (a) sodium hydride 0 (b) sodium nitride 0
(a) a single valency electron 0 (c) sodarnide 0 (d) sodium cynarnide 0
(b) one electron less than an inert gas confIguration 0 40. The name oxone is given to:
(c) high melting points 0 (a) ozone 0 (b) sodium peroxide 0
(d) high ionisation potentials 0 (c) sodium oxide 0 (d) sodarnide 0
28. One of the natural minerals of sodium is tincal. Its formula 41. The principal products obtained on heating iodine with
is: concentrated caustic soda solution:
(a) Na2C03'lOH20 0 (b) NaN03 0 (a) NaIO+ NaI 0 (b) NaIO + Nal03 0
(c) Na2B4~'lOH20 0 (d) NaO 0 (c) NaI0 3 + NaI 0 (d) NaI04 + NaI 0
29. Potassium when heated strongly in oxygen, it forms: 42. When a concentrated solution of ammonia is saturated with
(a) K20 0 (b) KOz 0 sodium chloride in the presence of pieces of dry ice, a water
(c) K202 0 (d) KO 0 cloud is formed. This is due to :
30. The reaction of sodium is highly exothermic with water. The (a) precipitation of sodium hydrogen carbonate from the
rate of reaction is lowered by: reaction mixture 0
(a) lowering the temperature 0 (b) precipitation of ammonium carbonate 0
(b) mixing with alcohol 0 (c) precipitation of ammonium hydrogen carbonate from the
(c) mixing with acetic acid 0 reaction mixture 0
(d) making an amalgam 0 (d) precipitation of sodium carbonate from the reaction
31. What product is obtained after electrolysis in Solvay trough mixture 0
cell ? [Hint: NH3 + H 20 + CO 2 (dry ice)---7 NH4HC03
(a) NaOH 0 (b) sodium amalgam 0 NaCI + N~HC03 ---7 NaHC0 3 + ~CI]
(c) Na 0 (d) Na2C03 0 43. A combustible gas is liberated when caustic soda solution
32 Rb0 2 is: is heated with:
(a) superoxide and paramagnetic 0 (a) S 0 (b)~0 0
(b) superoxide and diamagnetic 0 (c) 12 0 (d) Zn 0
(c) peroxide and paramagnetic 0 44. Caustic soda is:
(d) peroxide and diamagnetic 0 (a) efflorescent 0 (b) deliquescent 0
33. KOH is preferably used to absorb CO 2 gas because: (c) hygroscopic 0 (d) oxidant 0
(a) KHC0 3 is soluble in water while NaHC0 3 is sparing!'y 45. When ammonical common salt solution is saturated with
. soluble in water 0 carbon dioxide we obtain:
(b) KOH is cheaper than NaOH 0 (a) ~HC03 0 (b) CN'H4}zC03 0
(c) KOH is stronger base than NaOH 0 (c) NaHC0 3 0 (d) Na2C~ 0
(d) KOH is more soluble than NaOH in water 0 46. .The compound called microcosmic salt is:
34. What are the raw materials used in Solvay process? (a) Na2HP04'2H20 0 (b) NaCN'H4)HP04'4H20 0
(a) NaO, NH3, CaC03 0 (b) NaOH,C02 0 (c) Na2NlIJU4'2H20 0 (d) CN'H4}zHP04'2H20 0
(c) NaO,C02 0 47. From a solution of zinc chloride, zinc carbonate can be
(d) NaO, Cac03, C, H2SO4 0 obtained by adding:
35. The solubility of iodine in water is il'!-creased by: (a) NaHC03 0 (b) Na2C03 0
(a) boiling the solution 0 (c) Caco3 0 (d) MgC03 0
(b) cooling the solution 0 48, Sodium carbonate solution is alkaline due to:
(c) adding acid 0 (a) hydrolysis of Na+ 0
(d) adding potassium iodide 0 (b) hydrolysis of CO] 0
36. Potassium nitrate is called: (c) hydrolysis of both Na+ and CO]- ions 0
. (a) Mohr's salt 0 (b) Indian saltpetre 0 (d) none of the above [J
(c) Gypsum 0 (d) Chile saltpetre 0 49. When chlorine is passed through concentrated solution of
37. In the following reaction, KOH, the compound formed is:
NaOH + S ---7 A + Na2SS + H2O, (a) KOO 0 (b) KOOz 0
Ais: (c) Ka~ 0 (d) K004 0
(a) Na2S03 0 (b) Na2S04 0 50. If NaOH is added to an aqueous solution of Zn2+ ions, a
(c) Na2S203 0 (d) Na2S 0 white precipitate appears and on addiIl,g excess of NaOH,
304 G.R.B: Inorganic Chemistry for Competitions
the precipitate dissolves. In the solution, zinc exists in 62. A white solid reacts with di!. HCI to give colourless gas that
the: decolourises aqueous bromine. The solid is most likely to
(a) anionic part 0 be:
(b) cationic part 0 (a) sodium carbonate 0 (b) sodium chloride 0
(c) both in anionic and cationic parts 0 (c) sodium acetate D (d) sodium thiosulphate 0
(d) colloidalfonn 0 63. In the following sequence of reactions, identify the
51. Which of the following has lowest thennal stability? compounds (A), (B), (C) and (D) :
(a) Li2~ 0 (b) Na2C03 0 Na2C03 ~(A) Na2C03 )(B) H!at )(C) .AgN03 )(D)
(c) K 2C03 0 (d) Rb2C03 0 Solution
52. Which salt on heating does not give brown coloured gas? (a) Na2S03, NaHS03, Na2S, Ag 2S 0
(a) LiN~ 0 (b) KN03 0 (b) NaHS03,Na2S03,Na2S203,AgzS 0
(c) Pb(N03h 0 (d) AgN0 3 0 (c) NaHS03,Na2S04,Na2S,Ag20 0
53. Fire extinguishers contajn H2S04 and: (d) Na2S03, NaZS04, Na2S203, Ag 0
(a) NaHC03 and Na2C03 0 (b) NaHC03 solution 0 [Hint: Na2C03 + 15°2 + H 20--7 2NaHS0 3+ CO 2
(c) Na2C03 0 (d) Caco3 0 (A)
54. Which of the following compound is used in gun powder? 2NaHS03 + Na2C03--7 2Na2S03+ H20+C0 2
(a) LiN~ 0 (b) NaN03 0 (8)
(c) Pb(N03h 0 (d) KN03 0 Na2S03 + S--7 Na2S203

(C)
55. Which of the following compounds is(are) not soluble. in
water? Na2S203 + 2AgN0 3--7 Ag2S20 3 + 2NaN°3
(a) Li2C03 0 (b) LiF 0 Ag 2SZ0 3 + H20--7 Ag 2S + H2S0 4 ]
(D)
(c) Li3P04 0 (d) All of these 0
56. When a standard solution of NaOH is left in air for a few 64. ZnCl2 + NaHCOr--~ Heat (A) ~Heat ( B) + ( C) i + H 20
hours:
(a) a precipitate will fonn 0 (8) + NaOH -----7 D
(b) strength will decrease 0 Identify the compound D present in the solution :
(c) strength will increase 0 (a)ZnC03 0 (b) Zn(OHh 0
(d) the concentration ofNa+ ions will remain constant 0 (c) ZnO 0 (d) Na2Zn02 0
57. The pair of compounds which cannot exist together in [Hint: ZnC1 2 + 2NaHC0 3--7 Zn(HC0 3 h+ 2NaCI
(A)
solution is: Zn(HC0 3h--7 ZnC03 + H 20+C0 2
(a) NaHC03 and NaOH o (b) NI!2C03 and NaHC03 0 (8) (C)
(c) Na2C03andNaOH 0 (d) NaHC0 3 andNaCI 0 ZnC0 3 + 2NaOH--7 Zn(OHh + Na2C03
58. Which of the following reactionls is/are correct ?
Zn(OHh + 2NaOH--7 Na2Zn02 + 2H 20 1
(i) Cl 2 + NaOH -----7 NaCI + NaCI0 3 + H 20
Cone. and hot 65. .LiAlH4 is used as:
solution
(ii) P4 + NaOH + H 20-----7 NaH 2P0 2 + PH 3 (a) an oxidising agent 0 (b) a reducing agent 0
(yellow) (c) a mordant . 0 (d) a water softener 0
Heat· 0 66. Sodium sulphate is soluble in water whereas barium sulphate
(iii) S + NaOH ~ Na2S203 + Na2S + H2
.is sparingly soluble because:
(iv) C + NaOH ~Na2Si03 + Hi (a) the hydration energy of sodium sulphate is more than
its lattice energy ·0
(a) (i) and (ii) 0 (b) (ii) and (iii) 0
(b) the lattice energy of barium sulphate is less than its
(c) (i), (ii) and (iii) 0 (d) all are correct 0
hydration energy 0
59. The most abundant alkali metal in l1ature is:
(c) the lattice energy has no role to play is solubility 0
(it) lithium - 0 (b) sodium .0
(d) the hydration energy of sodium sulphate is less than its
(c) potassium 0 (d) caesium 0
lattice energy . 0
60. When sodium hydroxide solution is electrolysed:
67. Which of the following increases in magnitude as the atomic
(a) hydrogen is discharged at cathode 0
number of alkali metals increases?
(b) hydrogen is discharged atanode 0
(a) Electronegativity 0
(c) sodium is liberated at anode 0
(b) First ionisation potential 0
(d) no hydrogen is liberated 0
(c) Ionic radius 0
61. In the Castner process for the extraction of sodium, the anode
(d) Melting point 0
is made of: [E.A.M.C.E.T.2003]
68. Sodium lias, as compared to potassium:
(a) nickel 0 (b) iron 0
(aj less electronegativity 0
(c) copper 0 (d) sodium 0
(b) more ionisation potential 0
(c) larger atomic radius 0 83. Thermal stability of hydrides of first group elements follows
(d) lower melting point 0 the order: [C.B.S.E. 2008]
69. Which of the following alkali metals does not form alums? (a) LiH > NaH > KH > RbH 0
(a) Rb 0 (b) K 0 (b) LiH > KH > NaH > RbH 0 .
(c) Na 0 (d) Li 0 (c) LiH >RbH > KH > NaH 0
70. Incorrect match is : (d) LiH > KH > RbH > NaH 0
(a) Soda ash: Na2C03 0 (b) Bone ash : CuC03 0 84. There occurs loss of mass, when a rilixture of LhC03· and
(c) Pearl ash : K2C03 0 (d) Baking soda : NaHC030 Na2C03·lOH20 is heated strongly. ,The loss of mass is due
71. The metallic lustre exhibited by sodium is explained by: to:
(a) diffusion of sodium ions . . 0 (a) decomposition of LhC03 only 0
(b) loss of water by Na2C03·10H20 0
(b) oscillation of mobile valence electrons 0
(c) both (a) and (b) 0
(c) existence of free protons 0
(d) none of these 0
(d) existence of body centred cubic lattice 0 85. In certain matters, lithium differs from other alkali metals, the
72. Crude common salt is hygroscopic because of impurities of:
main reason for this is:
(a) CaS04 and MgS04 0 (a) small size of lithium atom and Li+ o
(b) CaCl2 and MgCl2 0 (b) extremely high electropositivity of Li o
(c) CaBr2 and MgBr2 0 . (c) greater hardness of Li o
(d) Ca(HC03nandMg(HC03n 0 (d) hydration of Li+ ion o
73. Which of the following compounds of potassium is known 86. Identify the correct statement. Elemental sodium:
as 'pearl ash'? (a) can be prepared and isolated by electrolysing an aqueous
(a) KzC03 0 (b) KMn04 0 solution of sodium chloride 0
(c) KCl 0 (d) KN0:3 0 (b) is a strong oxidising agent 0
74. In the electrolysis of NaCI solution for the manufacture of (c) is insoluble in ammonia 0
NaOH, the ion discharged at cathode is: (d) is easily oxidised 0
(a) Na+ '0 (b) cr 0 87. Which rea.cts directly with nitrogen to form nitride?
(c) IV 0 (d) d- 0 (a) Na 0 (b) Li 0
75. When sodium is added in scanty. water, it catches fire. In (c) K 0 (d) Rb 0
this process which one of the following burns? 88. Which of the following compounds on reaction with NaOH
(a) Na, 0 (b) H20 0 and H 20 2 gives yellow colour?
(c) CO 0 (d) H2 0 (a) Zn(OHn 0 (b) CI(OHh 0
76. Among LiCI, RbCI, BeCh and MgCl2 the compounds with (c) Al(OHh 0 (d) None of these 0
greatest and least ionic character respectively are: 89. The stability of the following alkali metal chlorides follows
(a) LiCl,RbCI 0 (b) RbC~BeC12 0 the order:
(c) RbCI,MgCl2 0 (d) MgC12,BeC12 0 (a) LiCl > KCI > NaCI > CsCI o
77. Stable oxide is obtained by heating the carbonate of the (b) CsCI > KCI > NaCI > LiCl o
element: (c) NaCI > KCI > LiCI > CsCI o
(a) Li 0 (b) Na 0 (d) KCl > CsCI > NaCI' > LiCI o
(c) K 0 (d) Rb 0 90. Which of the following has the' highest melting point?
78. The chloride that can be extracted with ether is: (a) NaCl 0 (b) NaP 0
(a) NaCl 0 (b) KCl 0 (c)NaBr 0 (d) NaI 0
(c) LiCI 0 (d) RbCI 0 91. Oxoneis: [P.M.T. (Manipal) 2001]
79. PrefIX 'alkali' for alkali metals denotes: (a) Cao 0 (b) N20 0
(a) silvery lustre 0 (b) metallic nature 0 (c) Na202 0 (d) NaB0:3 0
(c) active metals 0 (d) ashes of plants 0 92. In view of their low ionisation energies, the alkali metals are: .
80. LizS04 is not isomorphous with sodium sulphate: [P.M.T. (M.P.) 2002]
(a) due to small size of lithium 0 (a) weak oxidising agents o
(b) due to high hydrogen number of lithium 0 (b) strong reducing agents o
(c) due to high ionisation energy of lithium 0 (c) strong oxidising agents o
(d) none of the above 0 (d) weak reducing agents o
81. For the preparation of sodium thiosulphate by "Spring's 93. Which of the following has lowest melting point?
reaction", the reactants used are : [E.A.M.C.E.T.2003] [B.V. (Pune) 2002]
(a) Na2S + Na2S03 + Cl2 0 (b) Na2S + S~ 0 (a) Li o (b) Na o
(c) Na2S + Na2S03 + 12 0 (d) Na2S03 + S 0 (c) K o (d) Cs o
82. Ease with which hydrides are formed from Li to Cs: 94. When sodium is treated with sufficient oxygen/air, the
(a) decreases 0 (b) increases 0 product obtained is: [A.F.M.C. 2002]
(c) remains the same 0 (d) none of these 0
308·· GR.B. Inorganic Chemistry for Competitions
1. (d) 2. (c) 3. (a) 4. (a) 5. (b) 6. (b) 7. (c) 8. (c) 9. (d) 10. (c)
11. (a) 12. (d) 13. (d) 14. (a) 15. (b) 16. (c) 17. (b) 18. (d) 19. (a) 20. (c)
21. (d) 22. (a) 23. (ti) 24. (c) 25. (b) 26. (c) 27. (a) 28. (c) 29. (b) 30. (d)
31. (b) 32. (a) 33. (a) 34. (a) 35. (d) 36. (b) 37. (c) 38. (a) 39. (c) 40. (b)
41. (c) 42. (a) 43. (d) 44. (b) 45. (c) 46. (b) .47. (a) 48. (b) 49. (c) SO. (a)
51. (a) 52. (b) . 53. (a) 54. (d) 55. (d) 56. (b) 57. (d) 58. (c) 59. (b) 60. (a)
61. (a) 62. (d) 63. (b) 64. (d) 65. (b) 66. (a) 67. (c) 68. (b) 69. (d) 70. (b)
71. (b) 72. (b) 73. (a) 74. (c) 75. (d) 76. (b) 77. (a) 78. (c) 79. (d) SO. (a)
81. (c) 82. (a) 83. (a) 84. (c) 85. (a) 86. (d) . 87. (b) .8S. (b) 89. (d) 90. (b)
91. (c) 92. (b) 93. (d) 94. (b) 95. (a) 96. (d) 97. (a) 9S. (b) 99. (d) 100. (a)
101. (a) 102. (d) 103. (a) 104. (a) 105. (b) 106. (d) 107. (a) lOS. (b) 109. (a) 110. (d)
111. (d) 112. (d) 113. (b) 114. (c) 115. (c) 116. (c) 117. (a) I1S. (d) 119. (b) 120. (d)
121. (c, d) 122. (a,b) 123. (a,b,d) 124. (a,b,c) 125. (b,d) 126. (a,d) 127. (a, d) 128. (c, d) 129. (a,b,c) 130. (b,c,d)
131. (a,b,d) 132. (a,b,c) 133. (b) 134. (a,b)
•• Objective aues~ions for liT ASPIRANTS ,•••

1. Zinc on reaction with NaOH gives a salt (A) along with a [Hint: Ca(OH}z + Na2C03.~ 2NaOH + CaC0 3
gas (X) and (A) on reaction with a gas (Y) gives white pre~ (All (8) (C)
CO 2
cipitate (W). Which of the following is correct? ~~----~) CaC03 ]
(a) (A) is Na4Zn03, (y) is H 2S (b) (X) is H2o (W) is Zn (OHh 7. An aqueous solution of an halogen salt of potassium reacts
(c) (A) is Na2Zn02, (X) is 02 (d) (W) is ZnS, (X) is H2 with same halogen X to give KX3, a violet coloured solution
[Hint : Zn + 2NaOH ~ Na2Zn02 + H2 ; which is used in volumetric exercises (iodimetric titrations).
(A) (X) The halogen X is:
Na2Zn02 + H 2S ~ Zns + 2NaOH] (a) fluorine (b) bromine
(Y) (W) (c) chlorine (d) iodine
2. For Na + NH3 ~ (A) ~ gas
0 [Hint: KI + 12 ~ KI3 (violet coloured solution)]
N2 ) (B) (X),
Which of the following is correct? 8. In LiAIH4' metal Al is present in:
(a) (A) on reaction with water gives NaOH and N2 (a) cationic part
(b) (B) contains anion of linear geometry (b) anionic part
(c) (X) is coloured (d) All are correct (c) in both cationic and anionic parts
N20 (d) neither in cationic nor in anionic part
[Hint: Na + NH3 .~ NaNH z-----"--7 NaN3 ~ Na + N2
(A) (B) (X)
[Hint: LiAIH4 ~ Li+ + AlH.i]
Cation Anion
The anion in (B) is N3 which possesses a linear geometry.] 9. When sodium reacts with excess of oxygen, oxidation number
3. CO2 gas along with solid (Y) is obtained when sodium salt of oxygen changes from:
(X) is heated. (X) is again obtained when CO 2 gas is passed (a) 0 to -1 (b) 0 to -2
into aqueous solution of (Y). (X) and (Y) are: (c) -1 to -2 (d) + I to-l
(a) Na2C03,Na20 (b) Na2C03,NaOH [Hint:2Na + O2 (excess) ~ Na20z
(c) NaHC03,Na2C03 (d) Na2C03,NaHC~
t
[Hint: 2NaHC03 ~ Na2C03 + H 20 + CO2 ;
(X) (Y)
1
O.N. = zero
O.N. -1]
Na2C03 + H20 + CO 2 ~ 2NaHC03] 10. Sodium is heated in air at 350°C to form X. X absorbs CO 2
(X) (Y) and forms sodium carbonate and Y. Which of the following
4. For Na + PH3 ~ (A) + gas(X), Na + NH3 ~ (B) + gas is Y?
(X), which of the following is correct? (a) H2 (b) Oz
(a) The ani()n of (A) is trinegative while the anion of (B) on (c) H202 (d) ~
reaction with acetylene gives ammonia O2
[Hint :2Na ~ Na20z; 2Na202 + 2C0 2 ~ 2Na2C03 + 02]
(b) The anion of both (A) and (B) are uninegative
(c) The anion of both (A) and (B) are trinegative 11. Which disproportionates on heating with NaOH ?
(d) None of the above (a) P4 (b) S
[Hint: 3Na + PH3 ~ Na3P + ~ Hz
(c) Q 2 (d) All of these
(A) (X)
[Hint: P4 + 3NaOH + 3H20 ~ 3NaH2P02 + PH 3
(+1) (-3)
1
Na + NH3 ~ NaNHz + 2H2 ;
4S + 6NaOH ~ NazS + NazSz~ + 3H20
(8) (X)
(-2) (+2)
NaNH2 + C 2Hz ~ NaCzH + NH 3]
3C12 + 6NaOH ~ 5NaCl + NaCI0 3 + 3H20]
5. Sodium oxide can be obtained by heating: (-1) (+5)
(a) sodium carbonate alone (b) sodium nitrate alone 12. On heating a mixture containing 1 mole each of Li2C03 and
(c) sodium nitrite with sodium (d) none of these K2C03 .......... is/are formed.
[Hint : 2NaNOz + 6Na ~ 4NazO +. N2] (a) 2 moles of CO2 (b) 1 mole of C02
6. A + Na2C03 ~ B + C (c) 1.5 moles of CO2 (d) no carbon dioxide
[Hint : Li2C03 decomposes while K2C0 3 is stable and does not
I CO 2 Milky cloud, C
) decompose.
The chemical formulae of A, B and Care: LjzC0 3 ~ Li 20 + CO2 ]
ABC 1 mole I mole
(a) Ca(OHh NaOH CaC03 13. When a substance A reacts with water it produces a com-
(b) NaOH Ca(OHh CaC03 bustible gas B and a solution of a substance C in water. When
(c) NaOH CaO CaC03 another substance D reacts with this solution of C, it also
(d) CaO Ca(OHh NaOH produces the same gas B on warming, but D can produce B
GR.B. Inorganic Chemistry for Competitions
on reaction with dilute sulphuric acid at room temperature. A (a) NaHC03,Na2C03 (b) HCOONa, FOONa
imparts a deep golden yellow colour to a smokeless flame of
COONa
Bunsen burner. A, B, C and D respectively are:
(c) HCOONa,NaOH (d) NaHC03,NaOH
(a) Na, H2, NaOH and Zn
[Hint : CO -+ NaOH ~ HCOONa
(b) K, H2, KOH and Al
(c) Ca, H2, Ca (OHh and Sn
2HCOONa --=-=-7 COONa
I
(d) CaC2, C2H2, Ca (OHh and Sn COONa
[Hint: Na + H20 ~ NaOH + H2
(A) • (C) (8) FOONa + CaCI2~ yOO)ca + 2NaCI]
I
COONa COO
I (5) White ppt.
18. Select the correct statement:

Zn + H2S04 ~ ZnS04 + H2] (a) Solubility of alkali hydroxides is in order: .
(D)
CsOH > RbOH > KOH > NaOH > LiOH
14. What is the heat of solution of sodium chloride from follow-
ing data? (b) Solubility of alkali carbonates is in order:
Hydration energy of Na+ =
389.4 kJ mort LiZC03 > Na2C03 > K2C03 > RbzC03 > CSzC03
(c) both are correct
Hydration energy of Cl- =
382.3 kJ mol-': I
(d) none of the above is correct
Lattice energy of NaCI = - 776 kJ mol-' 19. ~CI + (A) ----7 Microcosmic salt
(a) + 8.6 kJ mol-' (b) + 4.3 kJ mor'
IHeat
(c) 4.3 kJ mol- l (d) - 8.6 kJ mor l (B) . Heat .) (C)
[Hint: AHsol. =Hydration ener~y Lattice energy + MnO Violet be'ld
Hydration energy of NaCI =
-389.4-382.3 (A), (8) and (C) are:
= - 77].7 kJ mor1] (a) Na3P04, NaP03, (Mnh(P04h
15. There is loss in mass when mixture of Li2C03 and (b) Na2HP04, Na3P04, Mn3(P04h
Na2C03·lOH20 is heated strongly. The loss is due to: (c) Na2HP04, NaP03, Mn(P0 3h
(a) Li2C03 only (d) Na2HP04,NaP03,NaMnP04
(b) Na2C03·lOH200nly [Hint : NH4C1 + Na2HP04 ~ NaN~HP04
(A) Microcosmic salt
(c) bothLhC03andNa2C03·lOH20
IHeat
16. A colourless solid (X) on heating evolved CO 2 and also gave NaPO 3 ~
+MnO
MnNaPO 4 ]
Violet bead
a white residue, soluble in water. Residue also gave CO2
when treated with dilute acid (X) is : 20. The aqueous solution of an unknown sodium salt gives the
(a) Na2C0:3 (b) CaC03 following reactions :
(c) NaHC03 (d) Ca(HC~h (l) It gives white turbidity with dilute HCI solution.
[Hint : 2NaHC03 ~ Na2C03 + H20 + CO2 ] (II) It decolourises a solution of iodine in potassium iodide.
/1Acid (ill) It gives a white precipitate with AgN03 solution which

changes colours and finally becomes black on
Soluble CO 2 standing.
in water The unknown sodium salt is:
200"C Heat (a) sodium sulphite (b) sodium sulphide
17. CO+NaOH 5-lOAtm) (A) ~ (B) (c) sodium bisulphite (d) sodium thiosulphate
lcacI 2 [Hint : (i)' Na2S203 + 2HCI ~ 2NaCI + S02 + H20 + S
White ppt. (li) Kl3 + 2Na2S203 ~ Kl + 2Nal + Na2S406
(A) and (B) are : (ili)2AgN0 3 + Na2S203 ~ Ag2S20 3 + 2NaN°3
1. (d) 2. (b) 3. (c) 4. (a) 5. (c) 6. (a) 7. (d) 8. (b) 9. (a) 10. (b) 11. (d) 12. (b)
U (a) 14. (b) . 15. (c) 16. (c) 17. (b) 18. (a) 19. (d) 20. (d)

1. Match List-I with List-II: S. Match List-I with List-II:
(a) Triphylite (p) Ore of lithium (a) Na (p) Stored in kerosine
(b) Amblygonite (q) Phosphate ore (b) NaHC0 3 (q) used in photoelectric cell
(c) Natron (r) Borax (c) K (r) Stored in benzene
(d) Tincal (s) Na2C03·H20 (d) Cs (s) Component of baking; powder
2. Match the compounds in List-I with their colour in List-II: 6. Match List-I with List-II:
List-( List-II List-I List-II
(a) Li3N (p) Pale yellow (a) Efflorescent (p) NaOH
(b) K20 (q) Orange (b) Deliquescent (q) KOH
(c) Cs 20 (r) Colourless (c) Fusion mixture (r) Na2C03 and K2C0 3
(d) Rb20 (8) Ruby red (d) Washing soda (s) Na2C03·lOH20
(e) Li 20 7. Match List-I with List-II:
3. Match the compounds of List-I with their composition of List-II: List-I List-II
List-I List-II (a) Refractory metal (p) Li
(a) Black ash (p) K2C0 3 (b) Metal used in the Grignard reagent (q) Mg
(b) Washing soda (q) CaS (c) The metal which form (r) Cs
(c) Nitrolim (r) Na2C03 hydrated chloride
(d) Pearl ash (s) CaCN2 + C (d) Metal used in the photoelectric cell (s) K
4. Match List-I with List-II: 8. Match List-I with List-II:
List-( List-II List-I List-II
(a) Alkali metal with highest m.pt. (p) Water (Alkali metal) . (Oxide)
(b) Alkali metal with least metallic character (q) Li (a) Na (p) Superoxide
(c) Sodium cannot be stored under (r) Ionic hydride (b) Cs (q) Coloured oxide
(d) CaH2 (s) Hydrolith (c) K (r) .Stable peroxide
(d) Li' (s) Normal oxide
1. (a-p, q) (b-p, q) (c-;s) (d-r) S. (a-p, r) (b-s) (c-p, q, r) (d-p, q, r) .

2. (a-s) (b-p) (c-q) (d-p) (e-r) 6. (a-s) . (b-p, q) (c-r) (d-s)
3_ (a-q, r) (b-r) (c-s) (d-p) 7_ (a-q) (b-q) '(c"':p, q) (d-f, s)
4. (a-q) (b-q) (c-p) (d-r, s) 8_ (a-r) (b-p, q) (c':"p, q) (d-s)
I Assertion-Reason Type Questions -,

The following questions consist of an Assertion (A) and' 2. (A) Lithium chloride is predominantly covalent compound.
Reason (R). Use the following key to choose the appropriate (R) . Electronegativity difference between Li and Clis ·small.
answer. [J.I.T. 1998J
(a) If both (A) and (R) are correct and (R) is the correct 3. (A) Alkali metals do not occur in native state.
explanation of (A). (R) Alkali metals are highly reactive metals.
(b) If both (A) and (R) are correct but (R) is not the correct 4. (A) K2C03 cannot be prepared by Solvay process.
explanation of (A). (R) K2C0 3 does not decompose on heating. .
(c) If (A) is correct but (R) is not correct. 5. (A) Soditim metal when dissolved in liquid ammonia forms a
blue coloured solution.
(d) If both (A) and (R) are not correct.
(R) The blue solution is a good conductor of electJ;icity.
1. (A) Lithium resembles magnesium, diagonally placed in IIA
6. (A) Among the' alkali metals, caesium salts exhibit. the
group.
maximum electrical conductance in aqueous solutions.
(R) The sizes of lithium and magnesium atoms and their ions
(R) Bigger the radius of the hydrated cation, higher is the
(Li+ and Mg2+) are nearly the same. /A.I.I.M.S. 1997J
electrical conductance of the aqueous solution.
Group
IIAor 2
Be
4
Beryllium
CHAPTER 7
2;
12
Mg
Magnesium
3;
Ca
20
Calcium
Alkaline Earth Metals
i
Sr
4;
38 ··and their Compounds
(Group lIA or 2, ns 2)
Strontium
5;
i 56
I !!~
6;
.
l Ra
88
7.JI POSITION OF ALKALINE EARTH METALS IN
PERIODIC TABLE
I R~,m Contents: The group ITA of the periodic table consists of six elements--beryllium, mag-
7.1 Position of Alkaline Earth Metals in Periodic nesium, calcium, strontium, barium and radium. These elements are collectively
Table called as alkaline earth metals because their earths (the old name for oxide)
7.2 Solubility of Compounds of Alkaline Earth are basic (alkaline) and group IIA is known as alkaline earth group. The
Metals oxides of three principal members calcium, strontium and barium were known
7.3 Difference between Alkaline Earth Metals and much earlier than the metals themselves. These oxides were alkaline in nature
Alkali Metals and existed in the earth and were named alkaline earths. The metals when
7.4 Abnonnal Behaviour of Beryllium discovered were also called alkaline earths. This term is now applied to all the
7.5 Similarities (Diagonal Relationship) between six elements of group ITA. The frrstmember beryllium is less active than other
Beryllium and Aluminium members and shows some abnormal properties like lithium inIA group. However,
7.6 Magnesium it shows resemblance with aluminium (a member of IIIrd group), i.e., diagonal
7.7 Calcium relationship. The last member, radium-l< is radioactive in nature. Each member
7.8 Compounds of Barium of this group occupies a place just after the members of IA· group in various
periods of periodic table except first period.
~
IA lIA lHA I IA Li 3 Na 11 K 19 Rb 37 Cs 55 Pr 87
Period 1 2 13 ITA Be4 Mg 12 Ca 20 Sr 38 Ba56 Ra 88
2 Ii Be B The members of this group show a marked resemblance in their properties
(3) (4) (5) and possess same electronic configuration. There is gradual gradation in the
3 Na Mg AI properties with the increase of atomic number. This justifies their inclusion in
(11) (12) (13) the same group of periodic table. The main properties are discussed below for
4 K Ca Ga this justification;
(19) (20) (31)
5 Rb Sr In 1. Electronic Configuration
(37) (38) (49) The valence electron configuration of the atoms of the group ITA elements
6 Cs Ba TI is ni, where n is the period number. The arrangement or the distribution of
(55) (56) (81)
7 Fr Ra Uut *RadiulII: and its all isotopes are radioactive, The longest lived isotope being Ra226 with
(87) (88) (113) half-life 1600 years. This isotope is fonned in natural decay series of U238 ,
Alkaline Earth Metals and their Compounds 31·1
electrons on various subshells in the atoms of alkaline earth metals is given below:
. Configuration of the.
Element At. No. Electronic Configuration
valency shell
Be 4 2,2 li,2i [He] 2i

Mg 12 2, 8, 2 Is 2, 2; 2p6, 3; fNe] 3;
Ca 20 2,8,8,2 Ii, 2; 2p6, 3; 3i, 4; [Ar] 4i
Sr 38 2,8, 18, 8, 2 1;, 2i 2p6, 3; 3/ 3d lO , 4i 4i, 5i [Kr] 5i
Ba 56 2, 8, 18, 18, 8, 2 Ii, 2; 2i, 3; 3p6 3d lO , 4; 4p6 4d1O , 5i 5p6, 6; [Xe] 6i
Ra 88 2, 8, 18, 32, 18, 8, 2 Ii, 2; 2p6, 3s2 3i 3dlO ,4i 4i 4d1O 4/ 4 , 5; 5p6 5d lO, 6; 6p6, 7; [Rn] 7;
The outennost shell of these elements has two electrons Be Mg Ca Sf Ba Ra

and the penultimate shell contains 8 electrons except the first Atomic radii (pm) 112 160 197 215 222
(Metallic radii)
member which contains 2 electrons. Since, the last electron
Ionic radii (pm) (M2+) 31 72 100 118 135 148
enters ns orbital, these are s-block elements. Beryllium shows
somewhat abnonnal. properties as its electronic configuration Atomic volume also increases as the atomic number
is slightly different than the rest of the members. Because of increases.
their similarity in electronic configuration [noble gas] ni, they Be Mg Ca Sr Ba Ra
are included in the same group, i.e.; IIA of the periodic table At. voL (mL) 4.90 13.97 25.9 35.54 36.7 38.0
and closely resemble each other in the physical and chemical (c) Density: These metals are denser than alkali metals
properties. in the same period because these can be packed more tightly
due to their greater nuclear charge and -smaller size. The
:!;;:J 2. Physical Properties density decreases slightly upto cltlcium and then increases
(a) Physical state: All the group IIA elements are metals considerably upto radium. Irregular trend is due to the difference
and too reactive, so that cannot occur in the uncombined state in the crystal structure of these elements.
in nature. They are all silvery white metals. They have.greyish Be Mg Ca Sr Ba Ra
white lustre when freshly cut, but tarnish soon after their Density (g mL- I ) 1.84 1.74 1.55 2.63 3.59 55
exposure in air due to surface oxidation (Fig. 7.1). They are (d) Melting and boiling points: The melting and boiling
points of these elements are higher than corresponding alkali
metals. This is due to the presence of two electrons in the
valency shell and thus, strongly bonded in the solid state.
However, melting and boiling points do not show any regular
trend because atoms adopt different crystal structures.
Be Mg Ca Sr Ba Ra
m.pt. (K) 1560 924 1124 1062 1002 973
b.pt. (K) 2745 1363 1767 1655 2078
(e) Ionisation energies and electropositive character: The.
first and second ionisation energies of these metals decrease
from Be to Ba: The second ionisation energy in each case is
Fig.7.1 Tarnished (a) and cleaned-up (b) magnesium higher than the first, nearly double the first ionisation energy.
Be Mg Ca Sr Ba Ra
soft in nature but harder than alkali. metals because metallic First I.E. (kJ mor 1) 899 737 590 549 503 509
bonding is stronger than IA elements due to possession of 2 Second I.E. (kJ mol-I) 1757 1450 1145 1064 965979
valency electrons. However, hardness decreases with increase
The ionisation energy of last member, radium, is slightly
in atomic number.
higher than that. of barium and it is difficult to explain this
(b) Atomic and ionic radii: The size of the atom increases .
anomalous behaviour.
gradually from Be to Ra, on account of the presence of an
extra energy shell at each step. The atoms are large but smaller Although, the ionisation energies of these elements are higher
than corresponding IA elements since the extra charge on the . than those of alkali metals, yet these are sufficiently low to
nucleus attracts the electron cloud inwards. Their ions are also make these atoms to lose two electrons of their valency shell to
· f h . . , f B
.' 1arge and SIZe 0 t e IOn mcreases rom e to a .2+ R 2+ fonn M2+ ions and achieve the inert gas configuration. These
Alkaline Earth Metals and their Compounds 323
7.3'~l DIFFERENCE BETWEEN ALKALINE EARTH METALS AND ALKALI METALS
Both alkaline earth metals:andalkali metals. are s..:block' elements as the last differentiating electron enters the ns-orbital. They
resemble with each other in many respects but still there are certain dissimilarities in their properties on account of different
number of electrons in the valency shell, smaller atomic radii, high ionisation potential, higher electronegativity, etc. The main
points of difference between alkaline earth metals and alkali metals are given below :
Properties Alkaline earth metals Alkali metals
(i) Electronic configuration Two electrons are present in the valency shelL The con- One f!lectron is present in the valency shell. The
figurations is ml . configuration is ns'. .
(ii) Valency Bivalent. Monovalent.
(iii) Electropositive nature Less electropositive. More electropositive.
(iv) Hydroxides Weak bases, less soluble and decompose on heating. Strong bases, highly soluble and stable towards heat.
(v) Bicarbonates These are not known in free state. Exist only in solution. These are known in solid state.
(vi) Carbonates Insoluble in water. Decompose on heating. Soluble in water. Do not decompose on heating
(Li 2C03 is an exception).
(vii) Action of nitrogen Directly combine with nitrogen and form nitrides. Do not directly combine with nitrogen.
(viii) Action of carbon Directly combine with carbon and form carbides. Do not directly combine with carbon.
(ix) Nitrates Decompose on heating evolving a mixture ofN02 and oxygen. Decompose on heating evolving only oxygen.
(x) Solubility of salts Sulphates, phosphates, fluorides, chrornates, oxalates, etc., are Sulphates, phosphates, fluorides, chromates,
insoluble iIi water. oxalates, etc., are soluble in water.
(xi) Physical properties Are less reactive and comparatively harder metals. High melting Soft, low melting points. Paramagnetic.
points. Diamagnetic.
(xii) Hydration of compounds The compounds are extensively hydrated.· MgCI2·6H20, The compounds are less hydrated. NaCl, KCl and
CaCl z·6HzO and BaClz:2HzO are hydrated chlorides. RbCl form non-hydrated chlorides.
(xiii) Reducing power Weaker; as Ionisation potential values are high and Stronger, as ionisation potential values are low and
oxidation potential values are low. oxidation 'potential values are high:
7.41~ ABNORMAL BEHAVIOUR OF (v) It has the tendency to form covalent compounds:
BERYLLIUM The polarisation effect of Be2+ ion is high due to its high charge '
density. The large distortion of electron cloud of the anion
Beryllium is a much less abundant alkaline earth metal, although brings covalent character. Be has high value of electronegativity
masses of the mineral beryl (Be3A12Si601S) that weigh as ( 1.5) and when it reacts with another element, the
much as a ton have been found. Pure beryl is colourless, but electronegativity difference is not so large and the bond is,
impurities give it colour; chromium as an impurity makes beryl therefore, covalent.
into emerald (Fig. 7.2) andiron makes it aquamarine. Beryllium (vi) It does not react directly with hydrogen: Beryl-
differs from rest of the alkaline earth metals on account of its lium hydride can; however, be formed by reducing BeClz with
small atomic size, high electronegati vity and slight difference LiAlH4. Beryllium hydride is a covalent compound. It is
in electronic configuration. Be2+ is very small. It exerts a high polymeric solid, (BeH2)n- It contains hydrogen bridges between
polarising effect on any ani9n associated with it. On account beryllium atoms.
of this, beryllium compounds show covalent character. Its The hydrides of Ca, Sr and Ba are largely ionic due to
compounds h~ve ~ow melting poin!s and are soluble .in organic greater electropositive character.
sblvents.These areh)'drolysed iIi water. (vii) It dissolves in alkalies with evolution of
The main· p()ints of difference are given below: . hydrogen:
(i) It is the hardest of aU alkaline earth metals: This·
Be + 2NaOH + 2H20---t Na2Be02·2H20 + H2
is due to the fact that maximum metallic bonding is present on Sodium beryllate
account of the smallest size amongst alkaline earth metals .. ,'
(ii) The melting and boiling points of the beryllium
other alkaline earth metals do not react with alkalies.
are the highest: This is also due to maximum metallic (viii) It does not liberate hydrogen from acids readily:
bonding. This is due to the fact that Be has lowest oxidation potential
(iii) It is not affected by atmosphere: Be is least
amongst alkaline earth metals.
reactive as its ionisation potential is. high. However, it does (ix) Its oxide is amphoteric in nature: Be is thus weak
react with oxygen and nitrogen at high temperatures. electropositive. in nature.
(iv) It does not decompose water: This is due to low BeO + H2S04 ---t BeS04 + H20
value of oxidation potential. BeO + 2NaOH ---t Na2Be02 + IhO
The oxide is sparingly soluble in water as it has high degree stable complexes, such as [BeF3r or [BeEi]2-. It forms many
of covalency. It has high melting point (approx. 2500°C). The chelate like complexes specially with oxygen donors.
high melting point of BeO is due to its polymeric nature. . (xx) It has the tendency to form aUoys : The metal and
The oxides of other alkaline earth metals are basic, soluble its alloys have the following important applications.
and ionic in nature. The basic nature increases in moving down (a) Low density of beryllium makes it important in the
the group. formation of missiles and satellites.
BeO has a 4 : 4 zinc sulphide (Wurtzite) structure, but all (b) Much of the metal that is produced is added in small
others have a 6 :6 sodium chloride structure. amounts to copper, the small beryllium atoms pin the
(x) Its hydroxide is amphoteric in nature: Be is thus copper atoms together in an interstitial alloy that is more
weak electropositive in nature. rigid than pure copper but still conducts electricity well.
Be(OH)z + 2HCI ~ BeCl 2 + 2H20 (c) The hard electrically conducting alloy is formed for
Be(OH)z + 2NaOH ~ Na2Be02 + 2H20 non-sparking tools for use in oil refineries and grain
The hydroxide is insoluble in water. It is covalent in nature. elevators, where there is a risk of explosions.
The hydroxides of other alkaline earth metals are basic, ionic (d) Beryllium is used as windows for X-ray tubes, because
and their solubility increases on moving from Mg(OH)z to beryllium atoms have so few electrons, thin sheets of
Ba(OH)z. the metal are transparent to X-rays and allows the rays
(xi) Its carbide. (DelC) on hydrolysis evolves methane: to escape.
Note : The element beryllium occurs mainly as beryl 3BeO,
Be2C + 4H 20 ~ 2Be(OH)z + CH4
A1 20 3.6SiOz. Sometime the crystals are so big that they weigh
The carbides of other alkaline earth metals (MC 2) evolve
several tonnes. The gemstone emerald is a form of beryl, its green
acetylene on hydrolysis.
colour is caused by the ions present as impurities.
(xii) Its carbonate (DeC03) is not stable towards heat:
The instability is due to strong polarising effect of small
Be2+ ion on the large CO~- ion.
(xiii) Its nitride (Be3Nl) is volatile: Be3N2 is covalent,
while nitrides of other alkaline earth metals are ionic crystalline
compounds.
(xiv) Its sulphate is soluble in water: It is due to high
degree of solvation of small Be2+ ions.
(xv) DeCtz is a covalent compound: It does not con-
duct electricity in fused state. It is soluble in organic solvents
and acts as a Lewis acid. It fumes in air.
The chlorides of other alkaline earth metals are ionic and
good conductors of electricity in fused state and in solutions.
(xvi) It is rendered passive by concentrated nitric acid:
Nitric acid is an oxidising agent. It forms unreactive thin layer
of oxide on its surface and makes the metal passive. Fig.7.2 An emerald is a crystal of beryl with some
(xvii) Its' cOmpounds do not impart any colour to Cr3+ ions which are responsible for the colour
flame : Very high' energy is required to excite electron from
lowest energy shell.
SIMILARI11ES (DIAGONAL RELATIONSHIP)
(xviii) Its salts can never have more than four
molecules of water of crystallisation as it. has only four
BETWEEN BERYLLIUM AND ALUMINIUM
available orbitals in its valency shelL Beryllium shows some similarities in properties with aluminium,
Is 2s .2p the second typical element of group IIIA (next group in
Mendeleev's periodic table) of the next higher period. This
[li][]] I~ I~ I~ I type of relationship between diagonally placed elements is called
i iii diagonal relationship (one of the characteristics of Mendeleev' s
°
H2 °°°
H2 Hz H2
periodic table).
Group ITA Group IIIA
Other alkaline earth metals can extend their coordination
Second period Be______ B
n~mber to 6 by using d-orbitals.
(xix) It has strong tendency to form complex com-
~ : Beryllium ion, on account of its small size, forms
Third period Mg ~Al
3MgO + 2Al ~ 3Mg + Ah03 chloride in the ratio of 35% (MgCI2); 50% (NaCI) and 15%
3MgO + CaC2 ~ 3Mg + CaO + 2CO (CaCI 2). The mixture is electrolysed at 700°C in presence of
The reduction is done at 2000°C in vacuum. The vapours an inert gas in an electrolytic cell as shown in Fig. 7.3.
of magnesium are condensed. Magnesium is produced at cathode and chlorine at the anode.
(ii) Electrolysis of anhydrous maguesium chloride:
Carnallite (KCI·MgCh·6H20) is a hydrated compound. It cannot +C12
be dehydrated by heating because the water of crystallisation Magnesium being lighter than the fused mass floats on the
reacts chemically with magnesium chloride to form magnesium surface from where it is removed periodically by perforated
oxychloride and finally magnesium oxide. ladles.
The purpose of addition of NaCI and CaCl 2 to anhydrous
MgC12·6H20~MgCI2·2H20~ MgCl 2 is to lower the fusion temperature and make the fused
Hexahydrate Dihydrate
mass good conductor of electricity.
Strongly , M 0
Mg2 0CI 2 heated in air 7 g
Oxychloride Properties
To make it anhydrous, it is first heated in air and then in a Physical Properties: Magnesium is a silvery-white metal.
current of HCI gas. It is a light metal. It is fairly hard and is malleable and ductile.
Its great advantage is its low density (1.74 f'cm\ which is
.MgCI 2·6H 20 .
In
Heated)
presence
MgCI 2 + 6H 20 only two-thirds that of aluminium 2.70 glcm. It is sold in the
of HCI gas form of ribbons or wire. It melts at. 650°C. It is good conductor
Anhydrous magnesium chloride can also be obtained from of heat and electricity.
MgO or sea water. Chlorine is passed over red hot mixture of Chemical Properties: (i) Reaction with air: Pure
MgO and carbon. magnesium metal is a relatively reactive element. It is not
MgO + C + C12~ MgC1 2 + CO affected by dry air. It is slowly tamished in moist air.
Sea water contains magnesium compounds. It is treated Once magnesium metal has been ignited, it bums vigorously
with calcium hydroxide when magnesium hydroxide gets in air to form the oxide with bright white light forming a dense
precipitated. It is dissolved in dilute HCl. The solution is then smoke.
concentrated when hydrated magnesium chloride crystallises 2Mg + 02 ~ 2MgO
. out. It is dehydrated as described above. 3Mg + N2(Air) ~ Mg3N2
Mg2+ + Ca(OHh ~ Mg(OHh + Ca2+ (ii) Reaction with water: Magnesium is not affected by
(Sea water, MgCl2 or M_gS04) ppt.
cold water. It decomposes steam or boiling water with evolution
Mg(OHh + 2HCI ~ MgCh·6H 20 of hydrogen.
Heated l' Mg + 2H20 ~ Mg(OHh + H2
----7~ MgCl 2 + 6H20 I
HCI(g) Anhydrous (Ui) Reaction with acids: It displaces hydrogen from
dilute acids. .
Finally, the magnesium chloride is dried. Theanhydrolls
Mg + 2HCI ~ MgCI2 + H2
magnesium chloride is fused with NaCI and anhydrous calcium
Mg + H2S04 ~ MgS04 + H2
Mg + 2HN0 3 ~ Mg(N03h + H2
Graphite anode
With hot concentrated H 2S04, it evolves S02.
Porcelain H 2S0 4 ~ H20 + S02 + 0
hood Mg+O ~ MgO
MgO + H 2S04 ~ MgS04 + H 20
Mg + 2H2S04 ~ MgS04 + S02 + 2H20
Iron (iv) Reaction with halogens: Magnesium on heating
cell with halogens, readily form halides.
Mg+X2 ~ MgX2
(X may be F, CI, Br or I)
Molten (v) Reducing property: Magnesium acts as a strong
electrolyte reducing agent as it has great affinity for oxygen at high
temperature. It even bums in the atmosphere of CO 2, CO,
S02, NO, etc.
Fig.7.3 An electrolytic cell
The following are the causes of diagonal relationship: (xi) Both combine with nitrogen when strongly heated in
(a) The polarising power of Bez+ and A1 3+ ions is high. its atmosphere.
Consequently the compounds develop covalent. nature. . 3Be + Nz ---'7 f,le3Nz
(b) The standard oxidation potential values of both the 2AI + Nz ---'7 2AlN
elements are very close to each other.
Nitrides on action with water evolve ammonia.
(c) The electronegativity values of both the elements are
the same. Be3NZ + 6H zO ---'7 3Be(OH)z + 2NH3
The similarities in properties are listed below: AlN + 3HzO ---'7 AI(OHh + NH3
(i) In nature, both the elements occur together in the mineral, (xii) Both the metals are obtained by the electrolysis of their
beryl, 3BeQ.AIz0 3·6SiOz. fused salts in the presence of fluorides.
,(ii) Both are not affected by atmosphere. (xiii) Be2+ and AI 3+ ions have strong tendency to form
(iii) They do not decompose water. chelate type complexes. Both form fluoride complexes, like
(iv) Both become passive when treated with concentrated [BeF4f-, [AIF6]3- respectively.
HN0 3 · (xiv) The carbonates of both the metals are unstable.
(v) Both dissolve in caustic alkalies liberating hydrogen. (xv) Both the ions give hydrated ions in solution (aqueous)
Be + 2NaOH ---'7 NazBeOz ~ Hz like [Be(H20)4f+ and [AI(HzO)6]3+ respectively,
2AI + 2NaOH + 2HzO ---'7 2NaAlOz + 3Hz (xvi) The salts of both Be and Al do not impart a colour to ,
Sod. meta the flame when heated in it.
aluminate
(vi) Both BeO and AI Z0 3 are amphoteric in nature. ~_ MAGNESIUM
BeO + HZS04 ---'7 BeS04 + HzO Occurrence: Magnesium does not occur free in nature.
BeO + 2NaOH ---'7 NazBeOz + HzO The british chemist Humphry Davy discovered the pure element
AIz0 3 + 6HCl ---'7 2AICl3 + 3HzO magnesium in 1808. The name magnesium comes from the
name of the mineral magnesite. In addition to minerals such
Al z0 3 + 2NaOH ---'7 2NaAlOz + HzO
as magnesite (MgC03), dolomite (MgC0 3·CaC03), kieserite
Oxides are extremely hard, non-volatile and have high melting (MgS04·HzO), epsom salt (MgS04·7HzO), carnallite
points. (KCI·MgClz,6HzO), asbestos [CaMg 3(Si0 3)4], it is found in
(vii) The hydroxides are also amphoteric in nature. sea water. However ~agnesium ion,Mg2+, is the third most
Be(OH)z + 2HCl ---'7 BeCl2 + 2HzO abundant dissolved ion in the oceans, after Cl- and Na+. The
Be(OH)z + 2NaOH ---'7 NazBeOz + 2HzO oceans, therefore, are a great source for the supply of the
magnesium ion, from which the metal can be obtained easily.
AI(OH)3 + 3HCI ---'7 AICl3 + 3HzO
It is an essential constituent of chlorophyll, the green colouring
N(OHh + NaOH ---'7 NaAJOz + 2HzO matter of plants.
The hydroxides are insoluble in water and decompose on Extraction: It is usually extracted by the electrolysis of
heating into corresponding oxides. fused oxide or fused anhydrous magnesium chloride.
Be(OH)z ---'7 BeO + HzO (1) From magnesite: The magnesite ore (MgC03) is
calcined into magnesium oxide (magnesia).
2AI(OHh ---'7 AI 20 3 + 3H20
(viii) Beryllium carbide (Be2C) and aluminium carbide (AI4C3) MgC0 3 Heated) MgO + CO
strongly. Z
both evolve methane on treatment with water.
BezC + 2HzO ---'7 2BeO + CH4 Magnesium may be obtained either by electrolysis or by
AI4C3 + 6H20 ---'7 2Al203 + 3CH4 thermal reduction of magnesium oxide. The oxide is dissolved
in a mixture of molten fluorides of magnesium, barium and
(ix) B()th the metals react with halogens and form halides.
sodium, The electrolysis of molten mixture is dorie by using
Chlorides can also be formed in a similar way.
carbon rods as anodes which suspend in molten mass and cast
BeO + C + Clz ---'7 BeCl2 + CO iron rods as cathodes at 650°C .. On electrolysis magnesium is
AI z0 3 + 3C + 3Clz ---'7 2AICl3 + 3CO obtained in molten state.
The halides (except fluorides) are covalent in nature. They The thermal reduction of magnesium oxide can be done by
have low melting points and are hydrolysed by water. They using reducing agents like carbon, silicon, aluminium or calcium
dissolve in organic solvents and fume in moist air. The halides carbide.
behave as Lewis acids. MgO + C ---'7 Mg+ CO
(x) Beryllium and aluminium both form polymeric covalent 2MgO + Si ---'7 2Mg + SiOz
hydrides ..
The following are the causes of diagonal relationship: (xi) Both combine with nitrogen when strongly heated in
(a) The polarising power of Bez+ and A1 3+ ions is high. its atmosphere.
Consequently the compounds develop covalent. nature. . 3Be + Nz ~ ~e3N2
(b) The standard oxidation potential values of both the 2AI + Nz ~ 2AlN
elements are very close to each other.
Nitrides on action with water evolve ammonia.
(c) The electronegativity values of both the elements are
the same. Be3NZ + 6HzO ~ 3Be(OH)z + 2NH3
The similarities in properties are listed below: AIN + 3HzO ~ AI(OH)3 + NH3
(i) In nature, both the elements occur together in the mineral, (xii) Both the metals are obtained by the electrolysis of their
beryl, 3BeO·Al z0 3·6SiO z. fused salts in the presence of fluorides.
,(ii) Both are not affected by atmosphere. (xiii) Bez+ and Ae+ ions have strong tendency to form
(iii) They do not decompose water. chelate type complexes. Both form fluoride complexes, like
(iv) Both become passive when treated with concentrated [BeF4f-, [AIF6]3- respectively.
HN0 3 · (xiv) The carbonates of both the metals are unstable.
(v) Both dissolve in caustic alkalies liberating hydrogen. (xv) Both the ions give hydrated ions in solution (aqueous)
Be + 2NaOH ~ NazBe02~ Hz like [Be(H20)4f+ and [AI(HzO)6]3+ respectively.
2AI + 2NaOH + 2H zO ~ 2NaAI02 + 3H2 (xvi) The salts of both Be and Al do not impart a colour to
Sod. meta the flame when heated in it.
aluminate
(vi) Both BeO and Al Z0 3 are amphoteric in nature. ~_ MAGNESIUM
BeO + H2S04 ~ BeS04 + H20 Occurrence: Magnesium does not occur free in nature.
BeO + 2NaOH ~ NazBeOz + H20 , The british chemist Humphry Davy discovered the pure element
Al 20 3 + 6HCI ~ 2AICl3 + 3HzO magnesium in 1808. The name magnesium comes from the
Alz0 3 + 2NaOH ~ 2NaAI02 + HzO name of the mineral magnesite. In addition to minerals such
as magnesite (MgC0 3), dolomite (MgC03·CaC0 3), kieserite
Oxides are extremely hard, non-volatile and have high melting (MgS04·H20), epsom salt (MgS0 4·7HzO), camallite
points. (KCI·MgClz·6H zO), asbestos [CaMg3(Si03)4], it is found in
(vii) The hydroxides are also amphoteric in nature. sea water. However magnesium ion, Mgz+, is the third most
Be(OH}z + 2HCI ~ BeClz + 2HzO abundant dissolved ion in the oceans, after CI- and Na+. The
Be(OH}z + 2NaOH ~ NaZBe02 + 2H zO oceans, therefore, are a great source for the supply of the
magnesium ion, from which the metal can be obtained easily.
AI(OHh + 3HCI ~ AICl3 + 3H20
It is an essential constituent of chlorophyll, the green colouring
Al(OHh + NaOH ~ NaAIOz + 2H20 matter of plants.
The hydroxides are insoluble in water and decompose on Extraction: It is usually extracted by the electrolysis of
heating into corresponding oxides. fused oxide or fused anhydrous magnesium chloride.
Be(OH}z ~ BeO + H20 (i) From magnesite: The magnesite ore (MgC03) is
calcined into magnesium oxide (magnesia).
2Al(OHh ~ Al20 3 + 3H zO
(viii) Beryllium carbide (BezC) and aluminium carbide (A4C3) MgC0 3 Heated) M 0 + CO
strongly g 2
both evolve methane on treatment with water.
BezC + 2H20 ~ 2BeO + C~ Magnesium may be obtained either by elecirolysis or by
Al4C3 + 6HzO ~ 2Al 203 + 3CH4 thermal reduction of magnesium oxide. The oxide is dissolved
,in a mixture of molten fluorides of magnesium, barium and
(ix) Both the metals react with halogens and form halides.
sodium. The electrolysis of molten mixture is dorie by using
Chlorides can also be formed in a similar way.
carbon rods as anodes which suspend in molten mass and cast
BeO + C + Cl2 ~ BeClz + CO iron rods as cathodes at 650°C. On electrolysis magnesium is
Alz03 + 3C + 3Clz ~ 2AICl 3 + 3CO obtained in molten state.
The halides (except fluorides) are covalent in nature. They The thermal reduction of magnesium oxide can be done by
have low melting points and are hydrolysed by water. They using reducing agents like carbon, silicon, aluminium or calcium
dissolve in organic solvents and fume in moist air. The halides carbide.
behave as Lewis acids. MgO+C ~ Mg'+CO
(x) Beryllium and aluminium both form polymeric covalent 2MgO + Si ~ 2Mg + SiOz
hydrides. '
3MgO + 2Al ~ 3Mg + Al 20 3 chloride in the ratio of 35% (MgCI 2); 50% (NaCl) and 15%
3MgO + CaC2 ~ 3Mg + CaO + 2CO (CaCI 2). The mixture is electrolysed at 700°C in presence of
The reduction is done at 2000°C in vacuum. The vapours an inert gas in an electrolytic cell as shown in Fig. 7.3.
of magnesium are condensed. Magnesium is produced at cathode and chlorine at the anode.
(ii) Electrolysis of anhydrous magnesium chloride:
MgCl Electrolysis) Mg + Cli
Carnallite (KCl·MgCI 2·6H20) is a hydrated compound. It cannot 2
be dehydrated by heating because the water of crystallisation Magnesium being lighter than the fused mass floats on the
reacts chemically with magnesium chloride to form magnesium surface from where it is removed periodically by perforated
oxychloride and finally magnesium oxide. ladles.
The purpose of addition of NaCI and CaCl2 to anhydrous
MgCI 2.6H 20 Heated) MgCI2'2H20~ MgCl 2 is to lower the fusion temperature and make the fused
Hexahydrate Dihydrate
mass good conductor of electricity.
Mg 0Cl __S_tr_on...:::g~ly_~) MgO
2 2 heated in ai r
Oxychloride Properties
To make it anhydrous, it is first heated in air and then in a Physical Properties: Magnesium is a silvery-white metal.
current of HCl gas. It is a light metal. It is fairly hard and is malleable and ductile.
Its great advantage is its low density (1.74 f/cm\ which is
MgCI 2'6H 20 . Heated) MgCl + 6H 0 only two-thirds that of aluminium 2.70 g/cm . It is sold in the
10 presence 2 2
of HCl gas form of ribbons or wire. It melts at 650°C. It is good conductor
Anhydrous magnesium chloride can also be obtained from of heat and electricity.
MgO or sea water. Chlorine is passed over red hot mixture of Chemical Properties: (i) Reaction with air: Pure
MgO and carbon. magnesium metal is a relatively reactive element. It is not
MgO + C + Cl 2 ~ MgCl 2 + CO affected by dry air. It is slowly tarnished in moist air.
Sea water contains magnesium compounds. It is treated Once magnesium metal has been ignited, it bums vigorously
with calcium hydroxide when magnesium hydroxide gets in air to form the oxide with bright white light forming a dense
precipitated. It is dissolved in dilute HCl. The solution is then smoke.
concentrated when hydrated magnesium chloride crystallises 2Mg + 02 ~ 2MgO
out. It is dehydrated as described above. 3Mg + N2(Air) ~ Mg3N2
Mg2+ + Ca(OHh ~ Mg(OHh + Ca2+ (ii) Reaction with water: Magnesium is not affected by
(Sea water, MgCl 2 or MJlS04) ppt.
cold water. It decomposes steam or boiling water with evolution
Mg(OHh + 2HCl ~ MgCI 2·6H 20 of hydrogen.
MgCI 2·6H20
Heated
--~) MgCl 2 + 6H 20
i Mg + 2H20 ~ Mg(OHh + H2
HCl(g} Anhydrous (iii) Reaction with acids: It displaces hydrogen from
dilute acids.
Finally, the magnesium chloride is dried. The. anhydrous
Mg + 2HCl ~ MgCl2 + H2
magnesium chloride is fused with NaCI and anhydrous calcium
Mg + H 2S04 ~ MgS04 + H2
Mg + 2HN03 ~ Mg(N0 3h + H2
Graphite anode
With hot concentrated H 2S04, it evolves S02'
Porcelain H 2S04 ~ H20 + S02 + 0
hood Mg+O ~ MgO
. Inert gas+---, MgO + H 2S04 ~ MgS04 + H20
Mg + 2H2S04 ~ MgS04 + S02 + 2H20
Iron (iv) Reaction with halogens: Magnesium on heating
cell
-::::-=-::- =+Magnesium with halogens, readily form halides.
_-:::.-_-:::. float on the
::::.~-::- surtace Mg +X2 ~ MgX2
(X may be F, Cl, Br or I)
Molten (v) Reducing property: Magnesium acts as a strong
electrolyte
reducing agent as it has great affinity for oxygen at high
temperature. It even bums in the atmosphere of CO 2, CO,
SOl> NO, etc.
Fig. 7.3 An electrolytic cell
,

2Mg + C02 ---7 2MgO + C (ix) Its alloys, however,contain aluminium and small
quantities of other metals to impart both strength and corrosion
2Mg + S02 ---7 2MgO + S
resistance. Magnesium alloys are used to make automobile,
SMg + 2NO ---7 2MgO + Mg3N2 aircraft parts, as well as power-tools. The important alloys
are:
It reduces oxides of metals and non-metals
Magnalium. 9S% AI } Used in the construction of airships,
B203 + 3Mg ---7 3MgO + 2B
S % Mg balances and pistons of motor engines.
With KCI03, it bums with explosion
3Mg + KCI0 3 ---7 3MgO + KCI
Electron metal 9S% Mg
4.5% Zn
1 ..
Used in the construction of air-crafts.
(vi) Formation of Grignard reagent: Magnesium 0.5% Cu .
dissolves in ether solution of alkyl halides and forms organo-
metallic compounds known as Grignard reagents. These
Duralumin
o~%~
S~ M' } Its strength and toughness is comp- .
reagents are used in organic synthesis. 'S 0 g arable with mild steel. It is used for
O. % Mn making, airships.
R 4%Cu
Mg + RI ---7 Mg(
I COMPOUNDS OF MAGNESIUM
Alkyl magnesium iodide
~ 1. Magnesium Oxide, MgO, (Magnesia)
(vii) Displacement reactions: Since, magnesium is highly
electropositive metal, it displaces less electropositive metals Preparation: It can be prepared by following reactions.
from their salts solutions. 2Mg + 02 Burning) 2MgO
Mg + 2AgN03 ---7 Mg(N0 3h + 2Ag
Mg(OHh Heated) MgO + H20
(viii) Reaction with FeCl3 or NH 4CI solution: Mag-
nesium dissolves in FeCl3 or NH4CI solution with evolution of 2Mg(N0 3h 2MgO + 4N0 2 + O2
hydrogen.
[Fe03 + 3H20 ---7 Fe(OHh + 3HCI] x 2 MgC0 3 Heated) MgO + CO2 .
[Mg + 2HCI ---7 MgCl2 + H 2] x 3 Properties: It is a light infusible white powder. It fuses
3Mg + 2FeCl3 + 6H20 ---7 3MgC12'+ 2Fe(OHh +3H2 at 2800"C. It is quite stable at high temperature and is a good
thermal insulator. It. is slightly soluble in water and forms
Mg + 2NH40 ---7 MgCl2 + 2NH3 + H2 magnesium hydroxide.
MgO + H20 ---7 Mg(OHh
Uses It is basic in nature. It reacts with acids to form corres-
(0 It is used for the extraction of boron and silicon. ponding salts.
(ii) Magnesium ribbon alongwith barium peroxide is used as
MgO + 2HCI ---7 MgCl2 + H 20
ignition mixture in alurninothermite process.
(iii) Magnesium powder mixed with potassium chlorate is MgO + H 2S04 ---7 MgS04 + H 20
used in flash bulbs for photography. . It is reduced by carbon at very high temperature.
(iv) It is used for making Grignard reagents. MgO + C ---7 Mg + CO
(v) It is employed as a deoxidiser in metallurgy and for the
removal of last traces of air from radio-valves. Magnesium oxide when mixed with. a saturated solution of
(vi) Large quantities of magnesium oxide are used in animal magnesium chloride sets to a hard mass like cement known as
feed supplements because magnesium ion is an important magnesia cement or Sorel cement. The composition is
nutrient for animals. The ion is also important for human MgCI 2·5MgO·xH20.
nutrition. . Uses: It is used:
(i) in medicine as antacid.
(vii) Magnesium metal is also used as a reducing agent in the
(ii) refractory bricks for furnaces.
manufacture of titanium and zirconium from their tetra-
(iii) as an insulator when mixed with asbestos for lagging
chlorides.
steam pipes and boilers.
ZrCl4 + 2Mg ---7 Zr + 2MgCl2
(iv) as an adsorbent in the manufacture of dynamite and in
(viii) Most commercial aluminium metal contains some
the vulcanization of rubber.
percentage of magnesium, whi~h improves the hardness and
(v) for making Sorel cement" which is employed in dental
corrosion resistance of the aluminium.
filling, in cementing glass and porcelain, in plaster casting, etc.
Hi 2. Magnesium Hydroxide, Mg(OH)2 (ii) in the form of basic magnesium carbonate (magnesia
alva) for making tooth powders, cosmetics and in medicine as
Preparation: It is prepared by dissolving magnesium
antaCid.
oxide in water or by treating magnesium salt with an alkali.
(iii) in the form of magnesite as a refractory material.
MgO + H20 -----7 Mg(OHh (iv) in glass manufacture, ceramics and inks.
MgCl2 + Ca(OHh -----7 Mg(OHh + CaCl2
MgCl 2 + 2NaOH -----7 Mg(OHh + 2NaCI III 4. Magnesium Chloride, MgC12.6H20
Properties: It is a white powder. It is sparingly soluble It occurs as mineral carnallite, KCl·MgCI2·6H20 and
in water. It is basic in nature and forms salts with acids. It bischofite, MgC1 2,H20.1t is found in sea water, mineral springs,
decomposes on heating. It readily dissolves in strong solution etc.
of NH4Cl. Preparation: (a) It is extracted from carnallite mineral.
Mg(OHh + 2NH4Cl ;;:::=!'; MgCl2 + 2NH40H The mineral is fused and cooled to 176°C when whole of KCI
is deposited while MgC12·6H20 remains in the fused state.
Uses: A suspension of Mg(OHh in water is 'used in (b) It can also be obtained by dissolving Mg, MgO,Mg(OHh
medicine as an antacid under the name, milk of magnesia, or MgC03 in dilute hydrochloric acid.
because the magnesium hydroxide reacts to neutralize excess The preparation of anhydrous magnesium chloride has
of hydrochloric acid present in the stomach. already been described in the extraction of magnesium.
Properties: It is a colourless crystalline solid, highly
• 3. Magnesium Carbonate, MgC03 deliquescent and highly soluble in water. It is the starting material
It is found in nature as magnesite (MgC03) and dolomite for various magnesium compounds.
(MgC0 3·CaC0 3)·
HCI gas Electrolysis
Preparation: It can be prepared by adding sodium M9C'2 .Mg
F
bicarbonate to a hot solution of magnesium salt. heated Anhydrous in presence
of NaCI
MgS04 + 2NaHC03 -----7 MgC0 3 + Na2S04 + H 20 + CO2
The magnesium carbonate cannot be obtained by the
Ca(OHh Heat
addition of sodium carbonate to the solution of magnesium Carnallite - MgCI 2 '6H 20 • Mg(OHh - - - - +
salt. A white precipitate of a basic carbonate of composition O~
3MgC03·Mg(OHh·3H20 is obtained. It is known as magnesia ,fl . ').

~~q; K-~
alva. It is suspended in water and CO2 is passed when mag- ~
nesium bicarbonate known as fluid magnesia is formed. Mg(NH 4)P04
The solution is boiled when normal magnesium carbonate
separates out.
2MgS04 + 2Na2C03 + H20 -----7
MgC03·Mg(OHh + 2Na2S04 + CO2
MgC03·Mg(OHh + 3C02 + H20 -----7 2Mg(HC03h
!Stron9lY
heated
Mg2P2~
Magnesium
pyrophosphate
. Mg(HC03h -----7 MgC0 3 + CO2 + H 20
Properties: It is a white powder, insoluble in water. It Uses : It is used :
dissolves readily in water containing excess of carbon dioxide. (i) for making Mg, MgO and other magnesium compounds.
(ii) for making Sorel cement. .
MgC03 + CO2 + H20 -----7 Mg(HC0 3h
(iii) in lubrication of cotton threads for spinning.
It dissolves in acids forming salts with evolution of CQ2' (iv) in the preparation of xylotite which is used as covering
MgC03 + 2HCI -----7 MgCl2 + H20 + CO2 for, floors, iaboratory tables, etc.
MgC03 + H2S04 -----7 MgS04 + H20 + CO2
On heating, it decomposes with evolution of CO2, iii 5. Magnesium Sulphate, MgS04·7H20
MgC03 -----7 MgO + C02 It occurs in nature as minerals kieserite (MgS04,H20),
It forms double carbonates with alkali carbonates. epsom salt (MgS04,7H20) and kainite (KCI·MgS04·3H20).
MgC03 + Na2C03 -----7 Na2Mg(C03h Preparation: It is formed by reacting magnesite (MgC0 3)
Soluble
or dolomite with dilute sulphuric acid,
Uses : It is used : MgC03 + H2S04 -1' MgS04 + H20 + CO2
(i) as a filler for paper, rubber and pigments. MgC0 3 ,CaC03 + 2H2S04 -1' MgS04 + CaS04 + 2C02 + 2H20
Dolomite (Insoluble)
It is commercially prepared by boiling kieserite mineral in their calcium carbonate skeletons eventually form enormous
water. The crystals are obtained when the solution is cooled. coral reefs in warm water. It occurs as:
MgS04·H20 + 6H20 ---t MgS0 4·7H20 (1) Carbonate-Limestone, marble, chalk, iceland spar and
calcite as CaC0 3 and dolomite as MgC0 3·CaC0 3.
Properties: It is a colourless crystalline compound,
(ii) Sulphate-Gypsum CaS04·2H20 and anhydrite
soluble in water. The crystals are efflorescent and bitter in
CaS04·
taste. It is isomorphous with ZnS04·7H20. It forms double
(iii). Fluoride-Fluorspar CaF2,
sulphates with alkali metal sulphates, K2S04·MgS04·6H20
Fluorapatite 3Ca3(P04)z·CaF2.
(Schonite).
(iv) Phosphate-Phosphorite Ca3(P04)z.
Heating effect: When heated-to 150°C, it changes to It is present in natural water and causes hardness in water.
monohydrate. On further heating, it becomes anhydrous at
It is an essential constituent of bones and teeth. Egg and sea-
200°C. On strong heating, it decomposes into MgO.
shells contain calcium carbonate.
°
M gSO4' 7H2 150ae ) MgSO4' H2 -----7)
a
200 e M gSO· Strong Extraetion : Calcium is obtained by electrolysis of a fused
° 4 )
heating
1
mass consisting six parts calcium chloride and one part calcium
fluoride at about 700°C in an electrolytic cell made of graphite
MgO + S02 + 2"°2
which acts as anode and a water cooled cathode of iron which
Magnesium sulphate is reduced by lampblack at 800°C. is suspended from the top in the fused mass. On passing
current, calcium is discharged at dthode. It gets solidified as
2MgS0 4 + C ---t 2MgO + 2S02 + C02
cathode is water cooled.
Uses :. It is used :
(a) as fertilizer. CaCl2 ~ Ca2+ + 2CI-
(b) as a laxative. and analgesic in medicine. At anode : 2Cr ~ Cl2 + 2e
(c) as a filler for paper. At cathode: Ca2++2e~ Ca
(d) as a mord;mt in dyeing and tanning industry.
(e) in the manufacture of paints and soaps and in fire- .
proofing fabrics.
CALCIUM +
Graphite anode
Occurrence: Calcium is a common element. In the combined (cell lining)
. state it is widely distributed in nature. Calcium is a rather
abundant element specially in the form of its carbonate, CaC03. Melt
This single compound takes on many different forms in nature (fused calcium
chloride, calcium
appearing as chalk, limestone, marble, or crystalline calcite fluoride)
and aragonite under different geological circumstances.
Fig. 7.5 Electrolytic extraction of calcium
Since metallic calcium is soluble in fused CaCl2 at electrolysis

temperature, it should be removed as soon as it is deposited.·
This is achieved by raising the cathode during electrolysis so
that only the extreme tip of the deposited cathode remains in
contact with the fused CaCI 2.
[Note : Na or K is obtained by doing electrolysis of fused NaOH or
KOH respectively but calcium cannot be obtained in the same
manner as Ca(OHh decomposes into CaO (quick lime) which
Fig. 7.4 Calcium carbonate (CaC03) occurs in two crystalline is difficult to fuse.]
forms: calcite (a) and aragonite (b). Limestone is an
aggregate of small crystals Propei1ies : (i) It is a silvery white metal. It is malleable
and ductile. It is good conductor of heat and electricity. Its
It is present in the earth's crust as silicates, which weather specific gravity is 1.5.
to give free calcium ion Ca++. The ion is about as abundant in (ii) On exposure, it is covered with a white powder consisting
sea water as magnesium ions. Calcium ion is an important Ca(OHh and Ca3N2' It burns in air forming quick lime (CaO)
nutrient for living organisms. Seashells are principally calcium and calcium nitride (Ca3N2)' It decomposes water evolving
carbonate. Corals are marine organisms that grow in colonies; hydrogen.
2Ca + O 2 ------t 2CaO

3Ca + N2 ------t Ca3N2
Calcium reacts gently with water at room temperature· to
produce hydrogen and calcium hydroxide.
Ca + 2H20 ------t Ca(OHh H2+
(iii) It has affinity for non-metals.
2Ca + O 2 ------t 2CaO (Calcium oxide)
Ca + H2 Heat) CaH2 (Calcium hydride)
Ca + Cl2 Heat) CaCl2 (Calcium chloride)
Ca + 2C Heat) CaC2 (Calcium carbide)
3Ca + N2 Heat) Ca3N2 (Calcium nitride)
Ca + S ~ CaS (Calcium sulphide)
(iv) It reacts violently with adds evolving hydrogen. Quick
lime
(v) It reduces many metal oxides.
Cr203 + 3Ca ------t 2Cr + 3CaO
V205 + SCa ------t 2V + SCaO
(vi) When heated in atmosphere of CO2, it forms calcium Fig. 7.6 Continuous vertical lime kiln with separate feed
carbide and calcium oxide.
Heat Calcium oxide is a white amorphous solid. It is the cheapest
SCa + 2C02 ) CaC2 + 4CaO form of alkali. It has a melting point of 2870 K. On exposure
(vii) It dissolves in liquid ammonia. On evaporation, calcium to atmosphere, it absorbs moisture and carbon dioxide.
ammoniate is formed. CaO + H20 ------t Ca(OHh
Ca + 6NH3 ------t Ca(NH3)6 CaO + CO2 ------t CaC03
On heating Ca(NH 3)6, calcium amide is first formed which Being basic in nature, it combines with acidic oxides at high
then changes into nitride. temperature.
Ca(NH3)6 Heat) Ca(NH2h + 4NH3 i + H2 i CaO + Si02 ------t CaSi03
Heat
3Ca(NH2h ) Ca3N2 + 4NH3 6CaO + P4010 ------t 2Ca3(P04h
Uses: (i) It is used as a deoxidiser for copper, cast iron
and steel. Slaked lime, Ca(OH)2(S) and
(ii) It removes sulphur during petroleum refining. lime water, Ca(OH)2(aq)
(iii) The metal is used in preference to sodium for the Lime is sparingly soluble in water. When water is added to
removal of last traces of water from alcohol as it does not lime, a hissing sound is produced alongwith clouds of steam.
react with alcohol. In this process a large amount of heat energy is given out. The
(iv) It is also used as a reducing agent. lime cracks with the formation of a powder called slaked lime
[Ca(OHh]'
COMPOUNDS OF CALCIUM
CaO + H20 ------t Ca(OHh + Heat energy
:t'l 1. Quick Lime, CaO Quick lime Slaked lime
Limestone, CaC03 found in nature is the starting material of The process is known as slaking of lime. The paste of
almost all the compounds of calcium. Calcium oxide (CaO) is lime in water is called milk of lime while the filtered and clear
also called quick lime or burnt lime. It is obtained on large solution is known as lime water. Chemically both are
scale by heating limestone (CaC03) in specially designed kilns Ca(OHh·
(Fig. 7.6). The decomposition of calcium carbonate is a reversible
process. Limestone _1_OO_O_oc4) Quick lime ~ Slaked lime
(CaC0 3 ) (CaO) [Ca(OHhl
CaC03 ~ CaO + CO2
The reaction moves towards right hand direction if CO2
formed is immediately removed from the kiln by allowing a Suspension ~
1
Suspended in water
blast of air to enter the kiln through fire boxes. The temperature (Milk of lime)
Ca(OHh
1
Filter
for the decomposition of limestone should be near about 1000°C
Clear solution
otherwise at higher temperature, the clay present in the (Lime water)
limestone as impurity will react with it to form silicate. Ca(OHh
Properties: It is a white amorphous powder and is manufacture of dye stuffs, bleaching powder, calcium carbide,
sparingly soluble in water. When CO 2 is passed through lime calcium salts, mortar, cement, glass, etc.
water, it turns milky due to the formation of calcium carbonate. Other uses of quick lime: (i) As it has high melting
On passing excess of CO2, the precipitate dissolves forming point (2600°C), it is used for furnace linings.
calcium bicarbonate, Ca(HC03)z. (ii) It is used as a basic flux in metallurgy as it combines
Ca(OHh + CO 2 - - ? CaC0 3 + H 20 with acidic impurities.
Insoluble CaO + Si02 - - ? CaSi03
CaC03 + H20 + CO 2 - - ? Ca(HC0 3)z (iii) It is used as a disinfectant and germicide, as a drying
Soluble
agent for ammonia and alcohol.
This reaction, with its formation of milky precipitate, is the
(iv) It is employed for the purification of coal gas and
basis of a simple test for carbon dioxide.
softening of water.
It reacts with Cl 2 to form bleaching powder.
(v) In the construction of buildings slaked lime is mixed
2Ca(OHh + 2Cl 2 - - ? ~aC12 + ~a(OClh, + 2H 20 with three to four times its weight of sand. The mixture is
": ."". _J31e,a.:;hil)g. p~wcie~ ':' made into a thick paste with gradual addition of water. This
or Ca(OH);:+ b2'~ ~)CadCI2 H 20' paste is called brick laying mortar and is used in building
, , , : ' 'Bleaching" powder' construction. It sets to a hard mass by loss of water and
gradual absorption of CO2 from the air. Sometimes coal ash is
• Uses mixed with lime instead of sand. A mortar obtained from
Quick lime is a commercial compound being used in various hydraulic lime is called hydraulic mortar. It has greater strength
chemical industries as caustic soda, in the purification of sugar, and is used for construction of bridges.
. ' ~,p C2 H2 Acetylene

Heated In electric C C
.-----++ C0 ke • a 2 IY.
furnace at 2000"C 'o? H 20
(CaO + 3C - CaC2 + CO) .
CaCN 2 + C - - NHs
,
Nitrolim
(Fertilizer)
NHs (Ammonia)
§:" Milk of lime (White washing)
:is ~'<J '
o~ ,;:,~
is'
"?'~ cp<S'/ 0,
~ Lime water (for the detection of CO 2)
CaO H0 ~
2
Quick lime --=---+- Ca(OHb
Slaked ~C4
lime ~"'- ~~Bleaching powder
I
Sodalime
Slaking with
NaOH solution
(A mixture of Ca(OHh and NaOH)

good absorbent for number
IS)g "a~ Ca(OHh + CI2 --CaOCI2 + H20
NaOH (Caustic-soda)
1Part + 3 or 4 parts + Water
Slaked
lime
silica
of gases
Mortar
(Building material)
FLOW CHART DIAGRAM FOR THE PROPERTIES OF QUICK L.IME
2. Calcium Carbonate, CaC0 3 Chalk is the softest form of calcium carbonate. Deposits of
chalk have formed from the shells of dead sea creations that
Limestone is one of the most important raw material for the
lived million of years ago. In some places the chalk covered
chemicals and building industries. It is found in nature in huge
with other rocks and put under great pressure. This changed
quantities in various forms such as,liu;les.to:re"marbl~"(;halk,
. ~ ":.. "- ,- ~ ~ -- -.' the soft chalk into harder rock-Umestone. In other places the
etc.
chalk was under pressure and heat. This changed the soft
Infact calcium carbonate is the second most abundant material
chalk into marble, the hardest form of calcium carbonate.
in the earth's crust after silicate like clay, sand and sandstone.
It can be obtained by passing carbon dioxide through lime (iv) A suspension of gypsum when saturated with ammonia
water or by adding sodium carbonat~ solution t~ CaClz. and carbon dioxide forms ammonium SUlphate, a nitrogenous
Ca(OHh +CO z ---7 CaC03 + HzO fertilizer.
CaClz + NaZC03 ---7 CaC03 + 2NaCI 2NH3 + CaS04 + CO2 + H 20 ~ (NH4hS04 + CaC03
The precipitate of CaC03 thus obtained is known as (v) When strongly heated with carbon, it forms calcium
precipitated chalk, a pure form of the finely divided sulphide. . .
compound. CaS04 + 4C ~ CaS + 4CO
It is a white powder, insoluble in water. It dissolves in Uses: It is used:
presence of COz due to formation of calcium bicarbonate. (i) for the manufacture of plaster of Paris, cement,
CaC03 + HzO + COz Ca(HC03h ammonium sulphate, sulphuric acid, etc.
Uses: (i) Precipitated chalk is used in tooth pastes, tooth (ii) for preparing blackboard chalk.
powders, and face powders, in medicine for indigestion, in (iii) in anhydrous form as drying agent.
adhesives in cosmetics and as a filler for paper.
(ii) Chalk is used in paints and distempers. 11\ 4. Plaster of PariS, 2CaS04.H~
(iii) Marble is used, (a) for building purposes, (b) in the (Calcium sulphate hemihydrate)
production of COz in laboratory.
Preparation : It is obtained when gypsum, calcium
(iv) Limestone is used, (a) in the manufacture of quick lime,
sulphate dihydrate (CaS04·2H20), is heated at 120°C.
slaked lime, cement, washing soda and glass, (b) as a flux in
the smelting of iron and lead ores. 2[CaS04·2H20] ---72CaS04·H20 + 3H20
Calcium sulphate dihydrate Calcium sulphate
II 3. Calcium Sulphate, CaS04.2H~ (Gypsum) (Gypsum) hemihydrate
(Plaster of Paris)
It is found in nature as anhydride (CaS04) and gypsum Properties: (i) Plaster of Paris is a white powder.
(CaS04·2HzO). (ii) It has the property of setting to a hard mass when a
It can be prepared by reacting any calcium salt with either paste with wate;r is allowed to stand aside for sometime. Slight
sulphuric acid or a soluble sulphate. expansion occurs during the setting as water is absorbed to
CaClz + H ZS04 ---7 CaS04 + 2HCI reform CaS04·2HzO (gypsum). The setting process is exother-
CaClz + NaZS04 ---7 CaS04 + 2NaCl mic. The process of setting takes place in two stages. In the
PropertIes: (i) It is a white crystalline solid. It is sparingly first stage, there is conversion of plaster of Paris into
soluble in water and solubility decreases as temperature orthorhombic form of gypsum (setting step) and in the second
increases. stage orthorhombic form changes into monoclinic form
(ii) It dissolves in dilute acids. It also dissolves in (hardening step).
ammonium sl1lphate due to the formation of double sulphate,
2CaS04.HzO S~ti~g) CaS04.2H20 Hardening) CaS04.2H20
(NH4hS04·CaS04· H20.
(iii) Gypsum when heated first changes from mono- Plaster of Paris 2 Orthorhombic Monoclinic
clinic form to orthorhombic form without loss of water. At The setting of plaster of Paris may be catalysed by sodium
120°C, it loses three-fourth of its water of crystallisation chloride while it is retarded by borax or alum. Addition of alum
and forms hemihydrate, (2CaS04·H20) which is commonly to plaster of Paris makes the setting very harei. The mixture is
known as plaster of Paris. At 200°C, it becomes anhydrous. known as Keene cement.
The anhydrous form is known as burnt plaster or dead (iii) When plaster of Paris is heated at 200°C, it forms
plaster. anhydrous calcium sulphate which is known as dead plaster.
lZ0·C It has no setting property as it takes up water only very slowly.
2[CaS04,2H20] -----'7 [2CaS04,H20]+ 3H20
Uses : It is used:
[2CaS04. H20 ] 2000C) 2CaS04 + H20 (i) in surgery for setting broken or dislocated bones.
When strongly heated, it decomposes to give calcium (ii) in making casts for statues, toys, surgical instruments,
oxide. etc ..
2CaO + 2S02 + O2 (iii) in making casts in dentistry.
(iv) in making blackboard chalk.
. Heated 120"C 200°C
CaS04 .2Hp -
Gypsum
(monoclinic) Ii.
CaS04 ·2Hp_2CaS04 ·Hp_CaS04
(OrthO. rhombic) Plarter of Paris Anhydrous
(burnt plaster)
II 4. Portland e..m
t ",0 'H,O heated I
sw.""Y
Portland cement is one of the most important building
materials at the present time. It is used in the construction of
02+ S02+ CaO buildings, roads, bridges, (lams, etc. It was discovered, in
(lime)
1824, by an English Mason, Joseph Aspdin who observed that CakinlltloD in rot.ry kiln: This step is mainly respon-
when strongly heated mixture of limestone and clay was mixed sible for the formation of cement. The heating of raw meal
with water and allowed to stand, it hardened to a stone-like (dry process) or slurry (wet process) is done in a rotary kiln
mass which resembled portland rock-a famous building stone at a very high temperature 1400-1600°C. The kiln consists of
of England. Since then the name portland cement has been a long cylinder 6 to 10 feet in diameter and 100 to 250 feet in
given to a mixture containing high percentage of lime with length. It is made of steel and lined inside with fire bricks
silica, iron oxide, alumina, etc_ (Fig.7.7).
Cement is a dirty greyish heavy powder containing calcium
for
aluminates and silicates. The silicates and aluminateswhich waste gases
form more than 90% of the cement are:
material
(i) Tricalcium silicate ·3CaO·Si02 hopper
(ii) Dicalcium silicate 2CaO·Si02
(iii) Tricalcium aluminate 3CaO·Al203
(iv) Tetracalcium alumino-ferrite 4CaO'AI203'Fe203
Of these, tricalcium silicate is most important
Composition of portland eement: The approximate
composition of portland cement is given below:
. Oxide Percentage by mass
Lime (Calcium oxide) (CaO) 61.69%
Silica (Si0 2) 18.24%
Alumina (A1203) 4-8% Fig. 7.7
Ferric oxide (Fe203) 1-8%
Minor oxides (MgO, Na20, 2-4% The charge (raw meal or slurry) is introduced in the kiln
K20, S03) with the help of a screw conveyer. It moves forwaro with the
rotary motion given to the kiln. The charge is heated by buming
The essential constituents are lime, silica and alumina. These
coal dust which is blown in from the other side with the help
are generally kept in the following ratio:
of a blower. In the upper portion of the kiln, the temperature
: !!~~: = 25 4.0
is about 750°C where whole of moisture is eliminated. In the
middle portion, the temperature is about 1000°C. The limestone
.. % CaO = I 9- 2 1 decomposes with evolution of CO2. At the lower end, the
% Si02 + % Al203 + % FeZ03 . . temperature is 1600°C. The following reactions occur:
The cement containing no iron is white. CaC0 3 ----., CaO + COz
Raw materials: The important raw materials needed for 2CaO + Si02 ----., 2CaO-Si02
the· manufacture of cement are:
(1) Limestone-This provides lime. 3CaO + Si02 ~ 3CaO·Si02
(ii) Clay-This provides alurllina and silica. 3CaO + Al203 ----., 3CaO'Al20 3
(iii) Gypsum, (CaS04·2H20). .
4CaO + Al20 3 + Fe203 ~ 4CaO·AI203·Fe203
Manuf8dure : There are two processes in use for the
manufacture of cement (i) Dry process and (ii) Wet process. The product formed is technically called as clinker. It is
Dry process: The process is used when limestone is cooled and mixed with 2 or 3% of its weight of gypsum. It is
hard in nature. The limestone is first broken into small pieces. then ground to an exceedingly fine powder. The powder is
It is then mixed with clay in proper proportions. The mixture packed in air tight bags.
is finally pulverised to such an extent that it passes through a . The purpose of the addition of gypsum (CaS04·2HiO) is to
100 mesh sieve. This homogeneous mixture is known as raw increase the setting time of the cement.
meaL SettinR of cement: When cement is mixed with water
Wet process: The process is u~ed when limestone and and left as such for some time, it becomes a hard mass. This
clay both are soft in nature. The clay is washed with water in is known as setting of cement The exact mechanism of this
wash mill to remove foreign materials like flint. The powdered setting process is not known. It is believed that various
limestone IS mixed with clay paste in the ratio of 75% (limestone) aluminates and silicates present in the cement form hydrates
and 25% (clay). The mixture is finely ground and made with water which separate in the form of geL
homogeneous. The homogeneous paste is known as slurry_ It Hydration
contains 40% (approximately) water. ) 3CaO'Al20 3-6H20
Colloidal gel
Na2S·9H20. Barium carbonate cannot be decomposed by heat.

Colloidal gel It is mixed with carbon and heated in a furnace to fonn barium
Hydration . oxide.
4CaO·Al203·Fe203 + 6H 20 ) .
BaC03 + C - - 7 BaO + 2CO
3CaO·Al20 3·6H20 + Fe203'CaO The barium oxide when heated at 540°C in purified air is
Colloidal gel
oxidised to barium peroxide.
At the same time some Ca(OHh and Al(OHh are fonned
as precipitates due to hydrolysis.
3CaO'Si02 + H20 Ca(OHh + 2CaO'Si02 Barium carbonate is used for the preparation of other salts
Hydrolysis as acetate, chloride and nitrate.
3C a 'Al20 3 + 6H20 ) 3Ca(OHh + 2AI(OHh
°
Gypsum combines with tricalcium aluminate to fonn calcium
BaC0 3 + 2CH3COOH
BaC03 + 2HCI --7
(CH 3COOhBa + C02+H20
BaCl2 + CO 2 + H 20
sulpho-aluminate.
BaC03 + 2HN03 - - 7 Ba(N03h + CO2 + H 20
3CaO'A1 20 3 + 3CaS04 +2H20--7 3CaO·Al203·3CaS04·2H20
When barium carbonate is heated to red heat ina current of
This reaction slows down the setting.
steam, barium hydroxide is fonned with evolution of carbon
The gels fonned start losing water partly by evaporation dioxide. . ::".
and partly by fonning hydrates with unhydrated constituents.
BaC03 + H 20 - - 7 Ba(OHh + C02
This results in the fonnation of a hard mass; Ca(OH)z binds
the particles of calcium silicate together, while Al(OHh fills the Barium chlorate, Ba(CI0 3h· carl be prepared by the action
interstices resulting in hardening the mass. of chlorine on barium hydroxide solution (hot and concentrated).
Setting of cement is an exothennic process. Hence, cement Barium chlorate being less soluble, separates out.
structures have to be cooled during setting by sprinkling water. 6Ba(OHh + 6Cl2 - - 7 Ba(CI03)z + 5BaCl2 + 6H20
Concrete: A mixture of cement, sand, gravel or small
pieces of stone and water is known as concrete. It sets to an
exceedingly hard structure. It is mainly used for construction
of floors. If the cement concrete is filled in and around a wire
netting or skeleton of iron rods and allowed to set, the resulting
structure is known as reinforced concrete. These structures
have great strength and are used for construction of roofs
bridges, etc. '
Cement industry in India: Cement industry was started
in India with the establishment of first factory in 1904 in Tamil
Nadu. India is, at present, one of top ten cement producing
countries in the world. There are about 60 cement factories in
public and private sectors producing near about 2.5 crore tons
cement annUally.
7.8A COMPOUNDS OF BARIUM

Preparation: Barium is found in nature mainly in the fonn Ba(CI03)2
of sulphate, BaS04, called barytes or heavy spar. Barytes is a
Uses: Uses of barium compounds:
source for the preparation of various compounds of barium
(i) BaO is an excellent drying agent especially for organic
which are of industrial importance.
bases like pyridine.
The natural barytes is ground, mixed with coke and the
Oi) Ba02 is used in the preparation of H20 2 and ignition
mixture is heated in a rotary kiln, barium sulphate is reduced
mixture used in therniite process. It is also used as an oxidising
to barium sulphide.
agent.
BaS04 + 4C ~ BaS + 4CO (iii) Ba(OHh is used for the preparation of astandard·a1kali
The kiln clinker is extracted. with water. The solution is
solution for titrating acids.
treated with sodium carbonate to precipitate barium carbonate.
(iv) BaCl2 is used as a laboratory reagent for the test of
BaS + Na2C03 ---:7 BaC03 + Na2S sulphate radical.
ppt.
(v) Ba(CI03h is used for producing green fire and for the
Barium carbonate is used further for barium compounds preparation of chloric acid.
and the filtrate is concentrated for sodium sulphide crystals,
(vi) BaS04 is used as a white pigment either as such or (viii) When barium hydroxide octahydrate. Ba(OHh·8H20,
mixed with zinc sulphide under the name of lithopone (BaS04 and ammonium thiocyanate, ~SCN, are ground together,
+ ZnS). It is also used as a filler in rubber and paper industry. one moderately, endothermic reaction takes place. An endo-
(vii) Barium titanate (BaTi03) is piezoelectric, which means thermic reaction absorbs heat. The reaction mixture becomes
that it becomes electrically charged when it is mechanically so cold that moisture from the air forms a layer of frost on the
distorted. This property leads to its use for undetwater sound outside of the beaker.
detection, in which a mechanical vibration is converted into an Ba(OHh·8H2 0 + 2NH4SCN ----f Ba(SCNh + 2NH3 + lOH20 -Heat
electrical signal.
Example 1. Explain the following: (v) Beryllium oxide is insoluble but BaO is soluble.
(i) Beryllium chloride fumes in air. (vi) BeCl2 can be easily hydrolysed. (I.I.T. 1999]
or Solution:
Beryllium chloride is acidic when dissolved in water. (i) Lattice energies of the sulphates are nearly the same. The
2 size of sulphate ion is large and small changes in cation size do .
(ii) Barium ion, Ba +, is poisonous, yet BaS04·isgiven to
patients prior to taking stomach X-ray. Why is it safe to use not affect the lattice energies. However, the hydration energies
BaS04 internally? decrease from Be2+ to Ba2+. Hence, solubility o{'sulphates
(iii) Alkaline decreases from top to bottom.
alkali metals. (ii) Lattice energies of hydroxides decrease as the size of
(iv) Alkaline earth metal salts are diamagnetic in nature. cation increases. It overcomes the effect of decrease in
(v) Magnesium oxide is used as a refractory material. hydration energy and hence, the solubility of hydroxides
Solution: increases from top to bottom.
(i) BeCl2 undergoes hydrolysis being a salt of a weak base (iii) NaCI is added as to lower the fusion temperature of
and a strong acid. Fumes of HCI gas are evolved in presence MgCl2 and to make the mixture as good conduCtor of electricity.
of moisture in atmosphere. (iv) Lattice energies of the salts of alkaline earth'metals are
or very high in comparison to alkali metal salts. High lattice energies
When dissolved in water, strong acid HCI is formed in are responsible for low solubility.
solution. (v) The lattice energy of BeO is higher than. BaO due to
BeCh + 2H20 ---1 Be(OH)z + 2HCI small size of Be2+ ion. The other reason may be that BeO is
covalent and polymeric while BaO is ionic in nature.
(ii) BaS04 is extremely insoluble and does not pass from
(vi) The Be2+ ions are easily hydrated because of high
digestive system into the circulatory system.
charge size ratio. The hydrolysis occurs because Be-O bond
(iii) Alkaline earth metals have high values of atomisation
is very strong.
and ionisation potentials in comparison to alkali metals. The
oxidation potentials have lower values than alkali metals and Example 3. Give the names andformula ofthe compounds
hence, alkaline earth metals are weaker reducing agents. indicated in the following statements:
(iv) The ions of alkaline earth metals, M 2+, have inert gas (a) A compound of Ca used in setting fractured bones.
configuration, i.e., all the orbitals are doubly occupied. (b) A compound of Mg, S, 0 and H used as a purgative in
Hence, alkaline earth metal salts. are diamagnetic in nature. medicine.
(v) MgO has very high melting point and does not decompose (c) A compound of Ca and C used for the production of
as its lattice energy is very high. It is, thus, used as refractory acetylene.
material. (d) A compound of Ca, C and N used as a fertilizer.
Example 2. Give reasons for the following: (e) A triatomic compound which on treatment with water
gives H2-
(£) Solubility of the sulphates of alkaline earth metals
Solution: (a) Plaster of Paris, 2CaS04'H20
decreases from top to bottom in the group.
(ii) Solubility ofhydroxides ofalkaline earth metals increases (b) Magnesium sulphate, MgS04'7H20
from top to bottom in the group . (c) Calcium carbide, CaC2
. (iii) Sodium chloride is. added during electrolysis of fused CaC2 + 2H20 ---1 Ca(OHh + C2H2
anhydrous MgCl2. (d) Calcium cyanamide (nitrolim), CaCN2
(iv) Alkaline earth metal salts are less soluble than the (e) Calcium hydride (hydrolith), CaH2
corresponding alkali metal salts.
"Example 4. 0.3 g of mag1'fesium ribbon was placed in a 2MN03 ~ 2MN02 + O2 (M = Na, K, Rb or Cs)
crucible and heated with the lid on until the magnesium began Nitrates of alkaline earth metals decompose fonning
to bum brilliantly. At the end of the experiment there was corresponding metal oxides, N02 and 02.
0.45 g of the white powder left. Show that this result does not M(N03h ~ MO + 2N02 + O 2
agree with the equation, (M Be, Mg, Ca, Sr or Ba)
2Mg(s) + 02(g) ~ 2MgO(s)· Lithium nitrate behaves like Mg(N0 3h due to diagonal
What might have gone wrong? relationship. '
Solution : The given equation is, 4LiN03 ~ 2Li 20 + 4N02 + O 2
2Mg(s) + 02(g) ~ 2MgO(s) (b) Carbonates: Carbonates of alkali metals are stable
2x24=48g 2x(24+ 16)=80g and do not decomposes on heating.
The equation shows that 48 g of magnesium should give Carbonates of alkaline earth metals decompose on heating.
80 g of magnesium oxide. Therefore, 0.3 g of magnesium However, stability increases as the decomposition tempera-
ture indicate which increase from BeC03 to BaC03'
should give 80: °.3 0.5 g of the oxide. The actual amount
8 MC0 3 ~ MO + CO 2
of MgO obtained is 0.45 g. Perhaps some of the oxide escaped
Li2C03 like MgC03 also decomposes on heating.
as smoke or the' magnesium did not react completely or the
magnesium may have combined with nitrogen to make Li2C03 ~ Li20 + CO2
magnesium nitride instead. (c) Sulpbates: Sulphates of alkali metals are stable and
do not decompose on heating.
'Example S. Beryllium gives a compound with the
Sulphates of alkaline earth metals decompose on heating
following percentage composition: Be, 6.1%; N, 37.8%;
into oxides and S03.
CI, 48%; H, 8.1%. One mole of the compound had a mass of
148 g. M(Be) = 9 g mor.
I ' MS0 4 ~ MO + S03
(i) What is the molecular formula of the compound? The stability increases as the temperature of decomposition
(li) In water, 1 mole of the compound reacts with 2 moles of these sulphates increase gradually.
of Ag+ ions. Li2S04 like MgS04 also decomposes on heating.
Suggest a structural formula for the compound. '<Example 7. (a) Why BaS04 is insoluble whereas BeS04
Solution: is soluble in water?
Determination ofempiricai formula . (b) What is the hybrid state of Be in BeCt2? What will be
Relative number the change in the hybrid state of BeCl2 in the solid state?
Element Percentage. At. mass atom Simplest ratio [C.B.S.E. (P.M.T.) 2005]
Solution: .
Be 6.1 9.0
,
~1 = 0.68
0.68
0.68
1
(a) The lattice energy of BaS04 is much more than its
N 37.8 14.0 = 2.7 2.7 4 hydration energy and hence it is insoluble in water. The
14 0.68 =
48.0 hydration energy of BeS04 is much higher than its lattice
1.35 _ 2
Cl 48.0 35.5
35.5
1.35 0.68 - energy because of small size of Be2+ ions. Hence, it is soluble
8.1 = 8 1 8.1 12 in water.
H 8.1 1.0 1.0. . 0.68 :::: (b) In the vapour state, BeCl2 is linear as Be is sp hybridized.
=
Empirical formula BeN4ClzH 12 However, in solid state, BeCl2 is polymeric. In the polymeric
Empirical mass = 9 + 4 x 14 + 2 x 35.5+ 12 x 1 148 structure, each Be has two covalent and two co-ordinate bonds,
Hence, molecular formula = BeN4CI2H 12 i.e., Be is sp3 hybridized.
The reaction with silver ions suggests that 2 chlorine Example 8. (a) Mg3N2 when reacted with water gives off
atoms are present as chloride ions. Thus, the structural formula ammonia but HCl is not obtained when MgCl2 reacts with
of the compound is [Be(NH3)4]CI2. water at room temperature. Give reason.
EDlDpie 6. Compare the thermal stability of the following (b) Chlorination of calcium hydroxide produces bleaching
compounds of the alkali metals with those of alkaline earth powder. Write the chemical equation.
metals: (a) nitrates (b) carbonates (c) sulphates. Solution:
Solution: (a) .\\1g3N2 is a salt of a strong base, Mg(OH)z, and a weak,
(a) Nitrates: Nitrates of both alkali and alkaline earth acid (NH3) and hence gets hydrolysed to give NH3.
metals decompose on heating. Mg3N2 + 6H 20 ~ 3Mg(OH)z + 2NH3
Nitrates of alkali metals decompose to form metal nitrites MgCl2 is a salt of a strong base and a strong acid (HCI) and
and O2, hence, its hydrolysis does not occur. .
(b) Ca(OHh + Cl 2 ~ Ca(OCI)CI + H 20 . Example 11. (a) State anyone reason for alkaline earth
Slaked Bleaching metals, why they have a greater tendency to form complexes
lime powder
Bleaching powder is also considered as a mixture of than alkali metals.
Ca(OClh, CaCl2 and Ca(OHh, (b) Alkaline earth metals cannot be obtained by chemical
reduction.
3Ca(OHh +2CI2~ Ca(OClh . Ca(OHh·CaCl2 ·2H20
Bleaching powder Solution.
Example 9. Draw the structure of(i)BeCh (vapour state) (a) Alkaline earth metal cations have smaller size and higher
(U) BeCl2 (solid). charge in comparison to alkali metal cations. These factors are
Solution. responsible for greater tendency to form complexes.
In vapour state, it has chlorobridged dimer structure which (b) Alkaline earth metals cannot be obtained by chemical
dissociates into linear monomer at lOOO"C. reduction as they themselves are stronger reducing agents than
common reducing agents. With carbon, they form carbides.
Example 12. How would you explain?
CI-Be-Cl (i) BeO is insoluble but BeS04 is soluble in water.
(U) BaO is soluble but BaS04 is insoluble in water.
.Monomer (iii) What is the difference between milk of lime and lime
In the solid state, it has a polymeric structure with dichloro- water?
bridges in which a halogen atom bonded to one beryllium atom (iv) Why do halides and hydrides of beryllium polymerise?
uses a lone pair of electrons to form a co-ordinate bond to Solution.
other beryllium atom. (i) The lattice enthalpy of BeO is higher than its hydration
enthalpy and thus it is insoluble in water. BeS04 on the other
hand has lower lattice enthalpy than hydration enthalpy and
hence it is soluble in water. The lower lattice enthalpy is due
to bigger size of SO~- ion.
(ii) In BaO, the lattice enthalpy is less than hydration enthalpy
Example 10. (a) Halides ofBe dissolve in organic solvents and thus it is soluble in water while in BaS04, the lattice
while those of barium do not. Why is it so? enthalpy is more than hydration enthalpy and hence, it is insoluble
(b) What is the difference between milk of lime and lime in water.
water? (iii) Both milk of lime and lime water are chemically same
(c) Why is calcium preferred over sodium to remove last i.e., Ca(OHh, The suspension of slaked lime in water is called
traces of moisture from alcohol? milk of lime while clear solution of slaked lime is know as lime
Solution. water. Slaked lime is sparingly soluble in water.
(a) Halides of beryllium are covalent due to small size of (iv) The monomeric molecules BeH2 and BeCl2 formed
Be2+ ion while halides of barium are ionic. with normal bonds will result in only four electrons in the outer
(b) The suspension of Ca(OHh in water is termed milk of shell of beryllium atom making it electron deficient. By
lime while clear solution of Ca(OHh is called lime water. polymerising, each atom shares its electrons with several
(c) Both Ca and Na can remove moisture from alcohol but neighbours and receives a share in their electrons making the
sodium reacts with alcohol also readily. Calcium reacts with situation more favourable. Therefore, the halides and hydrides
alcohol very slowly. . of Be polymerise.
" SUMMARY AND IMPORTANT POINTS TO REMEMBER I i

1. IIA group of the periodic table consists of six elements- 3. The outermost shell of these elements has two electrons, i.e.,
beryllium, magnesium, calcium, strontium, barium and radium. nl configuration. Because of their similarity in electronic
These elements are called alkaline earth metals. The oxides configuration [noble gas] ni, they are included in the same
of these elements are alkaline and exist in the earth-so they group and closely resemble each other. There is a gradual
are called alkaline earth metals. The last member is radioactive. gradation in their properties from top to bottom as atomic
2. The first element, beryllium, is less active than other elements number increases.
and shows abnormal properties like lithium in IA group on 4. Physical characteristics
account of small atomic and ionic size and high electro- (i).All are silvery white metals. They are soft but harder
negativity. It shows resemblance with aluminium (an element than alkali metals. Softness- increases from Be to Ba.
oflIIrd group), i.e., diagonal relationship. .
16. Plaster of Paris has the property of setting to a hard mass- For manufacture, limestone and clay are fused at 1400-1600"C
CaS04,2H20, slight expansion occurs during setting. in a rotary kiln. The product obtained is called clinker. It is
Addition of alum to plaster of Paris makes the setting very mixed with 2-3% gypsum and powdered.
hard. The mixture is known as Keene cement. When cement is mixed with water, it sets to a hard mass, this
Plaster of Paris is used for setting broken or dislocated bones, is called setting. Setting is an exothermic process. During
casts for statues, toys and in dentistry. setting hydration occurs.
When plaster of Paris is heated at 200"C, it forms anhydrous 19. Be shows diagonal relationship with aluminium, the second
calcium sulphate which is known as dead plaster. It has ~o element of ill A group.
setting property. (a) The polarising power of Be2+ and A1 3+ ions is high.
17. (a) Anhydrous CaCl2 is a good drying agent. It cannot be Consequently the compounds are covalent.
used for drying ammonia and alcohol as it forms addition (b) The electronegativity of both the elements is nearly the
products with them. same.
(b) Hydroxyapatite, Cas(P04h OH is the main component of (c) Both do not decompose water.
tooth enamel. Cavities are formed when acids decompose (d) Both become passive when treated with conc. HN0 3.
this enamel. This can be prevented by converting the (e) Both dissolve in caustic alkalies liberating H 2.
hydroxyapatite to more resistant enamel-fluorapatite, (t) The oxides and hydroxides are amphoteric.
Cas(P04h·F. (g) BezC and Al4C3 on hydrolysis evolve CH4.
(c) Most of the kidney stones consist of calcium oxalate, (h) Both combine with nitrogen.
CaC20 4·Hio. (i) Both form polymeric hydrides.
(d) Ml+and Ca2+ ions present in water are responsible for (j) Halides are formed in similar fashion.
hardness of water. Oxide + C + Clz ---t Chloride
(e) CaC 2 is obtained by heating a mixture of CaO and carbon. Halides except fluorides are covalent in nature.
It reacts with nitrogen forming nitrolim, used as a 20. Solutions of beryllium salts are acidic and dissolve ap~re
fertilizer. ciable quantities of Be(0H)2. In alkali solution [Be(OH)4] - is
CaC 2 + N2 ---7 CaCN 2 + C formed.
~
nilrolim [Be(H20)4f+ ~ [Be(H20h(OH)t + if
18. Cement is an important building material. The average
[Be(H20h(0H)]+ ~ [Be(H20)z(OH)z] + H+
composition of portland cement is : CaO 61.5%, Si02 22.5%,
Al20 3 7.5%. Cement is a dirty greyish heavy powder contain- [Be(H20)z(0H)2] ~ [Be(H20)(OHhr + H+
ing calcium silicates and aluminates. Cement consists of : [Be(H20)(0H)3r ~ [Be(OH)4]2- + if
Tricalcium silicate 3CaO· Si02
Dicalcium silicate 2CaO· SiOz 21. SrC03 is used in the manufacture of glass for colour TV
Tricalcium"aJ.uminate 3CaO· AlZ03 picture tube.
Tetracalcium alumino-ferrite 4CaO· Alz03' Fez03 22. BaS04 is used in medicine as a contrast medium for stomach
and intestinal X-rays.
I • • • _ PRACTICE PROBLEMS - ••• "- ~--~--
• Subjective Type Questions (v) Name two ores of magnesium.

(vi) Which element of alkaline earth metal has least density?
1. Give reasons : 3. (a) Name the element which is invariable bivalent and whose
(a) Halides of Beryllium are soluble in organic solvents. oxide is soluble in excess of NaOH.
(b) Beryllium chloride fumes in moist air. (b) Name the alkaline earth metal which shows resemblance
(c) CaC03 dissolves in water in excess of CO2, with aluminium.
(d) A piece of burning magnesium ribbon continues to burn (c) Name the alkaline metal hydroxide which is amphoteric.
inSOz· (d) Which elements of group 2 do not give charaCteristic
(e) CaCl2 cannot be used for drying ammonia. flame colouration?
2. Answer the following: (e) Which out of Mg2+, Ba2+, Ca2+ has maximum ionic
(i) Name three natural forms of calcium carbonate, mobility?
(li) Which alkaline earth metal is found in abundance in (f) What is dead burnt plaster?
earth's crust? (g) What is fly ash?
(iii) Name the alkaline earth metal which is radioactive in 4. Give the 9ame and formula of the compounds as indicated
nature. in the following statements:
(iv) Name the natural carbonate mineral in which both (i) A compound of calcium and hydrogen which is used as
calcium and magnesium are present. a portable source of hydrogen for filling balloons.
(n) A compound of Mg, 0, CI and H used as a cement for (c) Calcium nitrate from calcium sulphate.
joining cracked teeth. (d) Anhydrous MgCl 2 from hydrated magnesium chloride.
(iii) A compound of Ca, 0, CI and H used as a germicide. (e) Plaster of Paris from gypsum.
° °
(iv) A compound of Mg, Cl and used as drying agent.
(v) A compound of Ca and which when heated in oxycoal
gas flame gives lime light.
13. Arrange the followinJf
(i) Ml+, Sr2+, Be +, Ca2+ and Ba2+ ions in the increasing
order of their heats of hydration.
S. How do the following properties of the alkaline earth metals (ii) Cal2, CaF2, CaCh and CaBr2 in order of decreasing
change when we move from Be to Ba? melting points.
(i) Size of the atoms and ions (iii) CaCI2, BeCI2, MgC}Z, BaCh and SrCl2 in order of
(n) Ionisation energies (iii) Electrone,gativity decreasing ionic character.
(iv) Hardness (v) Oxidation potential (iv) MgO, srO, K20 and Cs 20 in order of increasing basic
(vi) Basic character of hydroxides character. [Il.T. 1991]
(vii) Solubility of hydroxides (viii) Solubility of sulphates (v) CaS04, BaS04 and MgS04 in order of decreasing
(Ix) Stability of carbonates (x) Reducing nature solubility in water.
6. Write the chemical formula of the following: (vi) BeC0 3, MgC0 3, CaC0 3 and BaC03 in order of
(a) Quicklime (b) Slaked lime (c) Anhydrone increasing stability.
(d) Baryta water (e) Marble (f) Anhydrite (vii) Sr, Ba, Ca, Mg in order of increasing reducing nature.
(g) Gypsum (h) Plaster of Paris (i) Asbestos (viii) BeS04, MgS04, CaS04, SrS04 in order of decreasing·
(j) Hydrolith. thermal stability. [U.T. 1997]
7. Write formulae of the following minerals: 14. Answer with giving reason:
(i) Beryl, (ii) Magnesite, (iii) Kieserite, (iv) Witherite, (i) Which are more electropositive alkali metals or alkaline
(v) Celestine, (vi) Epsom salt, (vii) Chrysoberyl, (v~ii) Baryta, earth metals?
(ix) Strontianite, (x) Fluorspar. ' (ii) Which one is a covalent hydride?
8. What happen when the following are heated? BeH2, NaH, CaH2
(i) Hydrated magnesium chloride, (ii) Gypsum, (iii) Bicar- (iii) Which is more hydrated?
bonates of alkaline earth metals, (iv) Epsom salt, Be2+, Na, + C a2+
(v) Barium nitrate. (iv) The solution of which one is acidic?
9. What is the action of water on the following? NaCl, BaCh, BeCh
(i) Beryllium carbide, (ii) Calcium carbide, (iii) Calcium nitride, (v) Which has least hardness?
(iv) Calcium cyanamide, (v) Hydrolith. N a, Be, Li, Ca
10. What happens when? (vi) Which has the maximum lattice energy?
(i) Magnesium is burnt in air and the products treated Li 20, Na20, MgO, BaO
with water. (vii) Which one are strong reducing agents?
(ii) Water is added, to CaC2 and the resulting gas is passed Alkali metals or alkaline earth metals.
through dilute H2S04 containing HgS04. 15. Describe the preparation, properties and uses of the follow-
(iii) Hydrated magnesium chloride is heated in presence of ing compounds:
ammonium chloride. (i) Slaked lime (Ii) Plaster of Paris
(iv) FeCl 3 is treated with magnesium. (iii) Calcium carbide (iv) Calcium cyanamide
(v) NH4Cl is heated with magnesium. (v) Magnesium chloride (vi) Magnesium sulphate
(vi) CO2 is passed through lime water. 16. (a) How can magnesium be extracted from magnesite?
(vii) S02 is passed through lime water. (b) How can magnesium be extracted from sea water?
(viii) Ch reacts with slaked lime under different conditions. (c) How various compounds of barium are obtained from
11. Complete and balance the following equations: barytes?
(a) Mg(HC0 3)z+Ca(0H)2 ~ MgC0 3 + .......... + H 20 (d) How portland cement is manufactured?
(b) MgO+CaC 2 ~ Mg+ ......... +2C (e) How metal calcium is manufactured?
(c) Be(OH)z+NaOH ~ ......... -I:H 20 17. Explain the following:
(d) BaC03 + H20(steam) ~ ......... + CO2 (1) Magnesium oxide is used for lining of steel making
furnace.
(e) BeCl 2 + LiA1H4 ~ ......... + LiC} + ........ .. [Hint.: MgO is a basic flux and helps in the removal of
(f) CaO+C
High temp'
') ..... +CO
High temp,
. N2
+
) .......... .
acidic impurities from steel through slag formation.
Si + O2 ~ Si0 2 ; MgO + SiOz ~ MgSi0 3
12. How will you prepare the following? Give chemical 4P + 502 ~ P40 IO ; 6MgO + P40lO ~ 2Mg 3(P0 4h
equations also : S + Oz ~ S02; MgO + S02 ~ MgS0 31
(a) Bleaching powder from CaC03 . (ii) Anhydrous calcium sulphate (anhydrite) cannot be
(b) Calcium sulphate from CaC03• used as plaster of Paris.
[Hjnt : Anhydrous calcium sulphate in presence of water (xi) Beryllium sulphate is soluble but BaS04 is insoluble.
does not set like plaster of Paris. However, it is [Hint : Because of high hydration energy of beryllium ion,
directly changed to gypsum.] its sulphate is soluble. Barium being a larger cation
(iii) Anhydrous magnesium chlOIide is prepared by heating has much lower hydration energy.]
MgC12'6B20 in a CUlTent of HCI. (xii) Beryllium does not exhibit a covalency beyond 4.
, ~t: Magnesium chlOlide undergoes hydrolysis with its [Hint : The outermost energy shell in beryllium is the
" ' own water of crystallisation. This hydrolysis is secorid. It cannot accommodate more than 8 electrons
prevented in presence of HCl.] and hence a covalency limit 4 cannot be ex~eeded.l
(iv) The reaction between marble and dilute H 2S04 is not (xiii) The crystalline salts of alkaline ealth metals contain
used to prepare carbon dioxide. more water of crystallisation than the corresponding
[Hjnt: Insoluble CaS04 is formed which deposits on the alkali metal salts. Why? [I.I.T.1997]
surface of marble and prevents further action ofdlIute [Hint : The ionic radii of alkaline earth metal ions are smaller
H2S0 4, so the evolution of CO2 ceases after some- than alkali metal ions.]
time.]
18. Element A bums in nitrogen to give an ionic compound B.
(v) Lime water becomes turbid on passing CO 2 through it,
Compound B reacts with water to give C and D. A solution
but becomes clear when more CO 2 is passed.
[Hjnt : Insoluble CaC0 3 is first precipitated which dis-
of C becomes milky on bubbling carbon dioxide. Identify A,
solves in excess of CO 2 in the form of Ca(HC0 3)z. B, C and D. [IJ.T.1997]
[Hjnt : The element A is calcium.
Ca(OHh + CO 2 ----7 CaC0 3 + H20;
3Ca + N2 --'-7 Ca3N2
(1nsoluble)
(Al (8)
CaC0 3 + H 20 + C02 ----7 Ca(HC0 3 hl Calcium nitride-an ionic compound.
(Soluble)
----7 3Ca(OHh + 2NH3
(vi) In the manufacture of Mg by carbon reduction of MgO, (C) (D)
the product is cooled in the stream of an inert gas. Calcium hydroxide . Ammonia
[Hjnt : Thc reduction of MgO is a reversible process. In Ca(OHh + CO2 ----7 CaC03 + H 20
order to prevent the reaction between Mg and CO, It brings milkiness to solution.]
the temperature of the products is reduced in a
stream of an inert gas. Inert gas does not permit the
reaction of Mg with air.
MgO + C ~ Mg + CO] Match the following:
(vii) Magnesium metal bums in air to give a white ash. When [A] (a) Anhydrite (i) CaS04
this ash is treated with water, the odour of ammonia (b) Carnallite (ii) KCI.MgCh·6H 20
can be detected. What is the reason? [B.I.T.1990] (c) Dolomite (iii) MgS04·7H20
{Hint: The white ash consists small amount of magnesium (d) Epsomite (Iv) Ca3(P04h-CaF2
nitride which is formed along with MgO when Mg (e) Fluorapatite (v) MgC0 3·CaC03
burns in air. Magnesium nitride is hydrolysed with
[B] (a) Gypsum (i) CaRz
water and NH3 is evolved.]
(b) Hydrolith (ii) Cao
(viii) The first ionisation potential of alkaline earth metals is (c) Marble (iii) Ca3(P04h
low and hence they should prefer to form M+ ions. In (d) Bone ash (iv) CaS04·2HzO
fact they form M2+ ions. (e) Slaked lime (v) CaC03
[Hjnt : M2+ ions are extensively hydrated to form hydrated (f) Quick lime (vi) Ca(OHh
ions and a large amount of energy is released. This [C] (a) Nitrolim (i) Calcium salts
energy more than counter balances the higher value
(b) Green flame (li) CaMg3(Si04)4
of second ionisation energy.]
(0) Brick red flame (iii) MgCI 2 ·5MgO·xH20
(ix) Alkaline earth metals have higher melting points than (d) Asbestos (iv) 95% Mg, 5% Zn
alkali metals. (e) Electron (v) CaCN 2 +C
[Hjnt: Metallic bonding is much stronger in alkaline earth
(f) Sorel cement (vi) Barium salts
metals as two electrons are present in valence shell.1
(x) Why gypsum is added to cement?
[Hint : The purpose of adding gypsum is to increase the'
setting time of the cement.]
Answers : Subjective Type Questions (iii) Ammonia is evolved. Ca3NZ + 6H20 ~ 3Ca(OH)z+2NH 3
1. (a) Beryllium halides are somewhat covalent in nature. (iv) Ammonia is evolved. CaCN z + 3H zO ~ CaCOj + 2NH3
(b) Beryllium chloride undergoes hydrolysis. HCI is given out. (v) Hydrogen is evolved. CaR2 + 2H20~ Ca(OH)z + 2H2
BeCl2 + 2H 20 ----7 Be(OHh + 2HCI 10. (i) Magnesium fonns magnesium oxide and magnesium nitride.
(c) CaC03 is converted into soluble calcium bicarbonate. 2Mg + 02 --7 2MgO
CaC03 + H20 + CO2 ----7 Ca(HC03h 3Mg + N z --7 Mg3N2
Soluble MgO combines with water very slowly fonning magnesium
(d) Mg reacts with S02 fonning MgO and S. hydroxide. Mg3NZ reacts with water evolving ammonia.
2~& + S02 ----7 2MgO + S MgO + H20 --7 Mg(OHh
(e) CaCl z reacts with ammonia. Mg3 N2 + 6H20 ----7 3Mg(OHh + 2NH3
CaCl z + 8NH3 ----7 CaCI 2· 8NH3 (ii) Acetylene is evolved. This is passed through dilute H 2S0 4
Addition product
when acetaldehyde is fonned.
2. (i) (a) Limestone (b) Chalk (c) Marble
Cac 2 + 2H20 --7 Ca(OH)z + C2H2
(ii) Calcium (iii) Radium (iv) Dolomite H?S0 4
(v) Magnesite, Epsom salt (vi) Calcium C2 H2 + H2 0 H~SO/ CH 3CHO
3. (a) Be; BeO dissolved in NaOH (iii) Anhydrous ammonium chloride is obtained.
(b) Be (c) Be(OHh (d) Be and Mg (e) Baz+
MgCI2·6H20 + NH4Cl--7 MgCI 2 ·NH 4CI·6H20
(f) Anhydrous calcium sulphate '(CaS04)
Double salt
(g) It is a waste product from steel industry and has properties
Heat Heal
similar to cement. It mainly consists calcium silicate. MgCI2·~Cl·6H20 -6H 0) MgCI2"NH4Cl ----7 MgCl z + ~Cl
2
4. (i) Calcium hydride, CaRl, (ii) Sorel cement, MgCh·5MgOxH20,
(iv) FeCl 3 + 3HzO --7 Fe(OHh + 3HCl
(iii) Bleaching powder, CaOCI2·HzO, (iv) Anhydrone, Mg(CI04h.
[Hint : It has strong affinity for water giving Mg(CI04}z·6H20. Mg + 2HCl --7 MgCh + Hz
It loses whole of water when heated at 250°C and drying (v) Mg + 2NH4Cl --7 MgCl2 + 2NH3 + Hz
property is regenerated.] (vi) The solution becomes milky due to fonnation of CaC03 . The
(v) Calcium oxide, Cao. solution again becomes colourless in excess of CO 2 as CaC03
S. (i) increases, (il) decreases, (iii) decreases, (i v) decreases, dissolves in the fonn of calcium bicarbonate.
(v) increases, (vi) increases, (vii) increases, (viii) decreases, Ca(OH)z + C02 ----7 CaC03 + H20
(ix) increases, (x) increases. CaC03 + H 20 + CO2 ----7 Ca(HC03h
6. (a) CaO, (b)Ca(OH)z, (c) Mg(Cl04}z, (d) Ba(OHh, (e) CaC03,
(vii) Ca(OHh + S02 ----7 CaS03 + H20
(f) CaS04, (g) CaS04·2H20, (h) 2CaS04·H20, (i) CaMg 3(Si04)4,
CaS03 + S02 + H20 ----7 Ca(HS03h
(j) CaHz·
(viii) (a) With cold milk of lime, calcium hypochlorite is fonned.
7. (i) 3BeO·AI20 3·6SiOz, (ii) MgC0 3, (iii) MgS04·H20, (iv) BaC03,
2Ca(OHh + 2Cl2 ----7 CaCl2 + Ca(ClOh + 2H zO
(v) srS04, (vi) MgS04·7HzO, (vii) BeO·Ah03, (viii) BaS04,
(b) With hot conc. solution of Ca(OHh, calcium chlorate is fonned.
(ix) srC0 3, (x) CaF2 .
. Heat' Heat . 6Ca(OHh + 3Cl2 --7 5CaCl2 + Ca(CI03h + 6H20
8. (t)MgClz·6Hz0----7 MgClz·2HzO ----7 Mg(OH)Cl + HCl + H20
(c) With cold solid Ca(OHh, bleaching powder is fonned.
Heat
Ca(OHh + Cl z ----7 CaOCl z + H20
MgO. 11. (a) Mg(HC0 3h + Ca(OH)z ----7 MgC03 + CaC03 + 2H 20
Heat
(b) MgO + CaC2 ----7 Mg + CaO + 2C
(Monoclinic) (Orthorhombic) Plaster of Paris
1
CaO + S02 + "2 O2 ~H---;I
Strongly
CaS04 .~
Heat I (c)
(d)
Be(OH)z + 2NaOH ----7
BaC03 + HzO(steam) ----7
Na2BeOz + 2HzO
Ba(OHh + CO2
eate Burnt plaster
(e) 2BeCl2 + LiAIH4 ----7 2BeHz + LiCI + AlCI)
(iii) M(HC03 h ~ MC0 3 + H20 + C~
(f) CaO + 3C ----7 CaCz + CO
Heat Heat
(iv) MgS04'7H20 ~ MgS04'H20 ~ MgS04 CaC z + N2 ----7 CaCN2 + C
Hepta hydrate Monohydrate Anhydrous
Strongly I 12. (a) CaC03 Heat) CaO H 2 0) Ca(OHh ~~~) CaOCl 2
Heated ) MgO + S02 + "2 O2
Hel
. (V)Ba(N03h ~ BaO + NOz + O 2 (b) CaC03 -=? CaCl z·6H2 0 CaS04·2HZO
9. (i) Methane is evolved. Be1C + 4H zO ~ .2Be(OHh + CH4 Dil.HN03
(c) CaS04. 2H2 0 Strongly) CaO ) Ca(N0 3h
(ii) Acetylene is evolved. CaC z + 2H zO ~ Ca(OHh + C ZH2 heated
HCI or NH4C1 M C (ii) BeHz, low electronegativity of Be, high ionisation potential.
(d) MgC12'6H 20 g 12
(iii) Bez+, smallest in size,
heated)
(e) CaS04,2H20 Heated at) 2CaS04,H20 . (iv) BeCl2,hydrolysis occurs, BeCI2 + 2H20-) Be(OH)z + 2HCI
120°C Weak Strong
13. (i) Bi+ < Sr2+ < Ca2+ < Mg2+ < Be 2+ (v) Na, lowest metallic bonding.
(ii) CaF2 > CaCI2 > CaBr2 > Cal2 (vi) MgO, Mg2+ ion is smallest in size and double the charge in
(iii) BaCI2 > SrCI 2 > CaCI 2 > MgClz > BeClz comparison to Li+ and Na+ ions,
(iV) MgO < srO < K 20 < CszO (vii) Alkali metals, the values of oxidation potentials are high.
(v) MgS04 > CaS04 > BaS04 Answers : Matching Type Questions
(vi) BeC03 < MgC03 < CaC0 3 < BaC03
[A] (a-i); (b-ii); (c-v); (d-iii); (e-iv)
(vii) Mg < Ca < Sr < Ba
(viii) SrS04 > CaS04 > MgS04 > BeS04 [B] (a-iv); (b-i); (c-v); (d-iii); (e-vi); (f-ii)
14. (i) Alkali metals, low ionisation potential. [C] (a-v); (b-vi); (c-i); (d-ii); (e--iv); (f-iii)
'LLllST~I'ONS OF OBJECTIVE QUESTIONS

1. Amongst the following hydroxides, the one which has lowest 7. Metallic magnesium is obtained by :.
value of Ksp at ordinary temperature is? (a) reduction of MgO with coke
(a) Be(OHh (b) Mg(OHh (b) electrolysis of an aqueous solution of MgCl2
(c) Ca(OHh (d) Ba(OHh (c) electrolysis of molten MgCl 2
Ans. (a) (d) displacement of magnesium by iron from MgCl2 solution
[Hint : Be(OH)z is least soluble in water.] Ans. (c)
2. Yellow phosphorus on reaction with Ca(OHh gives : 8. Among the alkaline earth metals, the element forming
(a) Ca(H2P04h (b) Ca(H2P02h predominantly .covalent compounds is :
(c) PH3 (d) both (b) and (c) (a) barium (b) beryllium
Ans. (d) (c) strontium (d) calcium
[Hint: SP + 3Ca(OHh + 6H zO ---7 3Ca(H2P02h + 2PH31 Ans. (b)
3. Slaked lime is obtained when water is added to: [Hint: Be 2+ ion has a small size. It has high polarising power.]
(a)
I
CaS04· 2: H20 9. Magnesium is an important component of which biomolecule
occurring extensively in living world?
(c) Cao (a) Haemoglobin (b) ATP
Ans. (c)
[Hint : The slaked lime is calcium hydroxide. It is obtained when (c) Chlorophyll (d) VitaminB 12
water is added to CaO (Lime), . Ans. (c)
CaO + H20 ---7 Ca(OH)z] 10. The solubilities of carbonates decrease down the magnesium
4. As compared to alkali metals, alkaline earth metals: group due to a decrease in :
(a) are more metallic (a) entropy of solution formation
(b) have higher densities (b) lattice energies of solids
(c) are stronger reducing agents (c) hydration energies of cations
(d) have larger atomic radii (d) inter-ionic attraction
Ans. (b) Ans. (c)
5. Which of the following carbides give allylene on 11. Several blocks of magnesium are fixed to the bottom of a ship
hydrolysis? to:
(a) CaC 2 (b)~
(a) prevent action of water and salt
(C)MgC2 (d) Mg2C 3 (b) prevent puncturing by under sea rocks
ADS. (d) (c) keep away the sharks
[Hint: Mg2C3 + 4H20 ---7 2Mg(OH)z + CH 3-C==CH ] (d) make the ship lighter
Ans. (a)
6. Black ash is :
12. A metal M readily forms water soluble sulphate MS04. water
(a) caS + NaHC0 3 (b) caS04 + Na2C03
insoluble hydroxide M(OHh and oxide MO which becomes
(c) caSo4 + NaHC03 (d) caS + Na2C03
Ans. (d)
inert on heating. The hydroxide is soluble in NaOH. Then M
is :
(a) Be (b)Mg an excess of C02 through 'f' in water a clear solution 'Z' is
(c) Ca (d) Sr obtained. On boiling 'Z' compound 'X' is reformed.The
Ans. (a) compound 'X' is:
[Hint : BeS04 - soluble; Be(OHh insoluble (a) Ca(HC03)z (b) CaC03
Be(OHh + 2NaOH ~Na2Be02 + 2H 20] (c) Na2C03 (d) K2CO:>
Soluble Ans. (b)
13. Dead burnt plaster is : [P.M.T. (Kerala) 2006] [Hint: CaC0 3 ~ CaO + C02;
'X' residue
(a) CaS04·2H20 (b) MgS04·7H20
I CaO + H20 ~ Ca(OHh
(c) CaS04'2'H20 (d) CaS04 'yo
Ans. (d) Ca(OHh + 2COz -----t Ca(HC03h;
14. WhiCh of the following statement(s) is/are not true about the 'yo
boiling
'Z'
diagonal relationship of Be and Al? Ca(HC03 h ) CaC03 + H20 + CO2 J

'Z' 'X'
A. Both react with NaOH to liberate hydrogen
B. Their oxides are basic 17. In which of the following, the hydration energy is higher than
C T4ey become passive by concentrated HN0 3 the lattice energy? [C.B.S.E. 2007]
D. Their carbides give acetylene on treatment with water (a) MgS04 (b) RaS04
(a) Only A (b) Band C (c) SrS04 (d) BaS04
(c) A and D (d) B and D Ans. (a)
Ans. (d) [Hint : Mg2+ ion is the smallest and hence has highest hydration
[Hint : Their oxides are amphoteric and their carbides give methane
energy,]
on treatment with water.] 18. Be and Al exhibit many properties which are similar. But the
15. The correct sequence of increasing covalent character is two elements differ in: [A.I.E.E.E.2007]
represented by: . (a) forming covalent bonds
(a) BeC12<NaCl<liCl (b) NaCl< liCI < BeClz (b) forming polymeric hydrides
(c) BeCI2<liCI<NaCI (d) LiCl<NaCl<BeCl2 (c) exhibiting maximum covalency in compounds
Ans. (b) (d) exhibiting amphoteric nature in their oxides
[Hint : The polarizing power of cation increases with decrease in Ans. (c)
size of cation and increase of charge on the cation.]
16. A solid compound 'X' on heating gives C02 gas and a
residue. The residue mixed with water forms 'f'. On passing
)
(a) ionic nature of BeF2 0 64. Which of the following is least soluble in water?
2
(b) greater hydration energy of Be + ion as compared to (a) BaF2 0 (b) SrF2 0
crystal lattice 0 (c) CaF2 0 (d) MgF2 0
(c) covalent nature of BeF2 0 65. When CaC2 is heated in atmospheric nitrogen in an electric
(d) none of the above 0 furnace, the compound formed is: (J.KE. (Orissa) 2007]
52. The order of increasing lattice energy of the following (a) Ca(CNh 0 (b) CaNCN 0
compounds is: (c) Ca3N2 0 (d) CaNC2 0
(a) NaCI < CaO < NaBr < BaO 0 66. Which among the following has the tendency to form
(b) NaBr< NaCl<BaO<CaO 0 covalent compounds?
(c) NaCI < NaBr < BaO < CaO 0 (a) Calcium 0 (b) Beryllium 0
(d) NaBr < NaCI < CaO < BaO 0 (c) Strontium 0 (d) Magnesium 0
53. Be(OHh is: 67. The hydration energy of Mg2+ ions is higher than that of:
(a) acidic 0 (b) basic 0 (a) Al 3+ 0 (b) Be2+ 0
(c) amphoteric 0 (d) neutral 0 (c) Na+ 0 (d) none of these 0
54. Hydrolith is the common name of :
68. Which of the following metals dissolves in KOH with the
(a) NaH 0 (b) CaF2 0 evolution of hydrogen?
(c) Cao 0 (d) CaR2 0 (a) Ca 0 (b) Mg 0
55. The salts of which of the following give green colour in fire (c) Sr 0 (d) Be [)
works? 69. Which of the following is used for taking the X-ray spectra
(a) Na 0 (b) K 0 of the digestive system?
(c) Ba 0 (d) Ca 0 (a) CaSo4 0 (b) BaS04 0
56. Which of the following hydroxides is most stable? (c) MgS04 0 (d) BaC03 []
(a) Mg(OHh 0 . (b) Ba(OHh 0 70. The formula of calcium cyanamide is:
(c) Sr(OHh 0 (d) Ca(OHh 0 (a) Ca(CNh 0 (b) CaC2NZ [)
57. When hydrated MgC12·6H20 is strongly heated: (c) CaCN2 0 (d) Ca3NZ 0
(a) MgO is formed 0 71. Calcium cyanamide reacts with steam to form ammonia and
(b) Mg(OH)2 is formed 0
(c) Mg(OH)CI is formed 0 (a) Ca(OH)z 0 (b) Cao 0
(d) anhydrous MgCl 2 is formed 0 (c) Ca(HC~h 0 (d) Cac~ 0
58.· On strong heating. gypsum gives: n The mixture of MgCl2 and MgO is called:
(a) Cao
. 1
o (b) CaS04 1
0 (a) sorel cement 0
(c) CaS04· H20 0 (d) CaS04·l H20 0 (b) mixed salt 0
2 2 (c) portland cement 0
59. The radioactive element X decays to give two inert gases.
(d) magnesium oxychloride 0
The element is:
73. Which of the following salts is used for clearing snow from
(a) 2~~U [) (b) 2~~Ra 0 roads during winters?
(c) 2~6Th 0 (d) 2~~Np 0 (a) CaClz 0 (b) CaF2 0
(c) MgCl 2 0 (d) SrCl2 0
roo Which of the following salts on heating gives a mixture of 74. Which of the following is the strongest base?
two gases?
(a) Ca(OHh 0 (b) Sr(OHh 0
(a) Ba(N03h 0 (b) NaN03 0 (c) Ba(OHh 0 (d) Mg(OHh 0
(c) KN03 0 (d) RbN~ 0
75. Portland cement does not contain:
6l. Gypsum is added to clinker during cement manufacture to:
(a) Ca3Al206 0 (b) Ca3Si03 0
(a) decrease the rate of setting of cement 0 (c) Ca2Si04 0 (d) Ca3(P04h 0
(b) bind the particles of calcium silicate 0 76. Which of the following carbides. on hydrolysis, yields
(c) facilitate the formation of colloidal gel 0 methane?
(d) all of the above 0 (a) BezC 0 (b) MgC2 0
62. Which of the following exists as polymeric chains in solid (c) CaC2 0 (d) Mg2C 3 0
state? 77. A fire work gave bright crimson light. It probably contained
(a) BeCl2 0 (b) MgCl2 0 a salt of:
(c) SrCl 2 0 (d) BaCl2 0 (a) Ca 0 (b) Sr 0
63. Which of the following is most soluble in water? (c) Ba 0 (d) Mg 0
(a) MgS04 0 (b) caS04 0 78. An1:).ydrous MgCl2 may be obtained by heating MgClz·6H20:
(c) srSo4 0 (d) BaS04 0 (a) until it fuses 0
(b) with lime 0
(c) with coal D 92. The right order of the solubility of sulphates of alkaline earth
(d) in a current of dry HCl D metals is:
79. Amongst the following hydroxides, the one which has the (a) Be > Ca > Mg > Ba > Sr D
lowest value of Ksp at ordinary temperature is: (b) Mg>Be>Ba>Ca>Sr D
(a) Mg(OHh D (b)Ca(OH)z D (c) Be>Mg>Ca>Sr>Ba D
(c) Ba(OH)z D (d) Be(OHh D (d) Mg>Ca>Ba>Be>Sr D
80. Compounds of alkaline earth metals are less soluble in water 93. Of the following the commonly used in the laboratory
than the corresponding alkali metal salts due to: desiccator is:
(a) their high ionisation energy D (a) Na2C03 D
(b) their low electronegativity 0 (c) NaCl D
(c) their low hydration energy D 94. A compound with water gives hissing sound and becomes
(d) their high lattice energy D very hot. It is:
81. Which of the following chlorides is covalent? (a) calcium carbonate D (b) calcium sulphate D
(a) Ba02 D (b) Na.O D (c) quicklime 0 (d) ca1ciumchloride D
(c) Ca02 D (d) Bea2 D 95. Slaking is the process of adding water to:
82. In the reaction, Be + 2NaOH ---7 A + H 2, A is: (a) caSo4 D (b) Caa2 D
(a) Be(OH)z D (b) BeO D (c) Caco3 D (d) Cao 0
(c) Na2Be02 D (d) none of these D 96. Which of the following is different from other three oxides?
83. Barium bums in excess of oxygen forming: (a) MgO D (b) SnO D
(a) BaO D . (b) Ba202 D (c) ZnO D (d) PbO D
(c) Ba02 D (d) none of these D [Hint : MgO is basic while the other three are amphoteric.]
84. Which of the following is barytes water? CJ7. Magnesium is manufactured by electrolysing fused
magnesium chloride using:
(a) Ca(OH)z D (b)LiOH D
(a) a nickel cathode and a graphite anode D
(c) Be(OHh D (d) Ba(OHh D
(b) the iron container as anode and a nickel cathode D
85. Which of the following represents calcium chlorite? (c) the iron container as cathode and a graphite anode D
(a) Cao~ D (b) Ca(CI04h D (d) the nickel container as cathode and iron anode D
(c) Ca(00:3h 0 (d) Ca(CI02h D 98. The most abundant metal present in the human body is:
86. Identify the correct statement: (a) C a D (b) K D
(a) Gypsum contains a lower percentage of calcium than (c) Fe 0 (d) Na D
plaster of Paris D 99. Soda lime is used extensively in decarboxylation reaction to
(b) Gypsum is obtained by heating plaster of Paris D obtain alkanes. Soda lime is:
(c) Plaster of Paris is obtained by hydration of gypsum D (a) NaOH D (b) NaOH and CaO D
(d) Plaster of Paris is obtained by partial oxidation of gypsum (c) Cao D (d) Na2C03 D
D 100. The highly efficient method of obtaining beryllium is:
87. The sodium is made by electrolysis of a molten mixture of (a) reduction of beryllium halide with Mg D
40% NaCI and 60% CaCl2 because: (b) reduction of beryllium oxide with carbon D
(a) CaCl2 helps in the conduction of electricity D (c) dissociation of beryllium carbide D
(b) ci+ can reduce NaCl to Na . D (d) electrolysis of fused beryllium chloride D
(c) Ca2+ can displace Na from NaCI D 101. Which of the following statements is not correct?
(d) this mixture has a lower melting point than NaCI D (a) Plaster of Paris is made by heating gypsum to 100°C and
88. Kieserite is an ore of: its formula is CaS04·H20 D
(a) Cu D (b) Fe D (b) Alkaline earth metal salts are diamagnetic D
(c) Mg D (d) AI D (c) Third ionisation energies of alkaline earth metals are very
89. The metal that is extracted from sea water is: high' 0
(a) Mg D (b) Be D (d) BeO and Be(OHh are amphoteric in nature D
(c) Ca D (d) Sr D 102. Identify the correct statement:
90. Ordinary blackboard chalk is made of: (a) BeH2 contains three-centre two-electron bond. D
(a) limestone D (b) gypsum D (b) CaH2> BaH2 and SrH2 are ionic in nature. 0
(c) fluorspar D (d) calcium phosphate D (c) Beryllium hydride and magnesium hydride are covalent
91. The most electropositive amongst the alkaline earth metals and polymeric. D
is: (d) All of these. D
(a) Be D (b)Mg D 103. The.compoufld which is insoluble in dil. HCl is:
(c) Ca o (d) Ba D (a) MnS D (b) ZnS D
(c) BaC03 D (d) BaS04 0
11. A sodium salt on treatment with MgCl2 gives white precipitate 15. Match (X) with (Y) and select the correct alternative.
on heating. The anioh of the sodium salt is : X Y
(a) HCO) (b) CO~- Sorel cement
A. 1. CaH2
(c) SO~- (d) NO"] Anhydrone
B. 2. BaS04+ Zns
CHydrolith 3. MgC12· 5MgO·xH20
[Hint :MgCI2 + 2NaHC03 ---7 Mg(HC03h ~ MgC0 3 1
Soluble White ppt. D.
Lithopone 4. Mg(G04h
A B C D
12. Lattice energies of BeF2> MgF2, CaF2 and BaF2 are -2906,
l (a) 1 2 3 4
-2610, -2459 and -2367 kJ mor respectively. Hydration
2 2 (b) 2 3 4 1
energies of Be +, Ml+, Ca +,Bi+ and F are-2494,~1921,
1
-1577, -1305 and - 457 kJ mol- respectively. Which of the (c) 3 4 1 2
fluorides is soluble in water? (d) 4 1 2 3
(a) BeF2 (b) MgF2 16. Which are correct statements?
(c) CaF2 (d) BaF2 (a) Ca3(P04h is present in bones
[Hint: (b) 3Ca3(P04h·CaF2 is part of enamel on teeth
BeF2 MgF2 CaF2 BaF2 (c) Ca2+ ions are important in blood clotting
Hydration -2494 + 2x (-457) -1921 + 2 x (-457) -1577+2x(-457) -1305 + 2 x (-457) (d) Chlorophyll is a compound of calcium
energy =-3408 = - 2835 =-2491 = 2219 17. Which are correct statements for Be and AI ?
Lattice " "-'29U6""" . '" - ':" 26fO --"2459 ',' '--'::: 236;:'- ., '(a) Both"have~p-hybridiziti~~their cOmP~unds~"'--'
energy
(b) Both are rendered passive by concentrated RN03.
AH - 3408 (- 2906) - 2835 - (- 2610) 1- 2491 (- 2459) - 2219 - (- 2367) (c) Both form amphoteric oxides.
solution = - 502 kJ morl = - 225 kJ mol-I =,-;: 32 kJ morl = 148 kJmol- 1
(d) Both form ionic hydrides.
llH solution is -ve in BeF2, hence BeF2 is easily soluble in water. ] 18. Chemical A is used for water softening to remove temporary
13. The name and the formula of a compound of Ca, C and N used hardness. A reacts with sodium carbonate to generate caustic
as a fertilizer is : soda. When CO2 is bubbled through A, it turns cloudy. What
(a) calcium cyanide, Ca (CNh is the chemical formula of A ?
(b) calcium cyanamide, CaCN2 (a) CaC03 (b) CaO
(c) calcium cyanide having carbon particles, (Ca(CNh + c) (c) Ca(OH)2 (d) Ca(HC03h
(d) calcium cyanamide plus carbon (nitrolim), (CaCN2 + C) [Hint: Ca(OH)z + Ca(HC03h ---7 2CaC03 + 2H20
14. The name and formula of the compound of magnesium;chlo- Ca(OHh + Na2C03 ---7 CaC03 + 2NaOH
rine and oxygen used as a drying agent is : Ca(OHh + CO 2 ---7 CaC0 3 + H20 1
(a) magnesium oxychlorite, Mg(OClh 19. Salt used as a purgative is :
(b) magnesium chlorate, Mg(CI03h (a) NaG (b) MgS04·7H20
(c) magnesium perchlorate, Mg(CI04h (c) MgClz·6H20 (d) Ca3Alz06
(d) none of the above 20. Water is added to calcium carbide and the evolved gas is
[Hint: Magnesium perchlorate (anhydrone) has strong affinity passed through dilute H2S04 containing HgS04 . The. organic
for water giving Mg(CI04h·6H 20. It loses whole of compound formed is :
water when heated at 25O"C and drying property is (a) HCHO (b) CH3CHO
regenerated. ] (c) CH3COOH . (d) HCOOH
1. (d) 2. (a) 3. (b) 4. (c) 5. (b) 6. (c) 7. (a) 8. (d) 9~ (b) 10. (c) 11. (a) 12. (a)
13. (d) 14. (c) 15. (c) 16. (a, b, c) .17. (b, c) 18. (c) 19. (b) 20. (b)
35,4 GR.B. Inorganic Chemistry for Competitions
Matrix Matching Questions for liT Aspirants

1. Match List-l with List-II: 4. Match the elements in List-I with their nature in List-II:
List-I List·n List·1 List·n
(a) Sorel's cement (p) MgCl2 (a) Be (p) Radioactive'
(b) Albite (q) MgO (b) Fr (q) Form covalent hydride
(c) A salt of carnallite (r) NaAlSi 30 g (c) Ra (r) Form amphoteric oxide
(d) Glauber's salt (s) Na2S04·lOH20
(d) Mg (s) Do not impart any colour
2. Match the metals in List-l with their ore in List-II and formula in
to Bunsen flame
List-III:
List·I List-n List-ill 5. Match List-I with List-II:
(Metal) (Name of ore) (Composition List-J List-n
of ore) (Compounds) (Use of compounds)
(a) Lithium (p) Kiesserite (u) LiAISi 20 6 (a) Magnesium oxide (p) Fertilizer
(b) Sodium (q) Spodumene (v) NaN0 3 (b) Barium sulphate (q) Purgative
(c) Calcium (r) Auorspar (w) MgS0 4·H 20 (c) Calcium cyanamide (r) As a constituent of sorel
(d) Magnesium (s) Chile saltpetre (X)CaF2 cement
3. ..Match thUommon!Lame of th~_compou~ds in List~l. with. its (d) Magnesium oSulphate .(.s.).As a constituent.oflitlropon.e.e~.- _
chemical formula in List-II: (t) Refractory material
List-J List-n
(a) Brine (p) KCI
(b) Rock salt (q) NaCI
(c) Sylvine (r) MgS04,7H20
(d) Epsomite (s) CaSi03
(e) Fly ash
1. (a-p, q) (b-r) (c-p) (d-s) 4. (a-q, r, s) (b-p) (c-p) (d-s)

2. (a-q-u) (b-s-v) (c-r-x) (d-p-w) 5. (a-r, t) (b-s) (c-p) (d-q)
3. (a-q) (b-q) (c-p) (d-r) (e-s)

In each of the following questions, two statements are given 4. (A) Beryllium compounds are covalent in nature.
as Assertion (A) and Reason (R). Examine the statements and 2
(R) The size of Be + ion is larger in comparison to the radii
answer the questions according to the instructions given below. of the other divalent ions of alkaline earth metals.
Mark: 5. (A) Lithium resembles magnesium.
(a) if both (A) and (R) are correct and (R) is the correct (R) Li+ has same size as Mg2+. fA.I.I.M.S. 1997]
explanation of (A). 6. (A) The fluorides of alkaline earth metals are almost
(b) if both (A) and (R) are correct and (R) is not the correct insoluble in water.
explanation of (A). (R) The lattice energies of the fluorides of alkaline earth
(c) if (A) is correct and (R) is wrong. metals are very high.
(d) jf (A) is wrong and (R) is correct. 7. (A) Sulphur is estimated as BaS04 and not as MgS0 4.
(e) if both (A) and (R) are wrong. (R) The ionic radius of Ml+ is smaller than that of Ba +
2
1. (A) Beryllium and magnesium do not impart characteristic ion. [UTa 1998]
colour to the Bunsen-burner flame. 8. (A) Na2S04 is solubJe in water but BaS04 is insoluble.
(R) Both Beryllium and magnesium have high ionisation (R) Lattice energy of barium sulphate exceeds its hydration
energy. energy. [A.I.I.M.S. 1997}
2. (A) Be(OHh dissolves in excess of NaOH. 9. (A) MgO is used for lining of steel making furnace.
(R) Be(OHh is an amphoteric compound. (R) MgO is an acidic flux.
3. (A) Alkaline earth metals are softer than alkali metals. 10. (A) Magnesium gets oxidised when heated in CO 2 or S02
(R) Atomic radii of alkaline earth metals are smaller than atmosphere.
corresponding alkali metals in the same periods of (R) Magnesium has a strong affinity for oxygen.
periodic table.
1. (a) 2. (b) 3. (d) 4. (c) 5. (a) 6. (a) 7.' (b) 8. (a) 9. (c) 10. (a)
111111111 THOUGHT TYPE QUESTIONS 11111111

THOUGHT 1 ,.~..._==,.•_",,_<_,,"=_'=_'~"'_~'~'~'~_"~'~'.,_. cium aluminates and silicates. The important raw materials needed
for the manufacture of cement are, limestone, clay and gypsum.
Both alkaline earth metals and alkali metals are s-block elements.
The main step in the manufacture of cement is the heating of raw
They resemble with each other in many respects but still there are
meal or slurry in .the rotary kiln at a very high temperature 1400-
certain dissimilarities in their properties on account of different
1600°C. Finally 2 or 3% gypsum is added.
number of electrons in the valency shell, smaller atomic radii,
When cement is mixed with water and left. as such for some
higher ionisation potential, higher electronegativity, etc.
time, it becomes a hard mass. This is known as setting of cement.
Like lithium. beryllium also differs from rest ()f the alkaline earth
It is believed that various aluminates and silicates present in the
metals on account of its small atomic size and high electro- cementform-hydrates-with-water-which-separatein the-form~o'+:-f-
negativity. z+ ion is very small and exerts ahigh polarising effect
Be gel. The gels formed start losing water partly by evaporation and
on any anion associated with it.
partly by forming hydrates with unhydrated constituents. This re-
1. The correct sequence of increasing covalent character is
sults in the formation of a hard mass.
represented by :
1. Portland cement does not contain :
(a) BeG2 < NaCI < LiCI (b) NaCI < LiCI < BeCl z
(a) CaSi04 (b) CaSi03
(c) BeC12 < LiCI < NaCI (d) LiCI < NaG < BeCl2
(c) Ca3·Al206 (d) Ca3(P04n
2. Which is least thermally stable ? 2. Setting of cement is :
(a) Li2CO:> (b) MgC03
(a) exothermic reaction (b) endothermic reaction
(c) BaC03 (d) BeC03
(c) hydration process (d) none of these
3. Which of the following statements are true for II A group 3. The percentage of lime in portland cement is approximately:
elements?
(a) 20
25 % (b) 30-40 %
(a) Lattice energy of oxides, carbonates, fluorides decreases
60-65%
(c) (d) 40-50%
from Be to Ba.
4. Concrete is a mixture of :
(b) All form nitrides in air.
(a) .cement, sand, qravel and water
(c) The solubility of the hydroxides increases from Be to Ba.
(b) cement, limestone and water
(d) All are correct. . (c) cement, slaked lime and water
4. The alkaline earth metal which does not directly combine with (d) cement, sand and water
hydrogen is :
5. Gypsum is added to portland cement :
(a) Be (b) Ca
(a) to fasten the process of setting
(c) Sr (d) Ba
(b) to slow down the process of setting
5. The solubility in water of sulphates down the IIA group is :
(c) to improve the colour of the cement
Be > Mg > Ca > Sr > Ba (d) all of the above are incorrect
This is due to :
(a) increase in melting point
THOUGHT
(b) increasing molecular mass
(c) decreasing lattice energy Metal nitrate (A) on heating decomposes, leaving asolid residue
(d) high heat of solvation for smaller ions (8) which goes into solution with dilute HCl. The solution of (8)
6. Which of the bicarbonate does not exist in solid state ? gives a white precipitate with ammonium carbonate solution. The
(a) NaHC~ (b) KHC03 precipitate (C) is dissolved in dilute HCI and the solution is treated
(c) Ca(HC03n (d) RbHC~ with potassium chromate to get yellow precipitate (D). The solution
7. The element which does not directly combine with carbon (8) with dilute H 2S04 also gives a white precipitate(E) insoluble
on strong heating : in diluteHCI and nitric acid. The precipitate (E) is a part of a white
(a) Li (b) Be pigment lithopane.
(c) K (d) Ca 1. The compound (E) is :
(a) BaS04 (b) MgS04'
THOUGHT 2 (c) caS04 (d) Na2S04
2. The yellow precipitate (D) is :
Cement is one of the most important building material of the
(a) PbCr04 (b) BaCr04
present time. It is a dirty greyish heavy powder containing cal,
(c) CaCr04 (d) none of these
3. The metal nitrate (A) is : manufacture of other alkalies and bleaching powder, in sugar
(a) Ca(N0:3)Z (b) Pb(N03n refining, in tanning hides and in water softening.
(c) Ba(N03n (d) KN03 1. The substance not likely to contain CaC03 is :
4. The solid residue (B) is : (a) dolomite (b) a marble statue
(a) CaO (b) PbO (c) sea shells (d) calcined gypsum
(c) ZnO (d) BaO 2. Slaked lime reacts with chlorine to give :
5. The nitrate (A) can be confirmed by flame test. The colour (a) Cao2 (b) CaO
imparted by the salt to the flame is : (c) Caoo2 (d) CaC03
(a) yellow (b) green 3. Quick lime is :
(c) blue (d) red (a) Cao (b) CaC03
(c) Ca(OHh (d) CaS04
THOUGHT 4 4. The drying agent which absorbs CO2 and reacts violently
with water is :
Limestone is a naturally occuring form of calcium carbonate. It
(a) sodium carbonate (b) quicklime
is used as building material (lj}d also for manufacture of other
(c) conc. H2S04 (d) alcohol
building materials such as Portland cement. It is used for the
5. Chemical compound 'A' is used to remove temporary hard-
production of quick lime and slaked lime which have wide
ness from water. It reacts with Na2C03 to generat~ caustic
applications in chemical, metallurgical and construction industry.
soda. When CO 2 is passed thr()lJgh 'A' it turns cloudy. Wh_a_t_ __
The pure GaCOJ,-Galled predpitated,calGium-Garbonate;-is-used--
is 'A'?
extensively as filler providing bulk to materials such as paint,
(a) CaC03 (b) Ca(HC03n
plastics, printing inks and rubber. It is also used in toothpastes,
(c) Ca(OHh (d) CaCl2
cosmetics and antacids. Quick -lime and slaked lime are the
6. Quick lime is used in electric power plants with carbon to
cheapest and most widely used bases for neutralising unwanted
check pollution. What product of calcium is formed?
acids. Lime is used to neutralise acidic soils. An important
(a) caS03 (b) caS04
application of quick lime is in air pollution control for the removal
(c) CaS (d) CaS04·lOH20
of S02 in electric power plants. Slaked lime is used in the
Thought 1 1. (b) 2. (d) 3. (d) 4. (a) 5. (d) 6. (c) 7. (c)

Thought 2 1. (d) 2. (a, c) 3. (c) 4. (a) 5. (b)
Thought 3 1. (a) 2. (b) 3. (c) 4. (d) 5. (b)
Thought 4 1. (d) 2. (c) 3. (a) 4. (b) 5. (c) 6. (a)
The answer to each of the following questions is a single 4. On heating calcium ammoniate, ammonia and hydrogen are
digit integer, ranging from 0 to 9. evolved. How many moles of ammonia are evolved when 1.5
1. How many alkaline earth metals are known? moles of calcium ammoniate are heated ?
2. How many water molecules are associated with 'Epsom salt'? 5. Magnalium is an alloy of aluminium and magnesium. What
3. Magnesium oxide when mixed with a saturated solution of is the percentage of magnesium in this alloy?
magnesium chloride sets to a hard mass like cement known 6. Calcium carbide reacts with nitrogen and forms an important
as 'sorel cement'. The composition of sorel cement is fertilizer, calcium cyanamide. How much calcium cyanamide
Mg02nMgOxH20. What is the value of n? is formed when 3.2 g of calcium carbide is completely
converted into cyanamide?
1. (6) Be, Mg, Ca, Sr, Ba and Ra are alkaline earth metals. 5. (5) MagnaJium: 95% Al + 5% Mg
2. (7) Epsom salt has the molecular formula, MgS04 -7H 20. CaCN 2 +C
3. (5) MgCI 2·5MgOxH20 80 g
4. (8) :3C::a(NH3)6~Ca3N2+16NH3+3H2
3 moles 16 moles
80 x 3.2 =4
1_5 moles 8 moles 64
-~
Revi§ion Exerl:i§e
Il:hap1:er 5 1:0 7] 2)
SINGLE CORRECT ANSWER TYPE (d) all of these 0
10. The deep colour produced when iodine is dissolved in a
I. The pair that yields the same gaseous product on reaction
solution of KI is caused by the presence of :
with water:
(a) K and KO z 0 (b) Ca and CaHz o (a) 13' 0 (b) 1- o
(c) Na and NazOz 0 (d) Ba and BaOz o (c) 12' 0 (d) I z o
11. Dissolving NaNHz in water will give:
2. Acidified KZCrZ07 on oxidation by HzOz gives:
(a) a solution containing solvated Na+ ions, OH- ions and
(a) Blue solution 0 (b) cr05 o NH3 . 0
(c) Chromium peroxide 0 (d) all of these o
(b) a solution containing solvated Na+ and NH2' ions 0
3. Select the reaction which does not occur.
(c) NH3 and metallic sodium 0
(a) NaNH2 + C 7S0"C) NaH + HCN o (d) solvated N:a+ionsandpyQl'Qgenga.s .-~ -r
---------.. ---- HeaC---'---" .. -.-
(b) 6NaOH+4S--7Na2SZ03 +2NazS+3HZO o 12. Temporary and permanent hardness can be removed by
Heat . 0 addition of .......... and .......... respectively.
(c) Na(NH4)HP04--7NaP03+NH3+Hz o (a) CaO,CaC0 3 0 (b) CaO,NaZC03 0
(d) 2KOz + 2H20---'t 2KOH +H20z + O2 o (c) Na2C03,CaO 0 (d) NaHC0 3,CaClz 0
4_ The order of increasing thermal stabilities of 13. CO 2 gas along with solid (Y) is obtained when sodium salt
KZC03, MgC03, CaC0 3 , BaC0 3 is: (X) is heated. (X) is again obtained when CO 2 gas- is passed
(I) (II) (ll) (IV) into aqueous solution (f). (X) and (f) are :
(a) IV ~ II < I <III 0 (b) IV <II <III < I 0 (a) Na2C03,Na20 0 (b) Na2C03,NaOH 0
(c) II < III < IV <I 0 (d) II <IV <III <I 0 (c) NaHC0 3, Na2C03 0 (d) Na2C03, NaHC0 3 0
5. Alkali metals form hydrated compounds. The hydration 14. A meta.l M readily forms water soluble MS04- It also forms
enthalpies of alkali metals are in the sequence of : oxide MO which becomes inert on heating. Hydroxide M(OHh
(a) Rb+ >Li+ >Na+>K+ >CS+ 0 is insoluble in water but soluble in NaOH solution. What is
(b) CS+ >Rb+ >K+ >Na+ >Li+ 0 M? ~.
(a) Mg (j (b) Ba o
~~>~>r>~>~ 0
(c) Ca o (d) Be o
(d) K+ > Na+ >Li+ > Rb+ >CS+ 0 15_ The correct order of equivalent conductivity at infinite
6. The strength of 10 volume solution of hydrogen peroxide is: dilution of LiCI, NaCI and KCI is :
(a) 22.79 gIL 0 (b) 30.36 gIL 0 (a) LiO>NaCl>KCI 0 (b) KCl>NaCl>LiCl 0
(c) 18.5 gIL 0 (d) 25.67 gIL 0 ec) NaCl>KCI>LiCI 0 (d) LiCl>KCl>NaCl 0
7_ Ozone reacts with H20Z to give oxygen. One volume of ozone 16. Strong reductant in IIA and IA group is :
gives: (a) Ba,Li 0 (b) Be,Li 0
(a) one volume of oxygen 0 (c) Ba, Cs 0 (d) Ca, K 0
(b) half volume of oxygen 0 17. The compound CA) on heating gives a colourless gas. The
(e) 1.5 volume of oxygen 0 residue is dissolved in water to obtain (B). Excess of COz is
(d) two volumes of oxygen 0 bubbled through aqueous solution of (B), (C) is formed_ (C)
8. Which of the following is incorrect? . on gentle heating gives back (A). The compound (A) is :
(a) Hydrogen> Deuterium> Tritium (% relative abundance) (a) CaC03 0 (b) Na2C03 0
o (c) KZC03 0 (d) CaS04·2H20 0
(b) Hydrogen> Deuterium> Tritium (melting point) 0 18. An alkaline earth metal (M) gives an insoluble sulphate. The
(c) Hydrogen < Deuterium < Tritium (boiling point) 0 mixture of the sulphate and a sulphide of 3d-block metal
(d) Hydrogen < Deuterium < Tritium (dissociation energy) forms a white pigment which is known as lithophone. Metal
o (M) is:
9. Highly pure dilute solution of sodium in liquid ammonia: (a) Ca 0 (b) Mg 0
(a) shows blue colour 0 (c) Ba 0 (d) Sr 0
(b) exhibits electrical conductivity 0 19. The electrical conductivity of sodium dissolved in liquid NH3
(c) acts as a reducing agent 0 is due to:
(a) ammoniated Na+ions 0 (b) ammoniated electrons 0 ONE OR MORE THAN ONE CORRECT
(c) both (a) and (b) 0 (d) none of these 0 ANSWERS TYPE
20. Which of the following compounds is known as pearl ash?
31. Identify the correct statements :
(a) KMn04 0 (b) K2C03 0
(a) Mass of H-atom is 1.66 x 10-27 kg. 0
(c) KI '\ 0 (d) KOH 0
(b) Cu dissolves in H2S04 and liberates H2. 0
21: Slaked lime is obtained when water is added to :
(c) H2 is liberated by the action of Al with conc. NaOH. 0
·!
(a) CaSo4 H20 0 (b) CaCl2 0 (d) Hydrogen contains at room temperature 25% para and
(c) CaC0:3 0 (d) CaO 0 75% ortho form. 0
22. Which of the following is generally used for clearing snow 32. Identify the incorrect statements :
from roads during winters in cold countries? ' (a) The reactivity of hydrogen towards halogens is in the
(a) CaF2 0 (b) MgCl2 0 order Cl2 > Br2 > 12 > F2. 0
(c) SrCl2 0 . (d)CaQ2 0 (b) The oxides of hydrogen and deuterium are neutral. 0
23. The hydride gap refers to inability of : (c) Molecular hydrogen reduces ZnO and CuO to Zn and
(a) noble gases to form hydrides 0 Cu respectively. 0
(b) elements of group 7, 8 and 9 of the d-block to form (d) Atomic hydrogen reduces KMn04 to metallic
hydrides 0 manganese. o
(c) hydrogen to react with saturated. hydrocarbons 0 33. When chlorine· is passed thro.ugh NaOR.solutio!] u,, , n,.,de,, , -r_ __
(d) s-electrons of valency shell of p-block elements to parti- different dilutions, the main products formed are :
cipate in bonding 0 (a) NaCI,NaCIO 0 (b) NaCI,NaCI02 0
24. Hydride of certain non-metallic element 'X' is amphoteric in (c) NaCI,NaCI0 3 0 (d) NaCI,NaCI0 4 0
nature. The hydride of 'X' also reacts with calcium hydride 34. Which of tpe following metals do react with nitrogen when
(hydrolith) to liberate dihydrogen gas. The element 'X' is: heated in its atmosphere?
(a) nitrogen 0 (b) carbon 0 (a) Ca 0 (b) Mg o
(c) oxygen 0 (d) sulphur 0 (c) Ii 0 (d) K o
25. In which of the following reactions water does not act as 35. Which of the following nitrates give N02 on heating?
hydrolytic agent? (a) NaN03 0 (b) Ba(N03n 0
(a) CaC2+H20--7 0 (b) PBr3+H20--7 0 (c) KN03 0 (d) LiN~ 0
(c) Ca3P2+H20--7 0 (d) NH3 +H20--7 0 36. Which of the following statements about alkaline earth metals
26. Which elements. out of the following do not produce are correct?
hydrogen on treatment with caustic soda? (a) Hydration energy of Sr2+ is greater than that of Be2+.D
(1) Zn (2) Sn (3) Mg (4) Co (5) Al (b) CaC03 decomposes at a higher temperature than BaC0 3.
(a) (1) and (5) 0 (b) (3) and (4) 0 o
(c) (4) and (5) 0 (d) (2) and (4) 0 (c) Ba(OHh is stronger base than Mg(OHh. 0
27. Which of the following hydrides does conduct electricity? (d) SrS04 is less soluble in water than CaS04. D
(a) GeH2 0 (b) Sil4 0 37. In which of the following alloys Mg is present ?
(c) B2Ht; 0 (d) NaH 0 (a) . Electron D
28. Sodium oxide cannot be obtained by heating which of the (b) Magnalium D
. following? '(c) Duraluminium D
(a) NaOCI 0 (b) NaHC03 0 (d) Aluminium bronze D
(c) NaN~ 0 (d) all of these 0 38. K0 2 finds use in oxygen cylinders used for space and
29. Portland cement contains the following amount of CaO : submarines. The fact(s) related to such use of K0 2 is/are:
(a) 70-80% 0 (b) 20-35% 0 (a) it produces 02 D
(c) 50-60% 0 (d) 5-15% 0 . (b) it produces 0 3 D
30. Magnesium is obtained by : (c) it absorbs CO2 D
(a) electrolysis of fused MgCl2 0 (d) it absorbs N2 and CO2 both D
(b) reduction of MgCl2 with carbon 0 39. In comparison to alkaline earth metals, alkali metals are:
(c) electrolysis of aqueous solution of MgCl2 0 (a) more reactive D (b) less reducing D
(d) roasting of MgC03 0 (c) more soft 0 (d) more basic D
40. Select the wrong statement : MATRIX MATCHING QUESTIONS
(a) The formula of plaster of paris is CaS04·2H20. 0
(b) MgC03 is commonly used in making toothpaste. 0
Column-I Column-ll
(c) BeO is a basic oxide. 0
(d) Calcium fluoride is insoluble in water. 0 (a) ,Na202 (p) Oxitii,sing·
(b) K02 (q) Reducing
ASSERTION-REASON TYPE QUES1-IONS (c) CaH2 (r) Oxone
Each of the following questions contains statements of (d) UAlli4 (s) Alanate
Assertion (A) and Reason (R). Mark the correct answer according (t) Hydrolith
to the following code : 52. Match Column-l with Column-II:
(a) If both (A) and (R) are correct and (R) is the correct Column-I Column-ll
explanation of (A). (a) Sodium (p)
Laboratory reagent
(b) If both (A) and (R) are correct but (R) is not the correct (b) Sodium carbonate (q)
Washing soda
explanation of (A). (c) Potassium (r)
Photoelectric cell
(c) If (A) is correct but (R) is incorrect. (d) Caesium (s)
Nuclear reactor
(d) If both (A) and (R) are not correct. (t) Special thermometers to
41. (A) Hydrogen peroxide in the form of aqueous solution acts
measure high J~I!lpe!ature
as a bleaching agent-of delicate materials such as wool,
silk, cotton, hair, etc.
Column-I Column-ll
(R) H202 acts as a bleaching agent due to its oxidising nature.
(a) NaG (p) Sylvine
Coloured material + [0] ---? Colourless
(b) KG (q) Brine
42. (A) Normal hydrogen is a mixture of two forms: ortho 75%
(c) MgCl2 (r) Sorel's cement
and para 25%.
(d) CaCN2 + C (s) Rock salt
(R) Pure para-form can be obtained at low temperature but
(t) Fertilizer
pure ortho-form cannot be obtained.
43. (A) Lithium when heated in the atmosphere of nitrogen forms
lithium nitride while other alkali metals do not combine
LINKED COMPREHENSION TYPE
with nitrogen.
(R) Lithium is the most reactive alkali metal as its ionisation
Passage 1
potential is lowest amongst alkali metals. Lithium and beryllium, the first members of alkali metals and
44; (A) K2C03 like Na2C03 can be prepared by Solvay's process. alkaline earth metals respectively, show anomalous behaviour i.e.,
(R) K2C03 on heating decomposes giving carbon dioxide. differ from the rest of the members of their family. The main reasons
45. (A) Alkaline earth metals are harder than alkali metals. for their difference are :
(R) The metallic bonding is higher in alkaline earth metals as (i) exceptionally small atomic and ionic size
these possess two electrons in the valence shell. (li) high ionisation energy
46. (A) Chemical reduction methods are not applicable for the (iii) absence of d-orbitals in their valence shell
extractioJl of alkali and alkaline earth metats. (iv) high polarising power of the cations
(R) Alkali and alkaline earth metals are themselves strong Answer the following questions :
reducing agents. 54. Which of the following has the lowest melting point? .
47. (A) Magnesium and beryllium do not impart colour to flame. (a) LiCI (b) NaCI
(R) Both have high ionisation energies. (c) KG (d) RbCI
48. (A) Li+ has low mobility in aqueous solution. 55. Mg and Li are similar in their properties due to :
(R) Lithium ion has low tendency of hydration as its size is (a) same elm ratio (b) same electron affinity
small. (c) same group (d) same ionic potential
49. (A) H20 2 is a neutral compound. 56. Which of the following alkali metal ions has the minimum
(R) H20 2 is an ionic compound. ionic mobility in aqueous solution?
50. (A) Superoxides are formed by K, Rb and Cs. (a) Na+ (b) K+
(R) Superoxides are paramagnetic and coloured. (c) Li+ (d) Cs+
57. Be(OHhis: has greater value, the solubility is less. In case, hydration energy
(a) acidic (b) basic is more, then the compound is freely soluble in waler.
(6) amphoteric (d) neutral Answer the following questions :
58. Which is least thermally stable? 62. Compounds of alkaline earth metals are less soluble in water
(a) li2C03 (b) MgC03 in comparison to alkali metals. This is due to :
(c) BaC03 (d) BeC03 (a) their higher ionisation energies
(b) their high lattice energies
Passage :2 (c) their high hydration energies
Hydrogen gas has been considered as one of the alternate (d) their increased covalent nature
sources of energy. The advantage of using hydrogen as a fuel is 63. Which of the following is most soluble in water?
that it is environmentally clean. The second advantage with (a) MgS04 (b) Cas04
hydrogen is that the heat of combustion of hydrogen per gram is (c) srS04 (d) BaS04
higher than any other fuel. But, there are many problems in storing 64. BeF2 is soluble in water whereas fluorides of other alkaline
and transportation of hydrogen gas. earth metals are insoluble because of :
Answer the following questions : (a) ionic nature of BeF2
59. Which fuel does produce least environmental pollution? (b) covalent nature of BeF2
(a) Gasoline (b) Hydrogen (c) greater hydration energy of Be 2+ ion
(c) Wood Cd) Coal .. (d) .gr.e;!.ter.lattice. enrgyof Re~+jQn.
60. liquid H2 has been used as a rocket fuel because of :
(a) high thrust INTEGER ANSWER TYPE
(b) small space it occupies 65. How many alkali metals are known?
(c) its reaction with oxygen is highly exothermic 66. How many neutrons are present in tritium atom?
(d) all the above are correct 67. How many isotopes of hydrogen are known?
61. Which methods can be used to store hydrogen? 68. In water, each H 20 molecule is surrounded by ........ neigh-
(a) By absorbing hydrogen on activated carbon bouring H20 molecules randomly by hydrogen bonding.
(b) Reacting hydrogen with lithium to form liH 69. What is the degree of hardness of a sample of water
(c) The alloy, LaNis, has high capacity to take up hydrogen containing 10.8 mg of MgS04 (Mol. mass 120) per kg of
(d) All of the above water?
70. Of all the alkali metals, only sodium and potassium are found
Passage 3 in abundance in nature i.e., they are .... th and .... th most
The solubility of an ionic compound in water mainly depends abundant elements by weight in earth's crust.
on two factors. 71. How many water molecules are present as water of
(i) Lattice energy and (ii) hydration energy crystallisation in the molecule of gypsum?
Both these factors oppose each other and the resultant of these
guides the solubility of the compound in water. If lattice energy
1. (b) Both Ca and CaH2 on reaction with water evolve hydrogen gas. 5. (c) Smaller the ion, higher is degree of hydration i.e., high is
Ca + 2H20 ~ Ca(OHh + H2 hydration enthalpy. Thus, the hydration enthalpies decrease as
CaH2 + 2H20 ~ Ca(OHh + 2H2 the size of ion increases from Li+ to Cs+.
2. (d) 17 17
6. (b) % strength =: 56 x volume strength = 56 x 10 3.036
K2Cr20] + H 2S04 +4H202~ 2CrOs + K2S04 +5H 20
Chromium i.e., 30.36 gIL
peroxide(blue)
7. (d) H202+ 03~H20+202
3. (a) NaNH2
. Heal
+C~ NaCN + H2
i I vol 2 vol
4. (c) Alkali metals carbonates except Li2C03 do not decompose on 8. (b) Hydrogen < Deuterium < Tritium
13.90 K 18.50 K 20.60 K (melting point)
heating. The thermal stability of alkaline earth metals carbonates
increases from top to bottom. 9. (d)
Revision Exercise: 2 (Chapter 5to 7) '361
10. (a) KI + 12 ----4 KI3 (13) 28. (d) 2NaOCI ----4 2NaCI + Oz
11. (a) NaNHz + H20 ----4 Na+(aq.) + OH- + NH3 2NaHC0 3 ----4 Na2C03 + H20 + C02
2NaN0 3 ----4 2NaNO z + Oz
12. (b) M(HC0 .3 h +CaO----4 MC03+CaC03+HzO
~
29. (c) 30. (a)
Insoluble
31. (a, c, d)
MCl 2 + Na ZC0 3 ----4 MC0 3 + 2NaCI 32. (a. d) The reactivity of hydrogen towards halogens is in the order
Insoluble Soluble
F2 > Clz > Br2 > 12- Atomichydrogen reduces acidified KMn04
MS04 + NaZC03----4 MC03+ Na2S04 . to manganous salt.
Insoluble Soluble
33. (a, c) Cl2 +2NaOH ----4 NaCI + NaCIO+H 20
13. (c) 2NaHC0 3 ----4 NaZC03+ CO 2 + HzO Dilute
(X) (Y) .
3Cl2 +6NaOH----4 5NaCI+NaCI03 +3H zO
Na2C03 + HzO + C02 ----4 2NaHC03 34. (a, b, c) 3Ca + N2 ---+ Ca3N2
(~ (Y) .
3Mg + N2 ---+ . Mg3N2
14. (d) BeS04 is soluble in water. BeO becomes inert on heating. 6Li + N2 ---+ 2Li3N
1
Be(OHh is insoluble and reacts with NaOH. Jbe product is 35. (b. d) Ba(N03h ---+ BaO + 2NOz + 2' O2
soluble in water.
2LiN03 ---+ Li 20 + 2N0 2 + ~ 02
Be(OHh +2NaOH----4 NazBe02+2HzO
Soluble 36. (c, d) 37. (a. b, c) 38. (a, c) 39. (a, c, d)
15. (b) Ionic mobility depends on the size of ion. The ionic size in 40. (a, c) The formula of plaster of paris is CaS04' ~ H 20.
case of hydrated cation is K;q < Na;q < Li;q . BeO is an amphoteric oxide.
41. (a) 42. (b) 43. (c) 44. (d) 45. (a) 46. (a) 47. (a)
16. (a) The maximum value of oxidation potential of lithium makes it
strongest reducing agent amongst alkali metals.
48. (c) 49. (d) 50. (b)
51. (a-p, r); (b-p); (c-q, t); (d-q, s)
The values of oxidation potentials increase from top to bottom
in lIA group. Thus, Ba is a strong oxidising agent.
52. (a-p, s, t); (b--p, q); (c-r, t); (d-r)
53. (a-q, s); (b-p, t); (c-r); (d-t)
·17.
(A) 1
(a) CaC03----4 CaO + COz
H 20
Colourles&
gas
54. (a) Due to high polarising power of Lt ion, LiCl shows somewhat
55. (d)
covalent nature.
Heat
CO 2 ----4 Ca(OH)z----4 Ca(HC03h ----.?CaC03 56.. (c) Li+ ion being smallest in size has high degree of hydration.
(8) (e) (Al
57. (c) Be(OH)z combines both with acid ,and alkali.
18. (c) (BaS04 + ZnS) is a white pigment known as lithophone. 58. (d) 59. (b) 60. (d) 61. (d)
19. (c) Na + (x + y) NH3 ----4 Na+(NH 3)x + e-1(NH3)Y
62. (b) The cations have small ionic size and double the charge in
20. (b)
comparison to alkali metal ions. Therefore, their lattice energies
21. (d) CaO + HzO ----4 Ca(OHh are high.
Slaked lime
63. (a) 64. (c) 65. (6) 66.(2) 67. (3) 68. (4)
22. (d) 23. (b) 69. (9) 10.8 mg of MgS04 is present in 103 g of water.
24. (c) 'X' is oxygen. H 20 is amphoteric. Thus, 106 g of water contains· 10800 mg of MgS04
CaH2 + 2H20 ----4 Ca(OHh + 2H2 "" 10.8 g of MgS04
25. (d) Water acts as a proton donor when it reacts with NH3. 120 g MgS04 == 100 g of CaC0 3
26. (b) '100
So, 10.8 gofMgS04 = 120 x 10.8= 9g CaC03
27. (d) NaH is an ionic hydride. In molten state, it conducts electricity.
Hardness of water 9 ppm=
70. (7 and 8)
71. (2)
Group
8
iliA or 13
5
B
Boron ';,
'bbpl CHAPTER
All
Aluminium
352 Sp1
31
Ga
Gallium
4s24pl
49
Elements of Group IlIA or 13
In
Indium
5s 2 5pl The Boron Family (ns2np l)
81
TI
Thallium
(Boron andAluminium)
681lpl
IU~tl
81~~
i Ununtrium ,
! ,7s 27pl I ~~, :.<~il
GENERAL CHARACTERISTICS OF
GROUP iliA OR 13 ELEMENTS
Contents IHA IVA
Group IlIA or 13 of the long fonn of the periodic table consists
8.l General Characteristics of 13 14
Group IIlA or 13 Elements of six elements-boron, aluminium, gallium, indium, thallium
B C
8,2 Abnormal Behaviour of 2 and ununtrium. These are p-block elements as the last
(5) (6)
Boron differentiating electron enters np orbital. The configuration of
8,3 Comparison of Boron and 3
Al
(13)
Si
(14)
the outennost energy shell is ns2 npl, i.e., this group marks
Aluminium the beginning of the p-block elements. Since the members of
8.4 Diagonal Relationship of Ga Ge
4 (31) (32)
this group possess three electrons in the outennost or in their
Boron and Silicon valency shell, they have many similarities in their properties.
8.S Boron In Sn
5 (49) (50)
However, the penultimate shell (next to tl)e outennost) contains
8.6 Compounds of Boron i-grouping in boron, s2p 6 (8 electrons) in aluminium and
8.7 Aluminium Tl Pb
6 (81) (82) s2p 6io (18 electrons) in other elements (Ga, In, Tl and Uut).
8.8 Compounds of Aluminium This shows why boron differs from aluminium and both boron
8.9 Goldschmidt's Alurnino- Uuq
7 and aluminium having noble gas kernel differ from other four
Thermic Process (114)
elements. The electronic configuration of these elements is
given below:
Element I At. No. Electronic configuration Inert gas core

B 5 2,3 Ii, 2i 2p' [He] 2i2p'
Al 13 2,8,3 Ii, 2i 2p6, 3i 3pl [Ne] 3i3pl
lO
Ga 31 2, 8, 18, 3 Ii, 2i 2p6, 3i 3p6 3d , 4i 4pl [Ar] 3d lO , 4i 4pl
In 49 2, 8, 18, 18, 3 Ii, 2s2 2p6, 3i 3p6 3d lO, 4i 4p6 4d lO , 5i 5p' [Kr] 4d lO , 5i 5pl
T1 81 2, 8, 18, 32, 18, 3 182, 2i 2p6, 3i 3p6 3d iO
, 4i 4i 4d iO
4114, 5i 5p6 5d lO
, 6i 6pl [Xe] 4/,4, 5d lO , 6i6p'
Uut 113 2, 8, 18, 32, 32, 18, 3 Ii, 2i 2p6, 3i 3p63dlO, 4i 4p6 4dlO 4/,4, 5i 5l 5dlO 5/,4, [Rn] 5/,4, 6d lO , 7i 7pl
lO
6i 6p6 6d , 7i 7pl
EJlements of Group lIlA or 13 (Boron and Aluminium) 363
The members of this group are less metallic in comparison Group 2 3

df
to elements IA (alkali metals) and ITA (alkaline earth metals) Ii > Be > B
groups. Bordn is regarded as a semi-metal: It is closer to non- (152 pm) (112 pm) (85 pm)
metals than metals in its properties. Aluminium and rest of the Na > Mg > Al
elements are metallic in nature. General characteristiCs of these (186 pm) (160 pm) (143 pm)
elements* are discussed below : This is due to the fact that effective nuclear charge increases
1. Abundance and occurrence: Aluminium is the most
and electrons are pulled inwards resulting in a decrease in
abundant metal and third most abundant element (after oxygen atomic size.
and silicon) by mass in the earth's crust. The most important
In isoelectronic species, thejonic size decreases with increase
ore of aluminium is bauxite. Boron is fairly rare element but it
in atomic number, i.e., ve ratio.
is well known because it occurs as concentrated deposits of
borax, kemite and tourmaline crystal.. Gallium is twice as Na+ > ' Mg2+ > AI 3+
abundant as boron, but indium and thallium are much less (102 pm) (72 pm) (53.5 pm)
common. All the three elements (Ga, In and TI) occur as 3. Density: Density increases from boron to thallium.
sulphides in traces in zinc and lead sulphide ores. However, boron and aluminium have comparatively low values.
2. Atomic and ionic radius: The atomic radius increases This is due to their lower atomic masses as compared to
from boron to thallium. Ionic radius (M 3+) also increases. gallium, indium and thallium.
However, gallium has an abnormal value of atomic radius,
Element B AI Ga In Tl
which is lower than that of aluminium. Density (g mL-1) 2.4 2.7 5.9 7.3 11.9
B AI Ga In TI 4. Melting and boiling points: The elements of this
Atomic radius (pm) 85 143 135 167 170
group do not show a regular change in their melting points
(Metallic)
Ionic radius M3+ (pm) 27 53.5 62 80.0 88.5 with)ncrease in atomic number. The melting point decreases
from B to Ga and then increases.
[There is no evidence for the existence of B3+ and the value
Element B Al Ga In TI
of ionic radius is an estimate.] Melting point (0C) 2300 660 30 157 303
The sharp increase of atomic radius, of Al is due to greater Boiling point (0C) 2550 2450 2240 2050 1470
screening effect in aluminium due to the presence of eight
The high melting point of boron is due to the fact that it
electrons in the penultimate shell than in boron which has.two
exists as a giant covalent polymer in both solid and liquid state.
electrons in the penultimate shell. Thus, outermost electrons in
The elements AI, In and TI all have close-packed metal structures.
boron experience greater nuclear attraction than in aluminium
Gallium has an unusual structure. It consists of only Gaz
resulting thereby smaller atomic radii in boron in comparison
molecules. It has, thus, low melting po~nt. It exists as liquid up
to aluminium.
to'2000°C and hence used in high temperature thermometry.
Ga, In and TI follow after a row of ten transition elements.
However, the boiling points of the elements of IlIA group
Thus, there are ten d electrons in the penultimate shell which
follow a regular decrease from boron to thallium. This shows
are less efficient in shielding the nuclear charge and outer
that the strength of the bonds holding the atoms in liquid state
electrons are firmly held by nucleus. Thus, atoms with a JO
decreases from boron to thallium.
inner shell are smaller than would otherwise be expected.
5. Ionisation energy or ionisation enthalpies: The follo-
The large difference in size between B and Al results in
wing trends are observed:
many differences in properties.
(i) The first ionisation energies of group 13 elements are
The smaller value of gallium in comparison to aluminium is
lower than the corresponding elements of group 2, i.e., alkaline
due to the fact that in going from Al to Ga the penultimate
earth metals in the same period. However, second ionisation
d-orbitals are filled in the first d-block series from Sc(2l) to
energies of group 13 elements are higher in comparison to
Zn (30). The d-electrons do not screen the nuclear charge in
corresponding alkaline earth metals.
an effective manner and therefore, the electrons in the outermost
(ii) On moving down the group from boron to thallium, a
shell of gallium experience more force of attraction towards
regular decreasing trend (expected) in the ionisation energy
nucleus than aluminium, causing thereby decrease in atomic
values is not observed. The ionisation energy decreases from
radius.
B to AI, increases in Ga and again decreases in In. The value
The atomic and ionic radii of group 13 elements are smaller
of ionisation energy of TI is higher than In.
than the corresponding elements of group 1 and 2 in the same
period. • (iii) The second and third ionisation energies for the elements
are successively higher.
*~allium, i.s kn?wn as DuckbUl P~typ~ as it shows s~milarities with many other elements. Ununtrium, the'last member of this group, is a
synthetic and radIoactive element. Very little IS known about Its characteristics.
The values of first, second and third ionisation energy 6. Electropositive or metallic character: The elements
of group 13 elements are tabulated below: of group 13 are less electropositive as compared to the elements
of groups 1 and 2 (s-block elements). This is due to their small
Ionisation energy (kJ mol-I)
Element size and high ionisation energy.
1st 2nd 3rd Sum of three The electropositive character increases from boron to
B 801 2427 3659 6887 aluminium and then decreases from aluminium to thallium.
Al 577 1816 2744 5137 Boron having very high ionisation energy is regarded as a
Ga 579 1979 2962 5520 semimetal. It is more closer to non-metals. Aluminium is a
In 558 1820 2704 5082 metal and is most electropositive. The increase in electropositive
nature from B to Al is due to increased atomic siZe. The remaining
Tl 589 1971 2877 5437
three elements Ga, In and Tl are less electropositive and less
The elements of group 13 have ns2npl_grouping in the metallic than aluminium and there is decrease from Ga to Tl.
outermost energy shell. For the first ionisation energy, the The presence of dlO -electrons in the penultimate shell in gallium
electron has to be removed from the p-orbital in case of group and indium and d lo and /4
-electrons in the inner shells of
13 elements while in alkaline earth metals (ni), the s-electron thallium do not shield the nuclear charge effectively and
of the same energy shell has to be removed. Since, s-electron therefore, these elements are less electropositive. Boron is a
is nearer to nucleus in comparison to p-electron, it is more bad conductor while aluminium is a very good conductor of
firmly held than p-electron due to strong attractive force. Hence, electricity. Gallium, indium and thallium also conduct
the removal of p-electron is easier and, therefore, the first electricity.
ionisation energy values of group 13 elements are lower than 7. Oxidation potential (Reducing nature): Boron does
the corresponding alkaline earth metals. not form positive ions in aqueous solution and thus has low
Be > B > Mg > Al value of oxidation potential. The oxidation potential values of
899 kJ mol- I 801 kJ mol- 1 737 kJ mol- 1 577 kJ mol- 1 other elements of the group are quite high. This is due to high
Ca > Ga heats of hydration on account of small size of trivalent cations
3
590 kJ mol- 1 579 kJ mol- 1 (M +). [Aluminium is a strong reducing agent and in fact
After the removal of p-electron, the elements of group 13 better than carbon. This is due to low ionisation energy of
acquire ns2 -configuration while alkaline earth metals acquire aluminium than carbon.]
. ns I -conifi guratlOn.
. I · to remove e Iectrons firom ns I In
t IS·easIer . 8. Oxidation states: It is in group 13 that we first
2
comparison to ns in the same energy shell. Hence, the second encounter elements possessing more than one oxidation state.
l
ionisation energy values of group 13 elements are higher than As i p grouping is present in the outermost energy shell of the
the corresponding alkaline earth metals. elements of the group IlIA, the expected oxidation states are
The first ionisation energy of boron is highest in the group +3 and + 1. Boron shows +3 oxidation state in all its compounds.
since, its size is smaltest and screening effect is lowest. The Other members show +3 and + 1 oxidation states. The stability
sharp decrease from B to Al is due to appreciable increase in of + 1 oxidation state increases from aluminium to thallium and
atomic.size and the screening effect of sand p-electrons of the the stability of +3 oxidation state decreases from aluminium to
penultimate energy shell. In case ofGa, there are ten d-electrons thallium, i.e., +3 is more important oxidation state for Al, Ga
in the penultimate energy shell which screen the nuclear charge and In whereas + 1 oxidation state is more important for T1.
less effectively and, thus, the outer electron is held firmly by Relative stability of M+ and M 3+ ions may be give as :
the nucleus. As a result, the ionisation energy remains nearly B3+ > Al 3+ > Ga3+ > In3+ > T1 3+
the same as that of aluminium. In case of In, the number of B+ < Al+ < Ga+ < In+ <Tl+
d-electrons and their shielding effect remain the same as in Tl+ ions are more stable than 113+ ions and thus, T13+ ions
gallium. The ionisation energy, however, decreases in indium change to Tl+ ions thereby acting as oxidising agents.
due to increase in atomic size from Ga to In. The increase in T13+ compounds + 2e ~ Tl+ compounds
ionisation energy from In to Tl is due to poor screening effect (Less stable oxidising agent) (More stable reducing agent)
of 14f-electrons present in the inner energy shell. [Tl(1) compounds resemble alkali metal compounds. Tl(OH)
After the loss of first electron, the effective nuclear charge
like NaOH is soluble in water and the solution is strongly
increases with the result that decrease in ionic size occurs and
alkaline. Like alkali metals, Tl 2S04 forms a double sulphate
thus, more and more energies are required for the removal of
with Al2(S04h
second, third and subsequent electrons.
K2S04·AI2(S04h·24H20; TI 2S04·AI2(S04h·24H 20
lEI < lEn < IEm < IE IV Tl2C03 like Na2C03 is soluble in water.]
Since, the sum of first, second and third successive ionisation In case of Ga and In, +3 oxidation is more stable than + I
energies of the elements of this group is very high, these oxidation state. The salts of both Ga+ and In+ undergo dis-
elements have little tendency to form trivalent ions. proportionation reactions in aqueous solutions.
Elements of Group rnA or 13 (Boron and Aluminium) 365
+1 0 +3 (i) Back-bonding: In BX3 , B is sp2 hybridised i.e., it has
3GaX ~ 2Ga + GaX3 one p-orbital vacant. X-atom has fJlled p-orbital. They overlap
3InX ~ 2In + InX3 resulting into 1t-bonding.
The decreasing stability of +3 is due to increase in inert
III
F
pair effect.
II
Gallium appears to show +2 oxidation state in GaCI 2. -B - - Resonance
F/""F F/""F
However, it is believed that this compound has the structure
Ga[GaCI4] which contains univalent and trivalent gallium ions.
Ga[GaCI ] = Ga+[Ga3+CI
4 4 r (U) Coordination with Lewis bases : B has vacant
p~orbital which accepts electron pair from donor.
9. Nature of bonding : The following points suggest that
For example, BF3 + IT ~ BF4
bonding in the compounds of group IIIA elements should be
Al(OHh + OH- ~ Al(OH)4
covalent.
(a) Small size of ions and their high charge are responsible (iii) Polymerization: Some compounds remove electron
for high polarisation. deficiency by dimerization.
(b) The sum of first three ionisation energies is very large. For example, 2Al03 ~ Al 2Cl6 .
(c) The electronegativity values are higher and thus, when Note: In aluminium compounds back bonding is not possible due to
reacting with other elements the difference is not large. following reasons;
(a) p-orbital of A1 is large, so Pcp overlap is not effective.
Boron is considerably smaller dian other members and its (b) 8-electron core in Al causes -larger repulsion, thus destabi-
ionisation potential is maximum' and hence it always shows Jising back bonding.
covalency. Many simple compounds of the other elements
10. Complex formation: Group IlIA elements form
such as AlCl3 and GaCl3 are covalent when anhydrous. However,
complexes much more readily than the s-block elements,
AI, Ga, In and Tl all form metal ions in solution. The change
.because of their smaller size, increased charge and availability
from covalent to ionic occurs because the ions are highly
of vacant orbitals.
hydrated and the amount of hydration energy evolved exceeds
11. Reactivity towards air: Boron exists in two forms
the ionisation energy. For example, AICl 3 releases 5808 kJ
(a) crystalline and (b) amorphous. Boron is unreactive towards
mor l of hydration energy which exceeds the ionisation energy
air in crystalline state. Amorphous boron on heating in air form
(Al -7 A1 3+ :::; 5137 kJ mol-I), so AlCl3 ionises. The hydrated
boron trioxide. At high temperatures, it also combines with
aluminium compounds which are regarded as ionic do not
nitrogen.
contain the aluminium ion, Al3+, as such but the hexa-
aquaaluminium ion, IAl(H20)6]3+. The relative stability of 4B + 302 700'C ) 2B 20 3
[M(H20)6]3+ ions decreases on moving down the group.
2B + N2 High temp. ) 2BN
Thallium compounds are ionic. Monovalfmcy of thallium is due
to increasing reluctance of the paired ns electrons to form Aluminium is not affected by dry air. However, a thin oxide
bonds: [Such inertness of ns electrons is observed when the layer* is formed on the surf;;tce of aluminium metal in moist air.
electrons are in fifth or higher energy shell and their removal It protects the metal from further attack. It also forms nitride
does not form a cation whose electroni.c configuration is that with nitrogen at high temperatures.
of an inert gas. This behaviour is termed as inert pair effect.]
4A1 + 302 Heat) 2Al20 3
In trivalent state, the number of electrons around the central
atom in a molecule such as BCI3, BF3, AICI 3, etc., will be only 2AI + N2 High temp. ) 2AIN
six and thus behave as electron deficient molecules. They
Gallium and indium are not affected by air. Thallium forms
act as Lewis acids.
an oxide layer on its surface. Thallium is preserved under oil
Cl3B + : NH3 ~ Cl3B ~ NH3 or by smearing with vaseline.
Base
12. Reactivity towards water: Boron is not affected by
However, Lewis acid character decreases down the group water or steam, however, steam reacts at red heat. Aluminium
as the atomic size increases. decomposes cold water if the oxide layer is not present on its
The electron deficient compounds remove -their electron surface.
deficiency by : 2B + 3H20 ~ B20 3 + 3H2
2AI + 3H20 -'---7 A1 20 3 + 3H2
*The oxide film on the surface of aluminium is so useful that in industry it is purposely increased by an electrolytic process called anodising.
Anodised cooking vessels are used now as non-stick cookware.
The tendency of accepting electron pair is also observed in (ii) Boron has maximum covalency of four due to nonavail-
the halides of aluminium and other members (act as Lewis ability of d-orbitals while the rest have maximum covalency of
acids). However, this tendency decreases with the increase in six.
size of the cation. They form complex halides of the type (iii) Boron alone exhibits allotropy.
[MX6 ]3- where the M-atom extends its coordination numher (iv) Boron shows +3 oxidation state while others can show
to 6 by the use of d-orbitals. These halides do not show back + 1 and +3 oxidation states.
bonding due to increase in the size of the element. However, (v) Boron does not form cations in aqueous solution as the
they make use of vacant p-orbital by coordinate bond, i.e., hydration energy is less than sum of three successive ionisation
complete their octet by forming dimers. energies.
(vi) Boron halides are mONomeric while the halides of the
CI)AI /Cl + ' 'AI<'CI, ---? Cl)
'AI <Cl> , <CI
' AI, other elements are dimeric. It does not show inert pair effect.
CI' n/ CI Cl ' ' CI '. ' CI (vii) Boron forms a number of volatile hydrides which are
electron deficient compounds. Others form only one polymeric
Dimer forms exist in vapour state and in non-polar solvents.
hydride. Thallium does not form hydride.
Dimer structure disappears when the halides are dissolved in
(viii) Boron does not decompose water or steam while Qther
water. This is due to high hydration energy when [M(H 20)6]3+
elements decompose hot water or steam.
and 3X- ions are formed making the solution as good conductor
(ix) The oxide of boron, B203, is acidjc in nature while the
of electricity.
similar oxides of the other elements are either amphoteric or
The solution hecomes acidic owing to hydrolysis.
basic.
AICl3 + 9H20 ---7 [AI(H20)6](OHh + 3H+ + 3CI- (x) Boron is not attacked by non-oxidising acids while other
In addition to trihalides, these elements form di as well as elements are attacked.
monohalides. Boron forms dihalides, B2X4. (xi) Boron dissolves in conc. RN0 3 forming H 3B03. The
X"
X/
B-B /x
""X
other elements become passive specially Al and Ga.
(xii) Boron combines with metals and form borides while
other elements do not combine. They can form alloys.
In solid state, B2X4 has planar structure but in liquid and
8.~tI COMPARISON OF BORON AND
vapour state, it has non-eclipsed stru<;::ture.
j~ ALUMINIUM
CI) <CI CI) <CI Since both boron and aluminium have three electrons in their
B-B B-B
CI CI CI CI valency shell, they have many similarities in their properties.
(Planar molecule) (Non-eclipsed
B 5 2, 3 Is2, 2~2 2pl . [He] 2i 2pl
structure)
Al 13 2, 8, 3 Is2, 2i 2l, 3i 3pl [Ne] 3i 3pl
Tetrqhalides can be synthesised by heating trihalides with
mercury at low pressure. On the other hand, they have different number of electrons
in their penultimate shell (2 in boron and 8 in: aluminium) and
2BCl3 + consequently show many dissimilarities also;
Gallium and indium also form dihalides. Gallium dihalide is' iii Points of Similarities
more properly represented as Ga+[GaCI4r showing gallium in
(i) Electronic configuration: Both have same number
+1 and +3 oxidation states.
The elements Of IlIA in gaseous state form monohalides, of electrons in the outermost shell (valency shell).
(ii) Valency: Both show trivalency.. They do not show
MX. These are, very unstable halides and they are covalent in
nature. The covalent nature decreases and thallium halides are variable valency because their kernels are stable. It is difficult
to get B3+ because large amount of en~rgy is required and
ionic in nature.
therefore boron forms tri-covalent compounds. Aluminium also
8.ai ABNORMAL BEHAVIOUR OF BORON forms covalent compounds. It can, however, form electrovalent
~X:!i
compounds when it combines with strong electron accepting
Boron differs markedly from the rest of the members of group atoms or groups. The size of AI 3+ ion is very small. On account
IlIA and this abnormal behaviour is illustrated in the following of small size and high charge, it has high polarising power.
properties : This accounts for a covalent character even in the case of
(i) Boron has very small atomic radii, hence greater nuclear electrovalent compounds, for example, AICI3, AIBr3 and AlI3
attraction on the outermost electrons. It has very high ionisation have covalent nature.
energy. This gives boron distinctly nonmetallic character while (iii) Oxidation state: Both show common oxidation state
the rest are metals. of +3 in majority of their compounds.
Elements of Group IDA or 13 (Boron and Aluminium) 369
Compound Oxid. state Compound Oxid. state Trichlorides are hydrolysed by water, i.e., both show
B2 0 3 +3 Al 20 3 +3 covalent nature.
BCl3 +3 Alel 3 +3 BCl3 + 3H20 -----7 H3B03 + 3HCI
H 3B03 +3 Al(OH}J +3 AlCl3 + 3H20 -----7 AI(OHh + 3HCI
Na2B407 +3 NaAlO 2 +3 Halides act as Lewis acids whenever donor molecules (Lewis
Boron, however, also shows an oxidation state of -3 in the bases) are available.
metal borides, e.g., in Mg3B2 (magnesium boride), oxidation H3N -----7 BCI3, H3N ~ AICl 3
state of boron is -3. (viii) Formation of nitrides; Both form nitrides of the
(iv) Action of alkalies: Both dissolve in alkalies and type MN when heated in the atmosphere of nitrogen or ammonia.
evolve hydrogen. 2B + N2 -----7 2BN i
2B + 2NH3 -----7 2BN + 3H2
2B + 6NaOH -----7 2Na3B03 + 3H2 2AI + N2 -----7 2AlN
Sodium borate
2AI + 2NH3 -----7 2A1N + 3H2
2Al + 2NaOU + 2H 20 -----7 2NaAI02 + 3H 2 . The nitrides undergo hydrolysis with steam.
Sodium meta
aluminate BN + 3H20 -----7 H3B03 + NH3
Boric acid
(v) Action of concentrated H2S04: Both react with
conc. H2S04 and evolve sulphur dioxide, S02' AlN + 3H 20 -----7 Al(OHh'+ NH3 .. ' !--
Aluminium
[H2S04 -----7 H 20+S02 +0]x3 hydroxide
2B +.30 -----7 B20 3 (ix) Formation of sulphides: Both form sulphides ,of
B203 + 3H20 -----7 2H 3B03 the type M2S3 when heated with sulphur. '.
2B + 3H2S04 -----7 2H 3B0 3 + 3S0 2 2B + 3S -----7 B2S3
2AI + 3S -----7 AlzS 3
6H2S0 4 +2AI -----7 A12(S04h +3S02 +6H20
Sulphides are hydrolysed with water.
(vi) Formation of oxides: Both form oxides of the type
B2S3 + 6H20 -----7 2H3B03 + 3H2S
M203 when heated in atmosphere of oxygen at high
Al2S3 + 6H20 -----7 2Al(OHh + 3H2S
temperature. . I
(x) Formation of alkyl compounds: Both form similar
4B + 30 2 7oo·e) 2B 20 3 (Boron oxide or boric anhydride) types of alkyl compounds, such as B(CH3h Al(CH3h· t
4AI+302 800ne) 2Al203 (Aluminium oxide or alumina) 2BCl 3 + 3Zn(CH3h -----7 2B(CH3h + 3ZnCl2
2Al + 3Hg(CH3)2 -----7 2AI(CH3)3 + 3Hg
The oxides are amphoteric in nature. B20 3 is more acidic
and less basic while Al203 is more basic and less acidic. (xi) Reducing nature: Both act as powerful reduC.(ing
agents.
B20 3 + 6NaOH -----7 2Na3B03 + 3H20
4B + 3C02 -----7 2B203 + 3C
Al203 + 6HCI -----7 2AICl3 + 3H20
3Si02 + 4B -----7 2B 20 3 + 3Si
Al20 3 + 2NaOH -----7 2NaAl02 + H20
2Al + Cr203 -----7 Al 20 3.+ 2Cr
(vii) Formation of chlorides: Both form trichlorides either
2Al + Fe203 -----7 Al20 3 + 2Fe
by passing chlorine over heated boron or aluminium or by 4AI + 3C02 -----7 2Al203 +.3C
passing chlorine over heated mixture of their oxides and
(xii) Action of steam: Boron reacts with steam at red
charcoal.
heat liberating hydrogen.
2B + 3Cl2 -----7 2BCl3
2AI + 3Cl2 -----7 2AlC13 2B + 3H20 -----7 B20 3 + 3H2
B203 + 3C + 3Cl2 -----7 2BCl3 + 3CO Aluminium decomposes boiling water.
Al203 + 3C + 3Cl2 -----7 2AlCl3 + 3CO 2Al + 6H20 -----7 2AI(OHh + 3H2
Dissimilarities between Boron and Aluminium
Boron and aluminium show dissimilarities in properties due to difference in their electronic configuration, size and ionisat;ion
potential. Main points of difference are given in the table. ./'
Boron Aluminium
(i) Boron is a non-metal. Aluminium is a metal.
(ii) It is a bad conductor of heat and electricity. It is a good conductor of heat and electricity.
(iii)
(iv)
It has high melting point (m.pt. 2300"C).
Boron shows allotropy. The allotropic fonns are crystalline boron
It has low melting point (m.pt. 660"C). •I.,
•
Aluminium does not show allotropy.

. and amorphous boron.
(v) It does not react with dB. HCI and dil. H2S04, It dissolves in HC) and H2S0 4 (dil.) evolving hydrogen.
2A1 + 3R 2S0 4 ~ AI 2(S04h + 3H2
(vi) It is attacked by cone. RN0 3. It becomes passive with cone. RN03' A thin layer of AIl 03 is formed
l2HN03 ~ H20+2N02 +Olx3 on the surface which makes the metal inert.
or B + 3RN0 3 ~ R3B03 + 3N0 2

(vii) Borates are very stable. Aluminates are less stable.
(viii) BCI3 is a fuming liquid. AICI 3 is a solid.
(ix) It combines with metals. The compounds formed are called borides. It forms alloys with metals.
3Mg + 2B ~ Mg3B2
(x) B(OHh is a weak acid. AI(OHh is amphoteric in nature.
(xi) The maximum covalency of boron is four and is shown in Aluminium has a maximum covalency of six which is shown in
compounds like potassium f1uoroborate, K[BF4l compounds like Na3[AlF6]. This is due to the involvement of
d-orbitals of the valency shell.
(xii) Boron forms a number of hydrides like B2H6, B4H 10, B IO H14, It does not form any stable and definite hydride. A polymeric hydride
etc. These are covalent and electron deficient in nature. (AlH 3 ).. has been reported.
(xiii) Boroiltnhalides exist' as
discrete molecules, i.e., monomeric in Aluminium trihaI1des Ti1<e'AIcI3',AiBr) exist as dimers~both in vapour
nature, BX3. state and in non-polar solvents as shown below.
C l > /CI~ <Cl

Al~ /Al
C) "cl CI
(xiv) It fonTIs covalent compounds only. It forms both covalent and electrovalent compounds.
(xv) It forms a covalent carbide, It forms an ionic carbide, A1 4C3, which on hydrolysis evolves C~.
8.4"] DIAGONAL RELATIONSHIP OF 2B + 3Mg ~ Mg3B2

BORON AND SILICON Si + 2Mg ~ Mg 2Si
(viii) Both do not directly combine with hydrogen. However,
Following are the properties where boron and silicon show
both form a number of hydrides. Hydrides are formed by
close resemblance :
almost identical manner. All are covalent hydrides.
(i) Bo~h boron and silicon are non-metals. Both have high
melting ,points [B = 23 ()()OC; Si = 141 O°C], high ionisation Mg3B2 --===-7 a mixture of boron hydrides
energies (B 8.3 eV, Si = 8.20 eV) and are bad conductors of Mg2Si Di!.HC1) a mixture of silicon hydrides
electricity at normal temperature. However, the conductance
4BCl 3 + 3LiAlH4 ~ 3LiCI + 3AICl3 + 2B2H6
improves as the temperature increases. Hence, both are
SiCl4 + LiAlH4 ~ LiCI + AICI 3 + SiH4
semiconductors.
[Note : Boron hydrides (boranes) are electron deficient while silicon
(ii) Both have nearly equal densities, electronegativities hydrides (silanes) are saturated compounds.]
[Density B = 3.30 g mL-!; Si = 3.52 g mL-!; Electronegativity
(ix) Orthoboric acid (H 3B03) and ortho silicic acid (H4Si04)
B = 2.0; Al 1.8]
form esters when treated with alcohols in presence of H2S04,
(iii) Both boron and silicon show allotropy.
(iv) Both boron and silicon do not form cations as their
ionisation energy is very high. Triethy! borate
(v) Most of the compounds of boron and silicon are H4Si04 + 4C2HsOH 2
H S0
4
) (C2Hs)4Si04 + 4H20
covalent. Tetraethyl silicate
(vi) Boron and silicon burn in air on heating fonning stable [Note: The vapours of triethyl borate bum with green edged flame. This
oxides B20 3 and Si0 2 respectively. The oxides are acidic and is the qualitative test of borates.]
combine with alkalies forming borates and silicates respectively. (x) Halides of boron and silicon are hydrolysed.
B10 3 + 2NaOH ~ 2NaB02 + H20 BCl 3 + 3H 20 ~ H 3B0 3 + 3HCl
or B:P~ + 6NaOH ~ 2Na)B03 + 3H20 SiCl 4 + 4H 20 ~ H4Si04 + 4HCI
Si02 + 2NaOH ~ Na2Si03 + H20 Both form complex halides.
(vii) Both boron and silicon combine with metals to form
BF3 + HF ~ H[BF4]
borides and. silicides respectively.
SiF4 + 2HF ~ H 2[SiF6]
Elements of Group IlIA or 13 (Boron and Aluminium) 371
(xi) Both react with fused alkalies and evolve hydrogen. The fused mass is extracted with hot water. CaC0 3 remains
2B + 6NaOH ~ 2Na3B03 + 3H 2 i as insoluble. The filtrate containing borax and sodium
Si + 2NaOH + H20 ~ Na2Si03 + 2H2 i metaborate is put to crystallisation when borax is obtained.
The remaining solution is treated with carbon dioxide which
(xii) Both combine with carbon to form carbides B4C and converts sodium metaborate into borax.
SiC. These are very hard substances and are used for cutting
and abrasing purposes. 4NaB02 + CO 2 ~ Na2B407 + Na2C03
The borax is then converted into B20 3 in the manner
8 BORON described above.
(ii) The other method of conversion of colernanite into
Occurrence: Boron is not found free in nature. In the B20 3 involves the suspension of mineral in water and passing
c~mbined state, it is found as the salts of boric acid. The of sulphur dioxide gas into the suspension.
important minerals of boron are :
Ca2B6011 + 4S02 + 4H 20 ~ 2Ca(HS03)2 + H4B60 11
(i) Borax (Tineal) Na2B40T lOH20-It is found in Tibet, Ceylon,
~B6011 + 7H 20 ~ 6H3B03
California arid Kashmir.
(ii) Colemanite Ca2B601l·5H20-It is found in Asia Minor Ca2B60U + llH20 + 4S02 ---7 2Ca(HS0 3)z + 6H3B03
and America .. On concentration and cooling, crystals of boric acid separate
Panderinite Ca2B6011·3H20 out. These crystals form B20 3 on strong heating.
(iii) Boracite 2Mg3B8015'MgCl2~It is found in Stass-furt,
Germany.
2H 3B0 3 ---7 B20 3 + 3HzO
(iv) Boronatro calcite CaB4~·NaB02·8H20~It is found in Chile.
(v) Kernite (Rasorite) Na2B40T4H20-It is found in Mojave desert '::' 2nd Step
in America. Reduction of 8203: The reduction of boric anhydride
(vi) Boric acid H3B03~It occurs in the jets of steam called (B 20 3), can be done with sodium, potassium or magnesium.
soflioni escaping from ground in the volcanic The boric anhydride is mixed with sodium, potassium or
~. regions of Tuscany.
magnesium powder and heated in a covered crucible.
Boron is also present to some extent in plants and some- B20 3 + 6Na ---7 2B + 3Na20
times in coal ash. B 20 3 + 6K ---7 2B + 3K20
Extraction: Boron is extracted from borax and cole-
B20 3 + 3Mg ---7 2B + 3MgO
manite minerals. The extraction involves two steps:
(i) Preparation of boric anhydride, B20 3, from one of the The fused mass is stirred with iron rod as to oxidise the
minerals. unreacted sodium or potassium. The mass is then boiled with dil.
(ii) Reduction of B20 3, to an impure brown, amorphous HCI when insoluble boron powder is obtained. It is washed with
form of boron. water and made dry. This is the amorphous variety of boron.
Amorphous boron of low purity is often known as Moissan
;~l 1st Step boron. It is about 95-98% pure and impurities are chiefly metal
borides. It is black in colour.
(a) Preparation of 8 2 0 3 from borax: The finely Modern method (Electrolytic method): Boron is
ground borax is heated with concentrated hydrochloric acid or obtained these days by the electrolysis of a fused mixture
concentrated sulphuric acid when sparingly soluble Olthoboric containing boric anhydride, magnesium oxide and magnesium
acid, H3B03 separates out. fluoride at 1100°C. The electrolysis is done in carbon crucible
Na2B407+2HCI ~ 2NaCI + H2B407 which acts as anode and iron rod is used as cathode. The
Borax Tetraboric acid
magnesium discharged at cathode reduces B20 3 to boron.
Na2B407 + H2S0 4~ Na2S04 + H2 B40 7 2MgO ---7 2Mg + O2
H 2B40 7 + 5H20 ~ 4H 3B0 3 B 20 3 + 3Mg ---7 2B + 3MgO
Orthoboric acid
Orthoboric acid is strongly heated to get B20 3. Boron thus obtained is heated electrically in vacuum at
1100°C when the impurities are volatilised off and pure boron
2H 3B0 3 ~B203+3H20 is obtained.
(b) Preparation of B2~ from colemanite: Crystalline variety of boron is obtained by the reduction of
0) The powdered mineral is fused with sodium carbonate. B20 3 with aluminium powder.
Ca2B6011 + 2Na2C03~ 2CaC0 3 + Na zB40 7 + 2NaB02 B20 3 + 2AI ---7 2B + Al 20 3
Colemanire Borax Sodium
metaborate Aluminium is removed by heating the fused mass with NaOH
solution.
High purity crystalline boron can also obtained by doing carbide (B 4C), when heated with carbon in an electric furnace.
reduction of boron tribromide with hydrogen on tungsten wire Boron combines directly with chlorine and brorrune at higher
at 1200°C. temperatures.
(vii) Reducing nature: It is a powerful reducing agent.
Wwire
2BBr3 + 3H 2 . ) 2B + 6HBr 4B + 3C02 ~ 2B20 3 + 3C
• I 200°C
4B + 3Si02 ~ 2B 20 3 + 3Si
Physical Properties Uses
Elemental boron exists in Boron is used :
two allotropic forms, (a) (i) as a deoxidiser in the casting of copper.
grey black, nonmetallic, (ii) for making boron steels which are very hard and are
high-melting point crysta- used as control· rods in atomic reactors.
lline solid and (b) a dark (iii) as a catalytic agent.
brown amorphous powder (iv) When boron fibres are incorporated in plastics, the
with a structure based on result is a very tough material that is stiffer than steel yet lighter
clusters of 12 atoms Fig. than' aluminium and used in aircraft, missiles and body armour.
8.2. Crystalline boron is (v) Boron steel or boron carbide rods are used to control the
black and chemically inert nuclear reactions. Boron has a very high cross-section to capture
Fig. 8.2 The structure of boron
in nature. It is very hard in is based on linked 12-atom the neutrons. According to another concept boron absorbs
nature. Amorphous boron is units. The unit has 20 faces, so neutron to make the boron having even number of neutrons.
brown and chemically it is called an icosahedron sBlO + onl ~ sBll
active. It melts at 2300°C
and boils at 2550°C. It is difficult to fuse it. It is bad conductor (vi) Boron is absolutely necessary as micronutrient for some
of heat and electricity. Its density is 2.4 g mL-1. green plants in trace amounts, but there is a relatively narrow
concentration range above which boron is toxic to most plants.
Chemical Properties Boron production remains quite low despites the element's
desirable properties of hardness and lightness.
(i) Reaction with air and oxygen: The element is very
inert and is attacked by only the strongest oxidizing agents. 8~' COMPOUNDS OF BORON
Amorphous form when heated in air or oxygen at 700°C, burns
with a reddish flame forming a mixture of oxide and nitride. .. 1. Boron Trioxide, B20 3 .,
4B + 30 2 ~ 'lB 20 3 It is also called sesquioxide. It is an anhydride oriiithob~c
2B + N2~ 2BN acid.
(ii) Reaction with water: Boron is not affected by water It is prepared by burning boron in oxygen,
under ordinary conditions, however, when steam is passed 4B + 30 2 ~ 2B20 3
over red hot boron, hydrogen is liberated. or heating orthohoric acid to redness,
2B + 3H20 ~ B203 + 3H2i 2H3B03 ~ B203 + 3H20
(iii) Reaction with acids: Boron is not affected by
non oxidising acids. It is attacked by oxidising acids like cone. Properties
H2S04 and HN03. It is 'a white hygroscopic solid. It absorbs moistUr~
B + 3HN03 ~ H3B03 + 3N02t (becoming opaque from transparent glassy mass) and finally
2B + 3H2S04 ~ 2H3B03 + 3S02 i converted into boric acid.
(iv) Reaction with' alkalies: Boron dissolves in fused B20 3 + H20 ~ 2HB02
alkalies, liberating hydrogen. Metaboric acid
2B + 6NaOH ~ 2Na3B03 + 3H2 t HB02 + H 20 ~ H 3B03

Orthoboric acid
(v) Reaction with metals: Boron combines with strongly
electropositive metals at high temperatures to form borides. B20 3 is, thus, the anhydride of orthoboric acid.
It is an acidic oxide. It combines with metal oxides when
3Mg + B2 ~ Mg3B2
fused and forms metaborates. Some of the metaborates have
(vi) Reaction with non-metals: Boron forms B2S3 when characteristic colours (this is the basis of borax bead test).
heated with sulphur. k forms extremely hard substance boron
CuO + B203 ~ Cu(B02h
Elements of Group llIA or 13 (Boron and Aluminium) 373
[The volatile part of the salt is displaced by B203' sing the solution at ordinary temperature. It is less soluble in
CUO·S03 + B20 3 - - 7 CuO·B 20 3 + S03 cold water but highly soluble in hot .Jvater.
(CUS04) Blue bead (b), Octahedral form, which is the pentahydrate,
[Cu(B02hl Na2B40?,5H20, is obtained by crystallising splution at 60°C.
Cr203·3S03 + 3B 20 3 - - 7 Cr203·3B203 + 3S03] This is jeweller'S borax.
[Cr2(S04hl Green bead (c) Borax glass is the anhydrous form, Na2Bi)7' It is
[2Cr(B0 2 hl
obtained by heating the common forn above its melting point.
It is reduced by magnesium. It is a colourless glassy mass and is not stable in moist air as
B20 3 + 3Mg Heated) 2B + 3MgO it absorbs moisture and is gradually converted into decahydrate
form.
When reacted with strongly acidic oxides, it behaves as a
(ii) Basic nature: The solution of borax is alkaline in
base.
nature. This is due to its hydrolysis (salt of strong alkali and
weak acid).
Uses Na2B407 + 7H20 ~ 2NaOH ~ 4H3B03
Strong alkali : Weak acid
Boron oxide, B20 3 is used in glass industry with composition (iii) Action of heat: On heating, borax first swells up
Si02, B20 3 and small amount of Al 20 3, to lower the coefficient due to elimination of water molecules. On further heating, it
of thermal expansion. The coefficient of thermal expansion is melts to a liquid which then solidifies to a transparent glassy
appreciably lower in certain borosilicate glasses, in which mass.
many of the silicon sites are occupied by boron. "Pyrex" and
"Kimex" are most familiar of these glasses, has a coefficient
of linear expansion about one third that of ordinary soda-lime
glass, Because borosilicate glasses do not expand much 2NaB02 + B20 3
when' heated, they survive rapid heating and cooling and Sodium Boric
metaborate anhydride
so far is the material of choice for laboratory glassware and '---~v'"'"----"
Glassy mass
household ovenware.
When hot glassy mass is brought in contact with a coloured
II2-: Borax (Sodium Tetraborate) salt and heated again in the flame, B20 3 displaces the volatile
Na2B407·10H20 oxides and combines with basic oxides to form metaborates.
Metaborates of basic radicals have characteristic colours.
Preparation CUS04 + B20 3 - - 7 CuO·B 20 3 + S03
It is prepared by following methods : J,
(i) Borax occurs naturally in dried up inland lakes of Tibet, Cu(B'02)z
Ceylon, California (U.S.A.) and India. In India, it is found in Blue
Laddakh and Puga valley of Kashmir. It is also called Tineal or
Suhaga. Tineal contains about 45% of borax. Advantage is [ Colour of metaborates of Blue
Cu Fe Co Cr
Green Blue Green
taken of its higher solubility in hot water (101 grams per 100 This is the chemistry of borax bead test
grams of water at 100°C) against low solubility at O°C (1.3 (iv) Various compounds of boron can be obtained from
grams per 100 grams of water at OOC) in its purification. The borax.
r
natural tineal is dissolved in hot water and insoluble impurities BN
are filtered off. The solution is concentrated and cooled when Boron nitrid
crystals of borax are obtained.
~ (} HB02 160°C. H2B40/'>&~!.
(ii) Borax can be obtained from colemanite mineral (see ~~~ Meta Tetraboric &0>0
section 8.5).
(iii) From boric acid: Small quantities of borax are
~0o~
,>..0?>
,. is
()
<::>
....
boric acid acid
1 Heated"
strongly
"/0,~
-':-9(\1"
obtained from boric acid by neutralising it with soda ash. Borax HCI • H B0 Heated •8 0 Na or K
3 3 2 3 •B
~
4H3B03 + Na2C03 - - 7 Na2B4~ + 6H20 + CO2 or H2S04 Boric acid strongly Boric Boron
. anhydride
Properties ~'?'Y 1 + C + X2(Halogen)
(i) Borax is known in three forms: BX3

(a) Prismatic borax, which is the common form and is the . Boron halide
NaB02
decahydrate form, Na2B40T IOH20. It is obtained by crystalli- Sodium
metaborate
(v) Aqueous solution of borax acts as a buffer because it (ii) It is less soluble in cold water but more soluble in bot
contains weak acid and its salt with strong base. water. It is steam volatile.
(iii) It is a weak (Ka I x 10-9) monobasic acid. It does not
Na2B407 + 7H20 ------1- 2Na[B(OH)4] + 2H3B03
act as a proton-donor, i.e., protonic acid but behaves as a
Structure of Borax: Borax can be represented as Lewis acid. It actually accepts a pair of electrons from OH- ion.
Na2[B40S(OH)4]-8H20. It has· two tetrahedral and two H-OH + B(OH» ------1- [B(OHhf + H+
triangular units joined together as shown in following figure. (iv) When heated at IOO°C, it loses water and converted
OH into metaboric acid.
I H3B0 3 lOQ"C) HB0 2 + H 20
Na2 HO-B < O-B--O)

)0
O-B--O
B-OH
When metaboric acid is heated at 160°C, tetraboric acid
results.
On strong heating, B20 3 is formed,

I
OH H2B40 7 ------1- 2B 20 3 + H 20
Uses (v) A tIDxture of ethyl alcohol with boric acid bums with
green edged flame due to the formation of volatile ethyl borate.
Borax is used :
(i) for the borax bead test in qualitative analysis. H3B03 + 3C 2 H sOH ) B(OC 2 H s h + 3H 2 0
Ethyl borate
(ii) as a flux. (This is based on its property to dissolve many
metal oxides to form borates of low melting points.) Uses
(iii) as an antiseptic. Orthoboric acid is used:
(iv) in water softening as it forms insoluble calcium and (i) as an antiseptic and eye wash under the name 'boric
magnesium borates (CaB 40 7, MgB 407)' lotion' .
(v) in the manufacture of enamels and glazes for pottery (ij) in the manufacture of enamels and glazes for pottery.
and tiles. (iii) as food preservative.
(vi) in making optical glasses and also borosilicate glass (iv) in glass industry.
which is very resistant to heat and shock. Structure of Boric Acid: The electronic configuration of
(vii) in leather industry for cleaning hides and skins. boron atom is 2i2pl. In the excited state one electron from
(viii) for impregnating match-sticks to prevent after glow. 2s is promoted to 2p orbitaL The three singly occupied orbitals
Ox) for glazing paper and playing cards. undergo sp2 hybridisation giving three hybridised orbitals. These
(x) for stiffening of candles. three hybridised orbitals overlap individually with p-orbital of
0- forming three B-O- bonds.
3. Orthoboric Acid, H3B03
0-
Preparation I
(i) From borax: A hot concentrated solution of borax is B
treated with calculated quantity of concentrated sulphuric acid. -0/ ~O-
When the solution is cooled, crystals of boric acid are obtained. Trigonal planar structure of BO~- unit
Na2B407 + H2S04 + 5H20 ------1- Na2S04 + 4H3B0 3 In boric acid, planar BO~- units are joined by hydrogen
(ii) From colemanite: A large quantity of boric acid is
bonds to give a layered structure as shown in Fig. 8.1.
made from colemanite mineral. The mineral is powdered and
mixed with boiling water. Sulphur dioxide is circulated through
the suspension when boric acid is formed. ~.. 4. Halides of boron
Ca2B6011 + 2S02 + IIH 20 ------1- 2Ca(HS03h + 6H3B03
On cooling, boric acid crystallises out. Preparation
(iii) From TUscany soffioni: Boric acid occurs in the jets Boron combines with halogens and forms the halides of
of steam called soffioni issuing from the ground in the volcanic type BX3, (X = F, CI, Br, I).
regions of Tuscany. The jets are caught in large tanks of water. Except BF3, other trihalides can be prepared by the treatment
The resulting liquid is concentrated by steam. On allowing the of halogens on a mixture of B20 3 and carbon at high
hot solution to cool, crystals of boric acid separate out. temperature.
Properties B20 3 + 3C + 3X2 ------1- 2BX3 + 3CO
(X2 = C1 2, Br2, 12)
(i) It forms soft, white, needle like crystals having a
soapy touch.
I
Elements of Group IlIA or l3 (Boron and Aluminium) 375

The most important is boron trifluoride, BF3 , an industrial are same. It is possible when double bond is delocalized. The
catalyst produced by the reaction between boric oxide, calcium delocalization may be represented as :
fluoride, and sulphuric acid. F F F
/).
3CaF2 + B20 3 + 3H2S04 ---7 2BF3 + 3CaS04 + 3H20 11 I I
Boron trihalides are also obtained by direct combination of A~A~A
boron and halogens under suitable conditions. F F F F F F
2B + 3X2 ---7 2BX3 This bond reduces the electron deficiency of boron atom hence
its Lewis acid character decreases. The tendency to form back
Properties bonding is maximum in BF3 and decreases from BF3 to BI3'
(i) These are covalent in nature due to small size and high Thus, BCI 3, BBr3 and BI3 are stronger Lewis acids than BF3 .
· on B 3+ Ion.
c h arge density . (v) All boron trihalides, except boron trifluoride, are
(ii) These are non-electrolytes, as in liquid state do not hydrolysed to boric acid.
conduct electricity. BCl 3 + 3H20 ---7 H 3B03 + 3HCl
(iii) The boiling points of halides are very low. The boiling The degree of hydrolysis increases from BCl 3 to BI3. Due
points increase as the atomic number of halogen increases. to resistance of BF3 to hydrolysis and its tendency to act as
BF3 is a colourless gas, BCl3 is a colourless fuming liquid Lewis acid, BF3 is used as a catalyst in organic reactions.
(b.pt. = 13°C), BBr3 is also a colourless fuming liquid (b.pt. =
90°C) while BI3 is a white fusible solid (m.pt. 3 J00e). 5. Hydrides of Boron or Boranes
(iv) The trihalides are electron deficient compounds. The B Boron forms a number of hydrides. These are called boranes
atom has an incomplete octet in all its halides. Boron atom by analogy with alkanes. The boranes are an extensive series
acquires six electrons on account of three B-X bonds, i.e., of highly reactive electron deficient binary compounds of boron
2 electrons short of an octet. Thus, the boron atom in BX3 and hydrogen, the boranes have three-centre bonds. These
molecule can accept two more electrons, i.e., an electron pair belong to one of the two series, viz., BIlHn+4 and B nHl1 +6' The
from the donor atoms like N, P, 0, S, F, etc., in NH 3, PH 3, members of BnHI1+6 are less stable.
H 20, H 2S, HF, fT, etc., respectively to form addition
compounds (donor-acceptor compounds).
BnHn + 4 BnHn + 6
B2~ B4H JO
H3N: + BF.3 ---7 [H3N ~ BF3] BsH9 BsHJJ
Donor Acceptor
(Lewis base) (Lewis acid) B6H JO B6H 12
BlOHI4 B9 H JS
The relative Lewis aci.d character of boron trihalides is
The simplest boron hydride, BH3, is unknown. The most
found to follow the following order,
important hydride is diborane (B2H6) which has been exten-
BI3 > BBr3 > BCl3 > BF3 sively studied.
but the expected order on the basis of electronegativity of
the halogens (electronegativity of halogens decreases from F
Diborane, B2HS
to I) should be, It is prepared:
(i) by the action of lithium aluminium hydride on boron
trichloride in the presence of ether.
This anomaly is explained on the basis of the relati ve tendency
of the halogen atom to back donate its unutilised electrons to 4BCl 3 + 3LiAlH 4 Ether) 2B2H 6 + 3LiCI + 3AIC1 3
vacant p-orbital of boron atom. In BF3, boron has a vacant (ii) by passing silent electric discharge at low pressure
2p-orbital and each fluOIine has fully filled unutilised 2p-orbitals. through a mixture of boron trichloride or tribromide and excess
Fluorine transfers two electrons to vacant 2p-orbital of boron, of hydrogen.
thus forming pTC-pTC bond. 2BCl + 6H_7 Silent electric) B H + 6HCl
3 dIscharge 2 6
'O/F (iii) by reacting lithium hydJide with boron trifluoride.

8BF3 + 6LiH ---7 B2H6 + 6LiBF4
X-,6~F Properties
(i) It is a colourless gas which is stable at low temperatures
This type of bond has some double bond character and is in the absence of moisture and grease. It bursts into flame in
known as dative or back bonding. All the three bond lengths air. At higher temperatures, it changes to higher boranes and
at red heat it decomposes to hydrogen and pure boron. It has x x

disagreeable odour and causes headache.! I I
/B"'--.. /B"'--..
B2 H 6 Red heat) 2B+ 3H 2 H-y-N N-X H N N-H
(ii) It burns in oxygen. The reaction is highly exothermic. I I I II
B2~ + 302 -----7 B 20 3 + 3H20 + X H-B B H B B
. 'N/ H / ,N / "'--..X.
(iii) It readily reacts with water liberating hydrogen.
B2H6 + 6H20 ~ 2H3B03 + 6H 2 I I
I H H
(iv) It reacts with strong alkalies to form metaborates and (i) (ii)
hydrogen ..
H x
B2H6 + 2KOH + 2H20 -----7 2KB02 + 6H2 I I
(v) It reacts with chlorine forming boron trichloride. /B"'--.. /B"'--..
B2H6 + 6Cli -----7 2BCl 3 + 6HCI H-N N X H N N-H
(vi) In presence of anhydrous aluminium chloride, it reacts
with dry HCl.
H-B I "
B H H I
B "
B-H
'N/ 'N/
B2H6 + HCI ~ B2H sCI + H2 I I
Chlorodiborane x x
(iii) (iv)
(vii) Lithium borohydride is formed when diborane reacts
with LiH in presence of ether. Uses
2LiH + B2H6 Ether) 2LiBH4 The important uses of diborane are :
(viii) It reacts with carbon monoxide under pressure to (i) as a catalyst in polymerisation reactions.
form carbonyl, BH3CO. (ii) as a reducing agent in organic reactions.
B2H6 + 2CO -----72BH3CO (iii) for making high energy fuels and propellants.
(ix) It reacts with sodium amalgam forming an addition (iv) for preparing hydrocarbons, alcohols, ketones and acids
compound. through hydroboration method.
B2H6 + 2Na (amalgam) -----7 B2H6·Na2 Structure: Diborane is an example of electron deficient
(x) At low temperatures, an addition product, B2H6·2NH3, compound. Boron atom has three half filled orbitals in excited
is obtained with ammonia. state, i.e., it can link with three hydrogen atoms. Thus, while
Low temp. each boron atom in diborane can link to itself three hydrogen
B2H6 + 2NH3 ) B 2H 6·2NH 3 atoms, there are no electrons left to form a bond between two
When the addition product is heated at 200°C, a volatile boron atoms as shown below:
compound borazole or inorganic benzene is formed.
3B2H6·2NH3 ~ 2B 3N 3·H 6 + 12H2 H .. H
Borazole
Borazole has a ring structure like benzene.
..H ..H
H:B ? ? B:H
H
I H Dilthey in 1921 proposed a bridge structure for diborane.
,;-B"'--.. /C, Four hydrogen atoms, two on the left and two on the right,
HN NH HC CH known as terminal hydrogens and two boron atoms lie in the
I U I II same plane. Two hydrogen atoms forming bridges, one above
HB BH HC:"., CH and other below, lie in a plane perpendicular to the rest of
'N/ ~C/
H molecule. This structure shows that there are two types of
I Benzene hydrogen atoms-Terminal and bridging. 4-terminal hydrogen
H
Borazole
Note : (i) The addition product B 2H6 · 2NH3 is considered as an ionic
product. It can be represented as [BH2(NH3ht[BH4 r.
(ii) When diborane with excess of NH3 mixture is heated at high
temperature, boron nitride (BN)x is formed.
B2H 6+ NH 3 Exc~ssofNH3) (BN)x
high temp. Boron nilride
(iii) The 1t bond in borazole (borazine) is formed by back bonding
involving filled p-orbital of N and vacant orbital of B.
However, borazole is more reactive than benzene.
(iv) Disubstituted borazole, B3N3H,.K2 can have four isomers Fig. 8.3
while benzene can have three.
Elements of Group lllA or 13 (Boron and Aluminium) 377
atoms can easily be replaced by methyl groups but when two (iii) by heating B20 3 with Hg(CNh.
bridging hydrogen atoms are attacked, the molecule is B20 3 + Hg(CNh ----7 2BN + CO + CO2 + Hg
ruptured.
According to molecular orbital theory, each of the two (iv) Pure BN is obtained by the action of NH3 on BCI3.
boron atoms is in sl hybrid state. Of the four hybrid orbitals, BCl3 + 6NH3 ----7 B(NH2h + 3NH4CI
three have one electron each while the fourth is empty. Two Boronamide
of the four orbitals of each of the boron atom overlap with two
terminal hydrogen atoms forming two normal B-H a-bonds. Boronimide
One of the remaining hybrid orbital (either filled or empty) of B2(NHh ----7 2BN + NH3
one of the boron atoms, Is-orbital of hydrogen atom (bridge Boron nitride is often prepared by chemical vapour deposition,
atom) and one of hybrid orbitals of the other boron atom a procedure used in the fabrication of several other ceramics
overlap to form a delocalised orbital covering the three nuclei as well. In this method, a controlled chemical reaction of gases
with a pair of electrons. Such a bond is known as three on a contoured, heated surface gives a solid product' of the
centre two electron bonds. desired shape. If a cup made of BN is needed a cup-shaped
mold is heated to a temperature exceeding lOOO°C, and a
H mixture of BCI3(g) and NH 3(g) is passed over its surface the
~B B
reaction, BCI3(g) + NH 3(g) ----7 BN(s) + 3HCI(g)
deposits a cup "shaped layer of BN(s).
Properties
Fig. 8.4 Formation of three centre bond (B-H-B) It is a white powder. It melts at very high temperature,
30000C. It is insoluble in water. However, it gets decomposed
Similar overlapping occurs in one hydrogen atom (bridging) when heated in steam under pressure to yield ammonia.
and fourth hybrid orbital of each boron atom. Thus, the
2BN + 3H20 ----7 B20 3 + 2NH3
formation of diborane molecule can be depicted as shown in
It is chemically inert compound. It remains unaffected by
the following figure :
mineral acids. It dissolves in HF yielding ammonium boro-
~~tfJ H" ~ /H
fluoride.
BN + 4HF ----7 ~BF4
It fails to react with alkalies. However, when fused with
AB~~---:/B~B"'H K2C03, it yields potassium cyanate and potassium metaborate.
Cd:Y~~ H K2C03 + BN ----7 KCNO + KB02
Fig. 8.5 Structure of diborane Structure: The structure of boron nitride, BN, resembles
to that of graphite (Fig. 9.3), consisting of flat planes of
On account of repulsion between the two hydrogen nuclei, hexagons. In. boron nitride, however, the hexagons consist of
the delocalised orbitals of bridges are drifted away from each alternating B and N atoms in place of C atoms (Fig.8.6).
other giving the shape of a banana. The three centre two
electron bonds are also known as banana bonds•
.-" 6. Boron Nitride, BN

Preparation .
It is prepared :
(i) by heating boron in the atmosphere of nitrogen or
ammonia.
2B + N2 ----7 2BN
2B + 2NH3 ----7 2BN + 3H2
(ii) by heating borax with ammonium chloride at red Fig. 8.S The structure of boron nitride, BN
heat.
Recently, another crystalline form of boron nitride called
Na2B407 + 2NH4Cl----7 2BN + 2NaCI + B20 3 + 4H20 borazon has been synthesised by application of high temperature
The resulting mass is treated with dil. HCI, B20 3 and NaCl and pressure. This form is even harder than diamond. It is
dissolve and BN is left insoluble. used as abrasive.
Boron nitride cups and tubes are used to contain and metal, the presence of these elements makes the aluminium
evaporate molten metals. One form of boron nitride powder, metal brittle and liable to corrosion. Thus, the extraction of
BN, is composed of flat, platelike crystals that can easily slide aluminium from bauxite ore involves the following three steps.
over one another. It is used in cosmetics, where it gives a silky (i) Purification of bauxite ore, i.e., removal of ferric oxide
texture. and silica.
Oi) Electrolytic reduction of Al20 3 .
8.i~ ALUMINIUM (iii) Electrolytic purification of aluminium.
Occurrence: Aluminium is a third most abundant element (i) Purification of bauxite ore: The following
forming 8.3% of the eaIth's crust. It is a constituent of clay, methods are used for puJifyingthe bauxite ore.
slate and many types of silicate rocks. It is found only in the (A) 8aeyer's Process
combined state. The important minerals are:
(i) Oxides: (a) Corundum (ruby, sapphire, emerald), This process is mainly applied to bauxite ore containing
A120 3. (b) Diaspore, AI 20 3 ·H20. (c) Gibbsite, Al20 3·3H20. ferric oxide as chief impurity. The colour of such ore is usually
(d) Bauxite, Al20 3 ·2H20.lt is the chief ore of aluminium from red and hence called red bauxite.
which extraction of aluminium is made. It is usually associated The powdered ore is first roasted at a low temperature as
with varying amounts of ferric oxide and silica. to convert any ferrous oxide, if present, into ferric oxide. It is
The pure aluminium oxide is colourless, but the presence of then digested with a concentrated solution of sodium hydroxide
l
impurities can give various colours to it. Naturally occurring (density 1.45 g mL- ) in an autoclave under pressure at 150a C
some impure forms of alumina, Al 20 3 are beautiful, rare and for several hours. The aluminium oxide dissolves in caustic
4 soda forming soluble sodium meta aluminate (NaAI02) while
highly pJized (a) Sapphire, alumina with and Ti + impuJities
(usually blue), (b) Ruby, alumina with Cr3+ and (c) Topaz ferric oxide and silica remain insoluble and settle down. These
alumina with Fe3+ impurities (usually red) are gem quality are removed by filtration.
corundum. 2NaAI0 2
Sodium metaaluminate
(soluble)
The sodium metaaluminate solution is agitated with fre..<;hly
precipitated AI(OHh for 36 hours when sodium meta-
.aluminate undergoes hydrolysis with the formation of AI(OHh
precipitate.
. NaAI0 2 + 2H 20 ----:t NaOH + AI(OHh
Precipiwte
The precipitate is washed and dried.
The solution of NaOH is concentrated and us":d again.
(8) Hall's Process

Fig. 8.7 Some of the impure forms of alumina (corundum) are Bauxite is. fused with sodium carbonate. Aluminium oxide,
prized as gems. (a) Sapphire is alumina with Fe3+ and Ti4+
impurities. (b) Ruby is alumina with Cr 3+ impurities.
Al20 3 combines with sodium carbonate forming sodium meta~
(c) Topaz is alumina with impurities aluminate. The fused mass is extracted with water where
Fe203 and Si02 remain as insoluble in the residue.
(il) Fluoride: Cryolite, Na3AlF6' It is the second important Al20 3 + Na2C03 ~ 2NaAI02 + CO 2
ore of aluminium. Aluminium Sodium
(iii) Basic sulphate: Alunite or alum stone, oxide me[aaluminate
K 2S04·AI 2(S04h·4AI(OHh· The solution containing sodium metaaluminate is warmed to

50-60a C and carbon dioxide is circulated through it. AI(OHh
(iv) Basic phosphate: Turquoise, AlP04·AI(OHh·H20.
separates out as precipitate.
It is usually blue coloured due to presence of copper phosphate.
(v) Silicates: Feldspar, KAISi 30 g, kaolin, porcelain, mica, 2NaAI0 2 + CO 2 + 3H20~ 2Al(OHh + Na2C03
china clay, slate, etc., AI 20 3 ·2Si02·2H20. The, precipitate is filtered, washed and dried.
Extraction: Aluminium is mainly isolated from bauxite The solution of Na2C03 is concentrated and used again.
ore which is generally contaminated with fenic oxide and
silica. The removal of ferric oxide and silica from bauxite ore (C) Serpeck'sProcess
is essential before it is subjected to electrolysis because it is This process is used· when silica is present in considerable
rather difficult to remove iron and silicon from aluminium amounts in bauxite ore. The ore is mixed with coke and heated
at 1800°C in presence of nitrogen, where AlN (aluminium concentration of the electrolyte decreases, the resistance of
nitride) is formed. the cell increases. This is indicated by the glowing of a lamp
Al20 3 + 3C + N2 -----7 2AIN + 3CO placed in parallel. At this stage more of alumina is added.
The exact mechanism of the electrolysis is not yet known.
Silica is reduced to silicon which volatilises off at this
Two concepts have been proposed.
temperature.
First concept: AlF3 from cryolite ionises as,
Si0 2 + 2C -----7 Si + 2CO
AlF3 ~ A1 3+ + 3F
AIN is hydrolysed with water into aluminium hydroxide.
This process has one distinct advantage that ammonia is A1 3+ ions are discharged at cathode and F- ions at anode.
obtained as a valuable by-product. Al 3+ + 3e -----7 Al (at cathode)
Calcination of alnminium hydroxide: The aluminium 2F- -----7 + 2e (at anode)
hydroxide precipitate obtained in the above process is calcined
at I500°C in a rotary kiln to obtain pure aluminium oxide, The liberated fluorine reacts with alumina to form AIF3 and
Al20 3 (commercially reffered as alumina). O 2. The oxygen attacks the carbon anodes to form CO and
CO 2 ,
2AI(OHh 1500°C) Al203 + 3H 20
(ii) Electrolytic reduction of pure alumina: The 2C + O2 -----7 2CO

electrolysis of pure alumina faces two difficulties: (i) Pure
alumina is a bad conductor of electricity, (ii) The fusion C + O2 -----7 C02
temperature of pure alumina is about 20000C and at this Anodes are replaced frequently.
temperature when the electrolysis is carried of fused mass, the Second concept: Alumina (AI 20 3) ionises as,
metal formed vaporises as the boiling point of aluminium is AI203 ~ Al 3+ + AIOj-
1800°C. Cathode Anode
The above difficulties are overcome by using a mixture Al 3+ + 3e -----7 Al (at cathode)
containing alumina, cryolite (Na3AlF6) and fluorspar (CaF 2) in
At anode AlO) is oxidised.
the ratio of 20: 40 : 20. The fusion temperature of this mixture
is 900°C and it is a good conductor of electricity. 4AIO~- -----7 2Al203 + 302 + 12e (at anode)
The electrolysis is carried out in an iron box lined inside Thus, the overall chemical reaction taking place during
with gas carbon which acts as cathode. The anode consists of electrolysis is,
carbon rods which remains dip in the fused mixture of the 2Al20 3 -----7' 4Al + 302
electrolyte from above. The fused electrolyte is covered with Aluminium of 99.8% purity is obtained from this process.
a layer of coke (Fig. 8.8). (iii) Refining of aluminium by Hoope's electrolytic
Frozen crust of alumina method: Aluminium is further purified by Hoope's process.
and electrolyte
The electrolytic cell consists of an iron box lined inside with
carbon. The cell consists of three layers which differ in specific
gravities. The upper layer is of pure aluminium which acts as
cathode. The middle layer consists of a mixture of the fluorides'
of AI, Ba and Na. The lowest layer consists of impure aluminium
which acts as anode. The middle layer works as electrolyte.
COPPER CLAMPS
Pure -.JllIcuruun==rr==n===rr==rr==rr==rr
aluminium
cathode
Carbon lining (cathode)
Fig. 8.8 Tapping
hole
1Iml~llli~§~
The current passed through the cell serves two purposes-
(i) Heating of the electrolyte-The temperature of the Iron cell
cell is automatically maintained at 900-950°C,
(ll) Electrolysis-On passing current, aluminium is dis-
charged at cathode. Aluminium being heavier than electrolyte Carbon lining
sinks to the bottom and is tapped out periodichlly from tapping
hole. Oxygen is liberated at anode. It attacks carbon rods Fig. 8.9
fomting CO and CO2, The process is continuous. When the
The graphite rods dipped in pure aluminium and Cu-AI alloy Physical Properties
rod at the bottom in the impure aluminium work as conductors.
(a) Aluminium is a bluish white lustre metal. The lustre is
On electrolysis, aluminium is deposited at cathode from the
destroyed on long exposure to air due to formation of a thin
middle layer and an equivalent amount of aluminium is taken
film of oxide on the surface. (b) The density of aluminium is
up by the middle layer from the bottom layer (impure 1
2.7 g mL- (light metal). It is malleable and ductile. (c) It is
aluminium). Therefore, aluminium is transferred from bottom
a good conductor of heat and electricity. (d) It melts at 660"C
to the top layer through middle layer while the impurities are
and boils at 1800"C. (e) It can be welded and cast but difficult
left behind. Aluminium thus obtained is 99.98% pure.
to solder.
FLOW SHEET FOR THE EXTRACTION OF ALUMINIUM
I Aluminium ore, A1203·2H20 (Bauxite) I

j,
REFINING OF BAUXITE
(a) Baeyer's Process:
Bauxite ore ~=~ as to convert FeO into Fe203
Hydrolysis
Roasted ore + NaOH NaAI0 2 . J Al(OH)3 + NaOH
m presence p t
Solution
of little AI(OH)3 p.
(b) Hall's Process:

Bauxite ore + Na2C03 FuSed) NaAJ02
1 Extracted with water
Solution
1 W_d 5"-""C
cO2 istirculated
AI(OHh + Na2CO)
ppt.
(c) Serpeck's Process:
Bau:ate ore + Coke 1800"C) AlN ~ AJ(OHh + NH3
Nltrogen ppt.' By-product
Crucination
AI(OHh 1500·C) Al203

Anhydrous alumina
Electrolytic Reduction
Electrolyte Al203 dissolved in Na3AIF6 and CaF2
Cathode--Carbon lining Anode-Graphite rods
°
Al 2 3 Electrolysis )
950·C
AI
99.8% ·pure
+ °2
Electrolytic Refming
(Hoope's process)
j,
Pure Al (99.98% pure)
Elements of Group lIlA or 13 (Boron and Aluminium) 381
Chemical Properties nitrogen, forms aluminium nitride.

2Al + N2 -----72AlN
Aluminium is a chemically reactive metal although much
Aluminium powder when fused with sulphur fOTIns
less reactive than the alkali metals or alkaline earth metals.
aluminium sulphide.
(a) Action of air: Aluminium is not affected by dry air 2Al + 3S -----7 Al zS 3
but in moist air a thin film of oxide is formed over its surface.
Finely powdered heated aluminium combines with halogens
Which protects the underlying metal from further reaction. It
to form corresponding halides.
burns in oxygen producing brilliant light. The metal will bum
2AI + 3X2 -----7 2AIX3
vigorously once started however.
(Xz = F2, Cl z , Brz, Iz)
4AI + 302 -----7 2Al20 3 All these compounds are hydrolysed with water.
The reaction is highly exothermic and the heat evolved is AlN + 3H20 -----7 Al(OHh + NH3
used in the thermite process for the reduction of oxides of Cr, Al2S 3 + 6H20 -----7 2Al(OHh + 3H2S
Fe, Mn, etc. AlX3 + 3H20 -----7 Al(OHh + 3HX
(b) Action of water: Pure aluminium is not affected by (f) Redncing agent: It is a good reducing agent and
pure water. The impure aluminium is readily corroded by water reduces oxides of metals like Cr, Fe, Mn, etc.
containing salts (sea water). Aluminium decomposes boiling CrZ03 + 2Al -----7 2Cr + Al z0 3 + heat
water evolving hydrogen. Fez03 + 2Al -----7 2Fe + AlZ0 3 + heat
2AI + 6H20 -----7 2AI(OHh + 3H2! 3Mn30 4 + 8Al -----7 9Mn + 4Alz03 + heat
It reduces oxides of non-metals also.
(c) Action of acids: The oxidation potential of al uminium
3C02 + 4AI -----7 2Alz03 + 3C
is 1.66 volts. Thus, it is strongly electropositive, very reactive
3Si02 + 4Al -----7 2AlZ03 + 3Si
and a powerful reducing agent. It dissolves in HCI (dil.and
(g) Displacement of other metals : Being more
conc.) and dilute sulphuric acid, evolving hydrogen.
electropositive it displaces copper, zinc and lead from the
2Al + 6HCI -----7 2AICI3 + 3Hz! solutions of their salts.
2Al + 3H2S04 -----7 A12(S04h + 3Hz! 3ZnS04 + 2AI'-----7 Alz(S04h + 3Zn
The reaction with dil. H 2S04 is very slow probably on 3CUS04 + 2Al -----7 Al2(S04h + 3Cu
account of the insolubility of the oxide film in this acid.
Hot concentrated sulphuric acid dissolves AI with evolution Uses
of SOz. (i) Aluminium being cheap and light metal is largely used for
2Al + 6H zS04 -----7 Alz(S04h + 3S0 z + 6H zO making household utensils, trays, frames, etc. Bodies of
Dilute and concentrated HN03 has no effect on AI, i.e., Al automobiles, aircraft and roofing are made of aluminium sheet.
is rendered passive by nitric acid. This is due to surface oxidation (ii) Thin foils of Al are used in wrapping soaps, cigarettes
and formation of a thin film of oxide on its surface. Organic and confectionary.
acids have little action on Al at ordinary temperatures: (iii) Al wire is used in transmission lines and coils for dynamos
(d) Action of alkalies: Aluminium is attacked by caustic and motors.
alkalies with the evolution of hydrogen. (iv) It is used for making silvery paints for covering iron
2AI + ~NaOH + 2H2~ -----7 2NaAIOz + 3H 2 ! and other materials.
Sol~tion Sodium meta- (v) It is used in thermite process for the extraction of Cr,
aluminate (soluble) Mn, etc.
Fused
2AI + 6NaOH ) 2Na3AI03 + 3H 2 ! (vi) Since it is not attacked by nitric acid, it is used in
Sodium aluminate chemical plants and for transporting nitric acid.
(e) Action of non-metals: Besides oxygen, aluminium (vii) Because of its lightness, good conductivity and resistance
reacts with non-metals directly to form corresponding to corrosion, it is used for making alloys which find appli-
compounds. Aluminium when heated in the atmosphere of cations in industries and arts. The important alloys of aluminium
are:
Name. of the alloy Approximate composition Uses
1. Magnalium 95% AI, 5% Mg In the construction of airships, balances and pistons of motor engines.
2. Duralumin 95% AI, 4% Cu, 0.5% Mg, 0.5% Mn Aeroplanes and automobile parts as its strength of toughness is comparable to mild
steels.
3. Aluminium bronze 90% Cu, 9.5% AI, 0.5% Sn For making utensils, cheap artificial jewellery, .photo frames, coins, golden paints.
4. Nickeloy 95% AI, 4% Cu, 1% Ni Aircraft parts.
5. Y-alloy 93% Al, 4% Cu, 2% Ni, 1% Mg For making pistons and machinery parts.
6. Alnico 77% Stl;!el; 2% Ni, 20% Al, 1% Co For making permanent magnets.
(viii) Aluminium amalgam is used as a reducing agent. turnings in absence of air. The vapours of aluminium chloride
(ix) Aluminium powder is used in fire works, flash light are condensed when solid anhydrous aluminium chloride is
powder and in thermite welding. ohtained.
2AI + 6HCI 2AICl 3 + 3H 2
8~~F":J COMPOUNDS OF ALUMINIUM 2AI + 3Cl 2 ----? 2AICl 3
It can also be obtained by heating a mixture of alumina and
1. Aluminium Oxide or Alumina, AI 20 3 carbon in an atmosphere of chlorine.
It occurs in nature as colourless corundum and tinted with
2AICl 3 + 3CO
metallic oxides as ruby (red), sapphire (blue), amethyst (violet), Vapours
emery (green), etc. These coloured oxides are precious stones. J"
Cooled
Hydrated oxide (AI20 3·2H20) occurs as bauxite. Solid anhydrous
It is prepared by igniting aluminium hydroxide, aluminium aluminium chloride
sulphate or ammonium alum. (ii) Hydrated aluminium chloride: AICI3·6H20, is
2AI(OH)3 ----? AI 20 3 + 3H20 formed when aluminium metal or aluminium hydroxide is
AI 2(S04h ----? Al 20 3 + 3S03 dissolved in dilute hydrochloric acid.
(NH4hS04·AI2(S04h24H20 ----? 2Al + 6HCl 2AICl] + 3H z
Ah03 + 2NH3 + 4S0 3 + 2SHzO AI(OH)3 + 3HCl AICl 3 + 3H20
It is obtained in crystalline form by strongly heating a mixture HCI gas is circulated through the solution to obtain crystals
of aluminium fluoride and boric oxide. of hydrated aluminium chloride.
2AIF3 + B20 3 ----? Al 20 3 + 2BF3
Properties: It is a white solid, insoluble in water. It is Properties'
a stable and unreactive substance. It begins to volatilise at (a) Anhydrous aluminium chloride is a white solid. It is
17S0°C and melts at 20S0°C. It boils at 22S0°C. deliquescent and fumes in air. On heating it sublimes at 180°C
It shows amphoteric nature. When it is fused with oxides and the vapour density corresponds to the formula AhCI6. It
of chromium, iron and cobalt, synthetic semi-precious stones is covalent when anhydrous as it does not conduct current in
are obtained. fused state. It is soluble in organic solvents such as alcohol,
Uses: It is widely used for making bauxite bricks which ether, benzene, etc. The dimeric formula is retained in non-
are used for lining furnaces. Fused alumina is used as refractory polar solvents but is broken into [AI(H20)6]CI3 on dissolution
material. When heated. in an electric arc at 3000OC, a hard in water on account of high heat of hydration. The molecule
powder known as alundun is obtained which is used as (dimer) is an autocomplex and is represented as,
abrasive. With lime, it is used as bauxite cement which is not
affected by sea water. It is used in chromatography, in extraction
of aluminium and in preparing precious stones. CI)AI<CI)AI<CI
CI CI CI
2. Aluminium Chloride, AICI 3
(i) Anhydrous aluminium chloride: It is prepared by (b) Anhydrous aluminium chloride fumes in moist air due to
passing dry HCI gas or chlorine gas over heated aluminium evolution of HCI.
AI 2Cl6 + 6H 20 ----? 2AI(OHh + 6HCI
Sodalime When dissolved in water, it changes into hydrated aluminium
chloride which is ionic in nature.
AI 2Cl 6 + 12H20 ----? 2AIC13·6H20
Anhydrous CaCI2 AICl3 ~ Ae+ + 3CI-
glass wool plugs
Small bottle (c) Anhydrous aluminium chloride forms an addition
product with ammonia gas.
Chlorine
AI2CI6 .+ 12NH3 2[AICI 3 ·6NH3]
(d) The solution of aluminium chloride in water is acidic in
Combustion tube T ~ Aluminium chloride
(AIClg)
nature due to hydrolysis.
AICl 3 +3H 20 ----? AI(OHh + 3HCI
Heat Weak base Strong acid
Fig. 8.10
(e) When ammonium hydroxide is added to the solution of The alums are effective in precipitating colloids, i.e., act as
aluminium chloride, a gelatinous precipitate of aluminium coagulants. The aluras have germicide properties. Alums are
hydroxide appears which does not dissolve in excess ofNH40H. thus used in the purification of water, tanning of leather, as
AICl3 + 3NH40H ~ AI(OHh + 3NH4CI mordants in dyeing and as antiseptics.
(f) When sodium hydroxide is added to the solution of
aluminium chloride drop by drop, a white gelatinous precipitate
appears which dissolves in excess of sodium hydroxide forming It is commonly known as alum.
sodium meta-aluminate.
Preparation
AICl 3 + 3NaOH ~ AI(OHh + 3NaCI
(i) From bauxite or aluminium sulphate: Bauxite is
AI(OHh + NaOH ~ NaAI02 + 2H20
boiled with sulphuric acid to form aluminium sulphate. To this
solution calculated quantity of K2S04 is added. The solution is
Uses concentrated and cooled. After some time crystals of potash
(i) It is used as a catalyst in Friedel-Craft's reaction. alum are obtained.
(ii) It is also used in the manufacture of gasoline by cracking Al20 3 + 3H2S04 ~ A1 2(S04h + 3H20
of high boiling fractions of petroleum. A1 2(S04h + K2S04 +24H20~K2S04·Al2(S04)3·24H20
(iii) It finds extensive use in the manufacture of dyes, drugs Potash alum
and perfumes. (ii) From alum stone or alunite: Alum stone is treated
with dilute sulphuric acid and the solution is boiled. A calculated
3. Alums quantity of K2S04 is added to the solution. The solution on
Formerly, the term alum was used to describe only one cooling yields crystals of potash.
double sulphate with 24 molecules of water of crystallisation, K2S04·AI2(S04h·4Al(OHh + 6H2S04 ~
potassium aluminium sulphate, K2S04·AI 2(S04h·24H20, but Alum stone K 2S04 + 3A1 2(S04h + 12H20
now this term is used for all the double sulphates having the
K2S04 + A1 2(S04h + 24H10 ~ K2S04,AI1(S04h-24H20
composition,
M 2S0 4 ·Mi(S04h· 24H 20
Properties
where M stands for monovalent basic radicals such as Na+,
K+, Rb+, Cs+, Ag+,n+, NH! and M' for trivalent basic radicals (a) It is a white crystalline compound,
suc h as A1 3+,C 3+ M-n3+ , C
r3+-, Fe, _ 0 3+ , etc~ (b) It is soluble in water and its aqueous solution is acidic
Some examples of alums are : due to hydrolysis of Al1(S04h.
Potash alum K2S04·AI2(S04h·24H20 (c) On heating it swells up on account of eHmination of
(commonly called alum) water molecules.
Ammonium alum (NH4hS04,Ah(S04)3·24H20
Sodium alum Na2S04·AI2(S04h·24H20
Chrome alum K2S04·Cr2(S04))·24H20 K2S04.AI1 (S04h K 1S04 + Al 203 + 3S0 3
Red hot)
FelTIC alum (NH4hS04·Fe2(S04h24H20 (d) Its aqueous solution contains K+, A13+ and SOr ions
Alums are generally obtained when hot solutions of equimolar and their usual tests can be performed.
quantities of their constituent sulphates are mixed and the
resulting solution is subjected to crystallisation. Uses
Alums are crystalline compounds. In alums each metal ion It is used:
is surrounded by six water molecules and the crystals of alums (i) as a mordant* in dyeing and calico printing.
consist of [M(H20)6t, [M'(H20)6P+ and SO~- ions. Alums (ii) in sizing of cheap quality of paper.
are fairly soluble in hot water but less soluble in cold water. (iii) in purification of water.
The solutions are acidic and have stringent taste. The solutions (iv) as antiseptic and in stopping bleeding from cuts.
show the properties of ions of the constituent salts. The alums (v) in leather tanning.
are isomorphous to each other and form mixed crystals.
Each alum has different melting point. Alums lose water of 4. Ultramarine
crystallisation when heated. If rapidly heated to a high
It is an artificial Lapis-Lazuli. Lapis-Lazuli is a rare mineral
temperature, the alum swells up and a porous mass called
which has fine blue colour. It isa complex silicate of sodium
burnt alum is left behind.
* A "mordant" is a compound that helps to attach the dye to the fabric.
and aluminium containing about 12 per cent of sulphur probably peroxide). The large amount of heat generated· in the reaction
in the fonn of sodium sulphide. fuses both the alumina and the element set free. Two distinct
It can be prepared artificially by heating a mixture of kaolin, layers are fonned which are removed easily.
soda ash, sulphur and charcoal to bright red heat. At first a (ii) Thermite welding of metals: Another application is
white mass is fonned which changes to a green mass in air. the welding of metals especially the welding of steel. The
It is powdered and heated with more of sulphur where the blue broken part to be welded is surrounded by a mould of sand and
variety having the composition NasAl3$i3S3012 is obtained. clay and heated to redness by means of a gasoline torch or a
Blue variety on heating in a current of dry chlorine changes to blast lamp. A mixture of aluminium powder and Fe203 in the
violet variety. ratio of 1 : 3 (known as thennite) is taken in a crucible lined
However, the blue variety is most common. It is used : with magnesite and having a plug hole (Fig. 8.11). This is
(i) in making blue paint. covered with a mixture of magnesium powder and barium
(it) in laundry for blueing purposes. peroxide with a magnesium ribbon inserted into it. The thermite
(ill) in making wall paper and blue tinted paper. is ignited with magnesium ribbon. Iron oxide is reduced to iron
(iv) in calico-printing.
8.~1 GOLDSCHMIDT'S ALUMINO-THERMIC Ignition

mixture
Fireclay
. PROCESS (Mg + Ba02)
crucible
Aluminium has the power of displacing elements less The rm ite

electropositive than itself from their oxides as it has great (AI + Fe203)
affinity for oxygen at high temperatures. The reaction being so Magnesite
strongly exothennic that the metal set free is obtained in the lining
molten condition and it is protected from oxidation by a layer Tapping
o plug
of fluid slag consisting of Al20 3. o
o
Oxide + Al ~ Al 20 3 + metal + heat energy o
~ Broken girder
Molten state Clay mould
The reaction fonns the basis of the alumino-thermic process.

It was discovered by Goldschmidt. The process has two main
applications:
.(i) Extraction of metals and non-metals: The metals
like Cr, Mo, Mn and non-metals like boron, silicon, etc., can
be extracted from their corresponding oxides.
Cr20J + 2AI ~ 2Cr + Al20 3 + heat energy
3Mn30 4 + 8AI ~ 9Mn + 4Al20 3 + heat energy
Fig. 8.11 Thermite welding
B203 + 2Al ~ 2B + Al203 + heat energy
3Si02 + 4Al ~ 3Si + 2Al203 + heat energy and temperature rises to about 2500°C. Molten iron thus
The oxide is mixed with aluminium powder. The mixture is produced is tapped into the parts to be welded. The heated
ignited in a fire clay crucible surrounded by sand with the help surface of the broken iron melts and mingles with the molten
of a cartridge (containing magnesium powder and barium iron, thus giving a perfect weld.
Example 1. Starting from boric acid how would you (b) Boric acid is first converted into boric anhydride. It is
prepare? now mixed with carbon and the mixture is heated in a current
(a) Boric anhydride, (b) Boron trichloride, (c) Boron of chlorine when boron trichloride is fonned. .
trifluoride, (d) Boron hydrides, (e) Ethyl borate, (j) Meta
B20 3 + 3C + 3Cl2 ~ 2BCl3 + 3CO
and tetraboric acids.
Solution: (c) It is prepared by heating boric acid with CaF2 and
(a) Boric acid on strong heating fonns boric anhydride. concentrated sulphuric acid.
2H 3B0 3 Red hot) B20 3 + 3H 20 CaF2 + H2S04 ~ CaS04 + H2F2
2H3B03 + 3H 2F 2 ------7 2BF3 + 6H20 (iii) Pure alumina has very high fusion temperature (Uld is
(d) Boric acid is first converted into boric anhydride. It is bad conductor of electricity. To reduce its fusion temperature
then heated with excess of magnesium powder in a covered and to make it as good conductor of' electricity, cryolite is
crucible. The magnesium boride so formed.is treated with added. '
dilute HCl when a ririxture of boron hydrides is obtained. (iv) Anhydrous aluminium chloride is hydrolysed in moist
Mg air and fumes of HCl are given out.
H 3BO J Red hot) B20 3 H ) Mg3 B2 --:----7
eat AICl3 + 3HzO ------7 AI(OHh + 3HCl
. A mixt. of boron hydrides (v) Alum acts asa germicide and strong coagulant. The"
(e) Ethyl borate is formed ~hen the mixtlire of boricacid muddy water consists colloidal particles of negative charge
and ethyl alcohol is warmed with concentrated sulphu.ric acid which are coagulated by Al3+ ions given by alum. The coagulated
in the form of vapours. mass then settles down.
3C2HsOH + H 3B0 3 ------7 \C2HshB03 + 3H20, Example 4. An inorganic Lewis acid (X) shows' the
(f) Orthoboric acid when heated at 100°C, decomposes into following reactions:
metaboric acid. (t) It fumes in moist air.
(it) The intensity of fumes increases when a rod dipped in ,
H3 B0 3 IOO·C) HB0 2 + H 20 NH40H is brought near to it.
When heated at 160°C, it decomposes into tetrabbpc acid. (iii) An acidic solution of (X) on addition of NHi;1 and
NH40H gives a precipitate which dissolves {n NaOH solution. .
4H 3B0 3 160·C) H 2B 2I0 7 + 5H20 (tv) An acidic solution of (X) does not give a precipitate
or 4HB02 ------7 H2B40 7 + HiO with HzS.
Identify (Xl and give chemical reactions at steps (i) to (iii).
,Example 2. Identify (A) and (B) in the following reactions: [Roorkee 1994]
Colemanite + (A) ------7 Na2B407 Solution:
Na2B407 + (B) ------7 H 3B03 X is a Lewis acid and fumes in air, it may be anhydrous
AlCI3·
Solution:
(i) AIC1 3 + 3H zO ------7 Al(OHh + 3HCl
(A) is sodium carbonate. Fumes
Ca2B6011 + 2Na2C03 ------7 Na2B407 + 2NaB0 2 + 2CaC0 3 The fumes intensify as HCl and NH 40H react t~ form'
Nl4Cl.
(B) is either concentrated H 2S04 or HCl.
(ii) , NH40H + HCl ------7 NH4Cl + H 20
Na2B4~ + H 2S04 + 5H20 ------7 Na2S04 + 4H3B03
(iii) AI(OHh is precipitated on addition of NH4CI and
Na2B407 + 2HCI + 5HzO ------7 2NaCI + 4H3B03 ' NH40H.
'EXample 3. Explain the following with appropriate This dissolves in NaOH forming sodium meta-
reason: aluminate-
(i) Although aluminium is above hydrogen in the electro- AlCl 3 + 3NH~OH --::--7 AlJQHh +:;\.Nli 4CI
chemical series, it is stable in air and water. [UT.1994] ppt.
(ii) In the electrolytic manufacture of aluminium, carbon Al(OHh + NaOH ------7 NaAl0 2 + 2H ZO
anodes are consumed. Soluble
(iii) Cryolite is added to alumina in the ,electrolytic No precipitate is formed by passing H 2S through solution.
manufacture of aluminium. Example 5. Explain the following:
(tv) Anhydrous Alel3 fumes in air ..
(i) Boron and aluminium halides behave as Lewis acids.
(v) Alum is used in settling muddy water.
Solution: (it) Boron tribromide is stronger.acid than boron trifluoride.
(i)The thin protective film of oxide, Al203, is formed which (iii) Aluminium forms [AIF6]3- ion but boron does notform
protects the metal from further attack of air and water and [BF6]3- ion.
thus, it is stable in air and water. (iv) Boron has high melting and boiling points.
(ii) During electrolysis of cryolite and alumina in the
(v) The p1t-p7t back bonding occurs in the halides of boron
manufacture of aluminium, oxygen is evolveC 'l.t anode.
and not in those of aluminium.
2F +2e (at anode); AlZ03 + 3F2 .' lAlF3 + ~ O2 Solution:
Oxygen reacts with carbon anodes forming CO and COz.' (i) Both boron and aluminium atoms in their halides (MX3)
Thus, carbon anodes are consumed. possess six electrons in their valency shell. To complete octet,
they can accept a lone pair of electrons from a donor and thus So, A = Ca2B6011·5H20 Colemanite and F = Co(B02h;
act as Lewis acids. , B = CaC0 3; C = Na2B40T lOH 20; D = NaB0 2; E= B20 3.
(ii) Back bonding occurs ip. boron halides to compensate the Example 7. AIF3 is insoluble in anhydrous HF but dissolves
electron deficiency and hence Lewis acidity is decreased. The on addition of NaP AIFi precipitates out of the resulting
tendency of back bonding is maximum in BF3 and decreases solution when gaseous BF3 is bubbled through. Give reasons.
from BF3 to BI3 as the size of the halogen increases. p-orbitals
Solution:
of high energy shells in bromine overlap less effectively with
Anhydrous HF is a covalent compound and is strongly H-
vacant p-orbital of boron in BBr3. Thus, BBr3 is stronger acid
bonded. Therefore, it does not furnish F ions and AlP3 does
than BF3 as it has still tendency to accept electrons to remove
not react to form [AIF6]3- and remains undissolved. When
ele~tron deficiency.
NaP is added, F ions are furnished as NaP is an ionic compound.
(iii) Maximum coordination number of boron is four as it
AlP3 with F ions forms a complex ion, the sodium salt of
does not have d-orbitals while the maximum, coordination
which is soluble.
number of aluminium is 6. Thus, Al forms [AIF6]3- ion while
boron does not form [BF6]3- ion. 3NaP + AIF.3~ Na3[AIF6]
Soluble complex
(iv) Boron has giant cQvalent polymeric structure both in
solid and liquid states and thus, it has high melting and boiling B, being smaller in size and having higher electronegativity,
points. II! has much higher tendency to form complexes than AI.
(v) The tendency to show prt-prt back bonding depends on Therefore, when BF3 is added to the AI-complex, AlF3 gets
the size of central atom. This tendency decreases as the size precipitated and B-complex comes into existence.
of the central atom increases. Since aluminium has larger size Na3AlP6 + 3BF3 ~ 3Na[BF4] + AlP3
than boron, the back bonding is not possible.
Example 8. Give reasons :
Example 6. (i) A white precipitate (B) is formed when a (i) A mixture of NaOH and aluminium pieces is used to open
mineral (A) is boiled with Na2C03 solution. the drain.
(ii) The precipitate is filtered and the filtrate contains two (ii) Aluminium utensils should not be kept in water overnight.
compounds (C) and (D). The compound (C) is removed by (iii) Aluminium wire is used in transmission cables.
crystallisation and when.. CO2 is passed through the mother (iv) Aluminium alloys are used to make aircraft body.
liquor left, (D) changes'to (C). Solution:
(iii) The compound (C) on strong heating gives two (i) N aOH reacts with Al and evolves hydrogen. The pressure
compou'nds (D) and (E). of the evolved hydrogen can be used to open the clogged
(iv) (E) on heating with cobalt oxide produces blue coloured drains.
substance (F). (ii) Aluminium is slowly attacked by water and dissolved
Identify (A) to (F) and give chemical reactions for the oxygen to fonn Al 20 3 on the surface. A very small amount of
Al 2 3 may d ISSO . AI 3+.IOns. S·lllce, Al 3+ IOns
· 1ve to gIve . are
reactions at steps (i) to (iv).
Solution:
[Roorkee 1995]
°
injurious to health, the drinking water is not kept in aluminium
(i) The mineral (A) is colemanite, Ca2B6011·5H20. utensils for long.
(iii) Al is a good conductor of electricity and also not affected
Ca2B601l + 2Na2C03(aq.) Boiled)
by atmosphere. Hence, it is used in transmission cables.
CA) 2CaC0 3+ Na2B407 +2NaB02 (iv) AI-alloys are light, tough and corrosion resistant. Hence,
(B) (e) (D)
AI-alloys are used for making aircraft bodies.
Insoluble
Soluble
Example 9. What is inorganic benzene? Why it is so called?
(ii) (C), the borax is crystallised. The mother liquor consisting
How will you get it from diborane? [W~st Bengal, J.E.E. 2005]
sodium metaborate is treated with CO 2.
4NaB02+C02~ Na2B407+Na2C03
Solution:
(D) (~ Borazine or borazole (B3N3~) is known as inorganic
benzene. It is so called because its structure is similar to that
(iii) Na2B407" lOH 20 Heated) Na2B407 + lOH 20
Anhydrous
of benzene.
H H
Na2B407 Strongly) 2NaB02 + B 20 3
heated (D) . (E)
I I
H-N'~B"-..;N-H H-C~C~C-H
(iv) CoO + B 20 3 Heat) Co(B0 2 )z
Cobalt metaborate
I' II I I
Blue coloured H - B.~::::~'N'/B- H H-C.~:::::~'C/C-H
(F)
I I
H H
Borazine. Benzene
Like carbon in benzene, both B and N in borazine are sp2 in TI do not shield the outer shell electrons very effectively. On
hybridized. The It-bonding in borazine is dative, i.e., a pair of account of this, the outer shell electrons are tightly held by the
electrons is donated by nitrogen to p-orbital of B. nucleus and hence higher energy is required for their removal.
At low temperatui'e, borazine reacts with ammonia to form This explains why Ga has higher I.E. than AI. From Ga to In
an addition compound. the shielding effect of additional 4d-electrons is slightly more
than the effect of increased nuclear, charge and hence, the I.E.
B2 H 6 + 2NHr--~ B2H 6 · 2NH3
of In is slightly less than Ga. In TI, the shielding effect of
When this compound is heated at 200°C, it decomposes to d- and f-electrons is less than the effect of increased nuclear
form borazine (volatile). charge and hence, the I.E. is higher than In.
3B2H 6 · 2NH3 ~ 2B3N3~ + 12H2 Example 11. Standard electrode potential values, EO for
Example 10. The first ionisation enthalpy of group 13 AI 3+IAI is -1.66 V and that of Tl 3+ITI is +1.26 V. Predict
3
elements are: about the formation of M + ion in solution and compare the
electropositive character of two metals.
Element B Al Ga In TI
1 Solution: '
1st I.E., (kJ mor )801 577 579 558 589
Standard electrode potential values suggest that aluminium
How will you explain this deviation from the general trend? has high tendency to make AI3+ ions whereas T~3+ is unstable
Solution: as it shows strong oxidising nature. Aluminium being able to
From B to AI, the ionisation enthalpy decreases as expected form +3 ions easily, it is more electropositive ,than Tl. '
doe to an increase in atomic size and screening effect. However,
Example 12. Account for the fact that aluminium chloride
I.E. of Ga is only slightly higher than that of Al while that of
thallium is much higher than those of AI, Ga and In. These exists as a dimer, AI2CI(y
deviations are explained as follows: , . Solution:
In periodic table? the position of AI, Ga, In and Tl in the In AICI 3, Al is electron deficient (six electrons around AI)
respective periods is: and chlorine atoms have lone pairs of electrons which can be
donated. AI metal atoms complete their octet by forming a
3rd period Mg (s-block element) AI. coordinate bond with chlorine atom of the other molecule,
4tll period Zn (d-block element) Ga
AICI3. Thus, coordinate bond forming bridges, by chlorine
5th period Cd (d-block element) In
atoms between two Al atoms make a dimer molecule.
6th period Hg (d-block element) Tl
Thus, Al follows just after s-blockelements while Cia and
In follow afterd-block elements and Tl after d- and f-block
elements. The d-electrons in Ga and In and d- and [electrons
[l.SUMMARY AND IMPORTANT POINTS TO REMEMBER E~

1. Group llIA or 13 of tJie periodic table consists of six elements- of Ga is nearly equal to that of AI. It is because the
boron, aluminium, gallium, indium, thallium and ununtrium. d electrons in Ga do not screen the nuclear charge effectively
These are p-block elements. The configuration of the and the outer electrons experience more force of attraction
outermost energy shell is ninpl, i.e., this group marks the and thereby causing decrease in its radius.
beginning of p-block. 5. Density increases from boron to thallium. However, boron and
2. The members of group llIA or 13 are less metallic in aluminium have comparatively low values.
comparison to elements of IA (alkali metals) and IIA (alkaline 6. The melting points decrease from B to Oa ,and then increase
earth metals) group. from Ga to Tl. The high melting point of boron is due to the
Boron is regarded as a semi-metal. It is closer to non-metals fact that it exists as a giant covalent polymer in both solid"
than metals in its properties. Aluminium and rest of the and liquid state. Gallium has an unusual structure. It consists
elements are metallic in nature. of only Ga2 molecules. Gallium melting point is 30°C and it
3. Aluminium is the most abundant metal and third most exists as a liquid up to 2000°C and hence used in high
abundant element after oxygen and silicon by mass in the temperature thermometry. '
earth's crust. Boron is fairly rare but occurs as concentrated AI, In and TI all have closed'packed metal structures. How-
deposits of borax. Gallium is twice as abundant as boron but , ever, boiling points follow a regular decrease from B to Tl.
indium and thallium are much less common. 7. Since p electrons are held less tightly thans electrons, the
4. The atomic radii of members of group 13 are smaller than that first ionisation energy of each element is rather low as
of corresponding group IIA elements. The observed radius compared to first ionisation energy of alkaline earth metal of
the same period. The second and third ionisation energies The structure of boron nitride (BN) is similar 10 the structure
are considerably higher. The sum of three ionisation en~rgies of graphite. Recently, a crystalline form of boron nitride called
of these elements change in oscillating manner. B has borazon has been synthesised by application of high
maximum value. It decreases from B to AI, increases from Al temperature and pressure. This form is even harder than
to Ga, again decreases from Ga to hi and then increases from diamond. It is used as abrasive. Boron carbide (B 4C) is the
In to Tl. hardest known artificial substance and is called uorbide:
8. Boron having very high ionisation energy is least electro- 17. Boron combines with metals on heating to form borides. Tl),e
positive, i.e., regarded as more non-metallic. Aluminium is rest of the elements do not combine with metals.
most metallic or electropositive. The remaining three are 18. All the members of group IlIA form oxides of the type M203'
weakly metallic in nature. On moving down the group, there is gradual change from
9.' B and Al exhibit an oxidation state of +3. Ga, In and TI show acidic to amphoteric and then to basic character.
+ 1 and +3 oxidation stilte due to inert pair effect.
. Relative stability of +3 and + 1 oxidation states can be given
as,
B ::. .t;l > Ga > In > Tl + 3 stability decreases from B to Tl . Thallium also forms Tl20 which is more stable and behaves
B < Al < Ga < In < Tl + 1 stability increases from B to TI as alkali metal oxide.
T1 3+ ions show oxidising properties as these are converted 19. All these elements form hydroxides of the type M(OHh The
into TI+ ions. Gallium appears to show +2 oxidation state in basic nature of the hydroxides increases down the group.
GaCI 2. However, it is believed that this compound has B(OHh·(H3B03) is acidic. B(OHh coordinates with OH- group
structure Ga [GaC41 which contains univalent and trivalent of water releasing proton.
gallium ions.
10. The bonding in the compounds of IlIA elements is mainly B(OHh + 2H20~ [B(OH)4f + H30+
covalent due to following reasons : It reacts with NaOH to produce the sodium salt.
(a) small size of ions and their high charge are responsible
-2H 20 \ -
for high polarisation, B(OHh + NaOH :;;=!:: Na[B(OH)41 \ NaB02
(b) the sum of three ionisation energies is very high, (Sodium metaborate)
(c) the electronegativity values are high, Boric acid contains triangular BO~- ion in which boron lies
Boron always shows covalency. Many simple compounds of in sp2 hybrid state. In solid state, B(OHh units are hydrogen
other elements such as AlCl 3 and GaCl 3 are covalent when bonded to form two dimensional sheet.
anhydrous. However, AI, Ga, In and Tl form metal ions in AI(OHh and Ga(OHh are amphoteric as the tendency to
solutions as the hydration energies are very high. . rupture O-H bond decreases as tlie size of the ion
Thallium compounds .are ionic in nature. increases. In(OHh and TI(OHh are basic in nature ..
11. Group IlIA elements form complexes much more readily than 20•. The elements of group IlIA do not directly combine with
s-block elements because of their small size, increased charge
hydrogen. Howevet:, a number of hydrides are known.
and availability of vacant orbitals.
Borori forms a number of stable covalent hydrides with a
12. Finely divided impure boron burns in air forming oxide while
general formulae BnHn + 4 and BnHn + 6' These are called
pure boron is less reactive.
boranes. Boranes are electron deficient compounds. The
Aluminium reacts with air forming its oxide which proteCts it
expected BH3 is uriknown. Aluminium forms a polymeric
from further action. The oxide film on Al is so useful that in
hydrid~, (AlH3)n known as alane. Gallium forms dimeric
industry it is purposely increased by an electrolytic process
hydride, Ga2~ (digaUane) and indium form a polymeric.
called anodising. Auodised cooking vessels are used as non-
stick cookware. Ga and In are not affected in air. TI forms an hydride. Thallium does not form any hydride.
oxide on its surface. B, Al and Ga form complex anionic hydrides such as NaBH4,
LiAI~ and LiG~.
13. Boron is not affected by water or steam. Al decomposes cold
water if the oxide layer is not present on its surface. Ga and 21. All the elements of group IlIA form trihalides. The boron
In are -attacked by -water only in presence of oxygen. Tl is halides are covalent. Tbe boron halides act as Lewis acids.
attacked by moist air. All boron halides except BF3 are hydrolyse<;l. to boric acid.
14. Boron is not affected by non-oxidising acids while other BF3 forms an addition product with water as B-F bond is
elements dissolving forqring trivalent salts. . very strong.
The oxidising acids attack all the elements. However, Al and
Ga become passive with .conc. HN0 3.
BF3 + H20:;;=!:: H+ [BF30Hf == H30+[BF30Hf
Boron halides for complex halides of the type H[BF4].
15. B, Al and Ga react with alkali solutions evolving H2. In and
The trifluorides of AJ, Ga, In and Tl .are ionic while the
Tl are not -affected.
chlorides, bromides and iodides are largely covalent when
16. All these elements combine with halogens forming corres-
ponding halides. arihydrous. However,· their covalent nature decreases on
Boron and aluminium combine with nitrogen and carbon on moving from Ga to Tl. Trihalides fume in air and undergo
heating to form nitrides and carbides respectively. hydrolysis. They. also act as Lewis acids. However, this
tendency decreases with increase in size of the cation. The benzene (B3N3H6) is formed which has structure similar to
form complex halides of the type [MX6] 3-. They have the . benzene.
tendency to complete their octet by forming dimers. Dimer In diborane molecule, four hydrogen atoms and two boron
forms exist in vapour state and in non-polar solvents. Dimer atoms lie in one plane. Above and below this plane, there .
structures disappear when dissolved in water. This is due to are two bridging hydrogen atoms. Each boron atom forms
high hydration energy, when [M(H 2Q)6]3+ and 3X- ions are fOl,lr bonds though it has three electrons. Each bridge
formed. hydrogen atom is bonded to two boron atoms by sharing of
AICl3 + 9H 20 ~ [AI(H 20)6] (OHh + 3H+ + 3Cl- two electrons. Such a covalent bond is called three centre
electron pair bond or banana bond. Every boron atom is sp3_
12. The important minerals of boron are : hybridized. Dibprane is used for making· high energy fuels
(a) Borax, Na2B4~·lOH20, and propellants. . ' .
(b) Colemanite,Ca2B6011·5H20, 25. On heating borazine, a product similar to naphthalene known
(c) Boricacid, H3B03. as inorganic naphthalene' is formed.
Borax is also called Tineal or Suhaga. Tincal contains about 26. The relative Lewis acid character of boron trihalides is found,
45% borax. Natural. tincal is. dissolved in hot water and to follow the order:
insohible impurities are filtered off. The solution is concen- BI3 > BBr3 > BCl 3 > BF3
trated and cooled when crystals of borax are obtained. It exists This is due to back donation by smaller halogen atoms to
in three forms (a) Prismatic borax-Na2B40T lOH 20 (b) boron atom, i.e., forming pTC-pTC bond. This tendency is
Octahedral-Na2B40T5H20. This is Jeweller's borax. It is maximum in fluorine and decreases from F to ~ as the size
obtained by crystallising solution at 60"C (c) Anhydrous- increases.
Na2B4~. It is also called borax glass. It is not stable form as 27. Aluminium is extracted from bauxite ore (Al20 3·2H20). It is
it absorbs moisture and gradually converted into decahydrate usually contaminated with ferric oxide and silica. The removal
. form. The solution of borax is alkaline in nature as it is a salt of these impurities is very essential before the pure alumina
of a weak acid and strong alkali. is put to electrolytic reduction. The rem.ovaL is done by. the
On heating if .first swells up due to elimination of water and application of the following processes.
then melts which solidifies to transparent glassy bead. (a) Baeyer's process-Applied when Fe203 is the chief
Heat N BO impurity. Conc. solution of NaOH used.
. Na2B4~·lOH20 -IOH 0) . a2 4 7 (b) Hall's process-8odium carbonate is used.
2 Anhydrous
740°C .> ~NaB02 + B203, (c) Serpeck's process-The ore is mixed with coke and
Glassy bead
nitrogenis passed at 1800°C.
AlN is formed which is hydrolysed into Al(OHh. This method
When the hot glassy bead is brought in contact with a
is applied when silica is present in abundance. Ammonia is
coloured salt and heated again inflame, B 20 3 displaces
obtained as a by-product.
volatile oxides to form metaborates. Metaborates exhibit
The electrolysis of pure alumina presents two difficulties ..
characteristic colours. This is known as borax bead test.
(i) It is bad conductor of electricity.
Cu Fe Co Cr Ni
(ii) The melting point is about 2000°C.
Colour ~f metaborates Blue Green Blue Green Brown These difficulties are overcome by using a mixture containing
23. Boron is known to exist in· two forms (a) amorphous and alumina, cryolite (Na3AIF6) and fluorspar (CaF2) in the ratio
(b) crystalline. of 20 : 40 : 20. The fusion temperature of this mixture is 900"C
Amorphous boron is obtained by reduction of B2~ with Na and the mixture is good conductor of electricity. The
or K or Mg at high temperature in a covered crucible. electrolysis is carried out in an iron box lined by gas carbon
Crystalline form is obtained by the reduction of :8203 with which acts as cathode. The anode consists carbon rods. The
AI-powder. Crystalline boron is black and chemically inert overall chemical reaction is : 2Al20 3 ~ 4AI + 302
in nature. It is very hard. Amorphous boron is brown and Al of99.8% purity is obtained. It is further purified by Hoope's
chemically active. Boron is used as a deoxidiser in the casting electrolytic process.
of copper and for making boron steel which are used as 28. Because of its lightness, good conductivity and resistance
control rods in nuclear reactors. to corrosion, it is used for making alloys. The important alloys
24. Diborane is the simplest hydride of boron. It is prepared by are:
action of LiAlH4 on boron trichloride in ether or by reacting (a)'Magnalium (95% Al + 5% Mg)
, lithium hydride with boron trifluoride. It is a colourless gas (b) Duralumin (95% Al + 4% Cu + 0.5% Mg + 0.5% Mn)
which is stable at room temperature. It has disagreeable (c) Aluminium bronze (90% Cu + 9.5% AI + 0.5% Sn)
odour and causes headache. It bums in air and reactiori is (d) Nickeloy (9S%AI + 4% Cu + 1% Ni)
.highly exothermic. It is decomposed by water and alkalies (e) y-alloy (93% Al + 4% Cu + 2% Ni + 1% Mg)
liberating hydrogen. At low temperature, it forms an addition ., (f) Alnico (77% Steel + 2% Ni + 20% Al + 1% Co)
product with ammonia (B2~·2NH3)' When this ' product is
Thin foils of Al are used for wrapping soaps, cigarettes and
heated at 200"C, a volatile compound, borazole or inorganic
confectionery. Al wire is used in transmission lines and coils
for dynamos and motors. It is also used for making silvery The most· commonly known alum is potash alum,
paints and in thermite process. K2S04·AI2(S04h·24H20. It is used in purification of water,
29. Anhydrous AICl 3 is prepared by passing dry HCl or Cl 2 gas as an antiseptic and in stopping bleeding, as a mordant in
over heated aluminium turnings in absence of air. It is also dyeing and in leather tanning.
obtained by passing Cl 2 gas over heated mixture of Al203 31. Ultramarine is an artificial Lapis-Lazuli, a rare mineral
and coke. It is used as a catalyst in Friedel-Crafl's reaction. (Na3AI3Sr3S30u) which has fine blue colour. It is used in
The molecule is an autocomplex and is represented as : making blue paint.
32. Highly toxic element of group IlIA or 13 is thallium.
Cl~ /Cl~ /Cl 33. Precious stones such as sapphire, ruby, topaz, etc., are Al20 3
Al Al containing oxides of other metals.
Cl/ ~Cl/ ~Cl 34; Double sulphates of divalent ions and trivalent ions with 24
water molecules of crystallisation are called pseudoalums, e.g.,
Anhydrous AICl 3 is a Lewis acid. Anhydrous form is covalent MS04·M2(S04h·24H 20. These are not isomorphous with
while hydrated form AICI 3 ·6H20 is ionic. alums.
30. The term alum is used to describe any double sulphate having 3S. Aluminium acetate is commonly known as red liquor which
thecompositionM2S04·Mz(S04h·24H20,whereMstandsfor is used as a mordartt in dyeing and calico printing.
monovalent basic radical and M' for a trivalent basic radical.
- • •• -
-------
PRACTICE PROBLEMS - ••• - ~---
• Subjective Type Questions (b) Write the formulae of the compounds, you would expect
. B and Al to form with halogens, oxygen, sulphur,
1. Answer the following: nitrogen and carbon.
(a) Which element among group 13 elements has the highest S. Answer the following:
ionisation enthalpy? (i) What is the outer electronic configuration of group IlIA
(b) Which has higher ionisation enthalpy? elements?
Al or Ga (ii) Name the first two elements of group IlIA.
(c) Name the element of group 13 which forms the most (iii) What is Tincal?
stable compounds in +1 oxidation sta~e. (iv) What is thermitemixture?
(d) Name the metal which is commonly used as a reducing (v) What is inorganic benzene?
agent in metallurgical operations. (vi) Name the two metals present in common mum.
(e) Name the most abundant metal in the earth's crust. To (vii) Name the aluminium compound used in Friedel-Craft's
which group does it belong? reaction.
2. (i) By means of a balanced equation show how H 3B03 (viii) What is silver paint?
behaves as an acid in water. (ix) Name the metal which is commonly used as a reducing
(ii) Anhydrous aluminium chloride is used as a catalyst. agent in metallurgical operations.
Explain. (x) Name the compound of aluminium which is used as
(iii) Which elements of group 13 form amphoteric germicide and coagulant in the purification of water.
hydroxides. ? 6. Wbathappenswhen? .
(iv) Why boron is unable to form [BF6]3- ion? (i) Dry chlorine gas is passed over hot mixture of alumina
(v) Does Ga has +2 oxidation state in GaCI 2? and coke.
3 . . (i) What are basic units in the structure of orthoboric acid? (ii) Borax is heated strongly.
How are they linked? (iii) Excess of caustic soda is added to a solution of
(ii) What types of bonds are present in diborane? aluminium chloride.
(iii) What is the nature of boron halides? (iv) Water is added to aluminium nitride.
(iv) Why boron halides do not exist as dimers? Why AICl 3 (v) Water is added to aluminium carbide.
exists as A1 2Ci 6? (vi) Aluminium is heated with caustic soda solution.
(v) Explain briefly why boron trichloride is a gas and [I.I.T. 1997]
aluminium trichloride is a dimer solid. (vii) A mixture of borax and cobalt oxide is heated in flame.
4. Give formula of the following: (viii) Alum is heated.
(a) (i) Panderinite (ii) Rasorite [M.L.N:R. 1996] (ix) Alum is added to copper sulphate solution.
(iii) Jeweller's borax (iv) Feldspar (x) Aluminium reacts with HN0 3.
(v) Cryolite (vi) Corundum 7. Starting from borax, how would you obtain?
(vii) Alunite (viii) Turquoise (i) Boric acid, (ii) Boron trioxide, (iii) Boron,
(ix) Colemanite (x) Mica (iv) Boron nitride, (v) Boron trichloride.
8. Starting from alumina, how would you obtain? (vi) Although the ionisation potential of boron (8.30 eV) is
(i) Potash alum, less than gold (9.22 eV), yet former is a non"metal while
(li) Anhydrous aluminium chloride, the latter is a metal.
(iii) Aluminium nitride, (iv) Sodium aluminate. [Hint : This is due to structural difference in the solid states.
9. How you will obtain? In general, metals have large number of atoms as
(i) Anhydrous aluminium chloride from potash alum. neighbours while non-metals have relatively less
(n) Aluminium bromide from aluminium chloride. number of atoms as neighbours. Gold has 12 atoms
(iii) Aluminium sulphate from potash alum, as neighbours while boron has 6 or less atoms as
(iv) Alum from aluminium. neighbours in solid states.]
10. Give an account for the following: . (vii) Why boron does not form B3+ ion?
(a) No visible reaction occurs when aluminium is left in [Hint: The total sum of all the three ionisation energies. of
contact with concentrated nitric acid. [M.L.N.R. 199\] boron is so higt that lattice energy liberated by
(b) The hydroxides of aluminium and iron are insoluble in interaction of B3+ and anions is not enough for
water. However, NaOH is used to separate .one from the formation of this ion.]
other. [I.I.T. 1991J (viii) Aluminium fluoride is ionic while AlCl 3 is covalent.
(c) Anhydrous aluminium chloride cannot be prepared by [Hint : The size of chloride ion is larger than fluoride ion.'
heating hydrated AICI 3·6HzO. Due to higher polarisation in AlCI3, it behaves as a
(d) Aluminium vessels should not be cleaned with cleansing covalent compound. The electronegativity difference
agent containing washing soda. between AI and CI is 1.5 while between AI and F it
(e) Duralumin is used in aircraft industry. is 2.5. Thus, the bond between Al and F is ionic
11. Explain the following with relevant reason. and between Al and CI covalent in nature.]
(i) Aluminium vessels can'l5e used to store concentrated (ix) First ionisation potential of Al is lower than that of Mg.
nitric acid. [Hint: The electronic configuration of Al and Mg are Ii,
[Hint : RN03 forms a protective film, AI20 3, on the walls 2i 2p6, 3i 3pl and Ii, 2s2 2p6, 3i respectively.
of the containers which is not acted upon by conc. It is easier to remove electron from unpaired
HN0 3 ·] p-orbital than the paired s-orbital.]
(n) AICl3 forms a dimer but BCl3 does not form dimer. (x) Borazine is more reactive than benzene.
[Hint: In benzene, C=C bonds are non-polar while in
[Hint : AICl3 lacks back bonding as in BCI3 because' of
borazine, the bonds between buron and nitrogen are
increase in size of aluminium. Aluminium metal
polar. Addition is frequent in borazine, the more
negative group generally attaches to boron atoms.]
CI) <CI) <CI
Al Al . (xi) Certain metallic oxides are reduced with aluminium
CI Cl CI rather than with carbon during extraction.
atoms complete their octet by coordinate bond [Hint: The metals which react with carbon to form carbides
forming bridges by chlorine atoms between two AI are extracted from their oxides by using aluminium
atoms.] as a reducing agent as it has high affinity for oxygen.]
(iii) Aluminium metal is frequently used as redllcing agent (xii) Al(OHh is amphoteric. [M.L.N.R. 1994J
forthe extraction of metals such as Cr, Mn, Fe, etc. [Hint : It dissolves in acid as well as in alkalL]
[Hint : AI has great affinity for oxygen. AI, thus, removes 12. Write short notes on the following:
oxygen from the oxides ofless electropositive metals (i) Goldschmidt alumino-thermic process.
and acts as reducing \l.gent (n) Ultramarines.
Cr203 + 2AI ~2Cr + A120 3; t:..H =- vel (iii) Alums.
(iv) Aluminium cannot be prepared by the electrolysis of (iv) Electrolytic refining of aluminium metaL
aqueous solution of its salt. (v) Relative strength of boron halides as Lewis acids.
(vi) Borax bead test.
[Hint : Discharge potential of aluminium is higher than the
discharge potential of hydrogen. Thus, the aqueous 13. Describe the preparation, properties and uses of following
3 compounds:
solution containing A1 + and W ions, when
electrolysed, the H+ ions rather than AI3+ ions are (i) . Borax. (n) Potash alum.
discharged at cathode and hydrogen is evolved.] (iii) Anhydrous aluminium chloride.
(iv) Boric acid. (v) Borazine.
(v) The B-X distance is shorter than what is expected
14. Compare the properties of boron and aluminium under the
theoretically in BX3 molecule (X:;: CI,F, Br, I)?
following heads:
[Hint: The bond B-X in BX3 has double bond character
(i) Electronic configuration. (n) Nature of oxides.
due to back bonding. This brings resonance in the
(iii) Nature of chlorides. (iv) Action of acids.
molecule which is responsible for shorter B-X
distance than expected. (v) Nature of hydrides. (vi) Nature of nitrides.
i3 ('1'X _X 15. A certain salt (X) gives the following tests:

x=i3(XX f--7 X f--7
.
X - B,<+ ]
"'X
(i) Its aqueous solution is alkaline to litmus.
(li) On strongly heating it swells to give a glassy bead. (iv) Addition of NH40H and NaOH separately to the
(iii). When concentrated sulphuric acid is added to a hot solution of (A) gives a gelatinous precipitate which is,
concentrated solution of (X), white crystals of a weak however, soluble in excess of NaOH. Identify the
acid separate out. Identify (X) and write down, the compound (A).
chemical equations for reactions at steps (i), (li) and (iii). [Ans. (A) is A12Cl 61
[Roorkee 1992J 18. The metallic salt XY is soluble in water.
!HInt: (X) is borax, Na2B40T IOH20 When the solution is treated .with NaOH solution, a white
(i) Na2B4~ + 7H20 ~ 2NaOH + 4H3B03 precipitate (A) is formed. This precipitate is soluble in excess
(Strong) (Weak)
of NaOH solution to form a compound (B). When this
Due to presence of NaOH, the aqueous solution is solution is boiled with solid NH4CI. a precipitate of a
alkaline to litmus.
compound. (C) is formed. An aqueous solution of XY upon
(ii) Na2B407 ·lOH 20 Hea]t )
swe ls
Na2B407 + IOH20~ 'treatment with BaClz solution gave a white precipitate (D)
2NaB02 + B20 3 which was insoluble in dilute HCI. The salt XY forms a double
. . Glassy bead
salt with potassium sulphate. ,
(iii) Na2B407 + H2S04 + 5H 20 ~ Na2S04 + 4H3BO~1
[Ans. XY Al 2(S04h; [AJ = AI(OHh; [B] NaAI02;
16. A white crystalline compound (A) swells upon heating and [C] Al(OHh; [D] = BaS041
gives violet coloured flame on bunsen flame. Its aqueous 19. Furnish the following information in connection with the
solution gives the following reactions. .extraction of aluminium by the electrolytic process :
(a) A white precipitate with BaClz in presence of HCI. (i) the composition of the electrolyte;
(b) When treated with excess of N~OH, it gives white (li) the reactions that take place at the electrodes;
gelatinous precipitate. The white precipitate dissolves (iii) the component of the electrolyte consumed;
in NaOH and reappears on boiling with concentrated (iv) collection of the extracted metal;
solution of NH4Cl. (v) the nature of the electrodes;
(c) It gives yellow precipitate with cobaltinitrite solution. (vi) the temperature of electrolysis;
Identify the compound (A) and explain the reactions. (vii) the role of different components of the electrolyte in
!HInt: The. compound (A) is potash alum, the process of extraction.
K2S04·Al2(S04h·24H20. It swells upon heating 20. Compound (X) on reduction with LiAl~ gives a hydride (Y)
due to evolution of water molecules. containing 21.72% hydrogen along with other products. The
K2S04'
.
Al 2(S04h· 24H~0 swesup
He~~ng ) K ZS04 · A12(S04h + 24H 20 compound (Y) reacts with air explosively resulting in boron
trioxide. Identify (X) and (Y). Give balanced reactions
It gives violet colour to flame due to presence of potassitim
involved in the formation of (Y) and its rea~tion with air. Draw
salt.
(a) The solution consists. sulphate ions which combine with Ba2+ tile structure of (Y). II.LT.2001J
ions to form white insoluble precipitate. 1BInt: 4BCl3 + 3LiAlH4 ~ 2B2H6 + 3AlCl 3 + 3LiCI
. Ba2+ + SO~- ~ BaS04 (X) (n
% of hydrogen in B2 H 6 = 27~62 x 100 = 21.72
(b) With NH40H, aluminium hydroxide is precipitated which
dissolves in NaOH forming sodium meta-aluminate. B2H6 + 302 Explosion) B20 3 + 3H 20
AI2(S04h+6NH40H 2Al(OHh + 3(NH4hS04 (Air)
AI(Ol:lh + NaOH ~
ppt.
NaAI02 + 2H20
Soluble
Structure of B2~
H) ,R~>B <H
B< ]
H °H' H
The solution on heating with amrilonium chloride gives a
precipitate of Al(OHh. 21. (a) How is boron obtained from borax? Give chemical
NaAl0 2 + NH4CI + H20 ~ AI(OHh + NaCl + NH3 equations with reaction conditions. Write the structure
(c) Potassium salt gives yellow precipitate with cobaltinitrite .. of B2H6 and its reaction with HCI. [I.I.T. 2002J .
solution. IBInt s See the text.J
2K2S04 + Na4ICo(N02)6J ~ ~[CO(N02)6J + 2Na2S04J (b) Write balanced equations for reactions of BF3 and
, Yellow ppt. .
A4C 3 with water. [UT.2002J
17. An inorganic compound (A) shows the following reactions: [1IJat, 4BF3 + 6H20 ~ H3B03 + 3H30 + 3BF4
(i) It is white solid, exists as dirrier and fumes in wet air. A4C3 + 12H20 ~ 4Al(0H)3 + 3Cf4]
(li)It sublimes at 18O"C and forms monOmer if heated,to
4000C.
(iii) Its aqueous solution ttirns blue litmus to red and gives
a white precipitate with AgN03 solution which is
soluble in NH4 0H. .
• Matching Type Questions [C] (it) Inorganic benzene (i) NazB4O,·lOH20
(b) Jeweller's borax (ii) Bz~
Match the following : (c) Borax (iii) Na2B4O,·5HzO
[A] (a) Anhydrous AlCl 3 (i) Antiseptic
(d) Diborane (iv) Mordant
(b) Alum (ii) Alloy (e) Alum (v) B~3~
(c) Ultramarine (iii) Friedel-Crafts reaction
[0] (a) Good thermal (i) Building ships and
(d) Borax, (iv) Complex blue coloured
conductivity aircrafts
silicate
(b) Good electrical (ii) Utensils
(e) Magnelium (v) Tincal
conductivity
[B] (a) Colernanite (i) Na3AlF6 (c) Low density and (iii) Electric wires
(b) Cryolite (ii) KAl(S04)z·12HzO resistance to corrosion
(c) Bauxite (iii) Ca2B60 j r5HzO (d) Non-toxicity (iv) Adsorbent
(d) Borax (iv) NazB4o,·lOHzO (e) GelnatureofAl{OHh (v) Food packing
(e) Potash alum (v) Alz~·2HzO
Answers : Subjective 'JYpe Questions 5. (i) ns2 npl, (ii) Boron and aluminium, (iii) It is a mineral of boron.
1. (a) Boron (b) Gallium (c) Thallium Its composition is Na2B40?, lOH20, (iv) Mixture containing 1 part
(d) Aluminium (e) Aluminium, Group 13 Al powder and 3 parts Fe203, (v) Borazole or borazine, B3N3H6
2. (i) B(OHh + H-OH [B(OH)4r + H+ is known as inorganic benzene, (vi) Common alum is the double
(ii) At atom in AlCI 3 has only 6 electrons in its ,valence shell. It sulphate of potassium and aluminium. Its composition is.
K2S04·A12(S04h·24H20, (vii) Anhydrous aluminium chloride,
needs two more electrons to complete its octet. It acts as a
AlCI 3, (viii) Finely divided aluminium powder suspension in linseed
Lewis acid in reaction. It helps to generate electro'phile R+ or
oil, (ix) Aluminium; (x) Common alum, K2S04,Al2(S04h24H20.
RCO+, etc., which attacks benzene, i.e., the aromatic ring.
6. (i) Al2~ + 3C + 3Cl2 ~ 2A1C1 3 + 3CO
(iii) Aluminium and gallium
Al(OHh + 3HCI AlCl3 + 3H20 (ii) Na2B407·1 OH20 -IOHzO) Na2B407----> 2NaB02 + B203
2Al(OHh + 2NaOH + 6H20 ~ 2NaAl(OH)4 + 3H2 (iii) AlCl3 + 3NaOH ~ Al(OH)3 + 3NaCl.
Ga(OHh + ,3HCI ----> GaCI3 + 3H20
AI(OH)3 + NaOH ~ NaAl02 + 2H20 .
2Ga(OH)3 + 2NaOH + 6H20 ----> 2NaGa(OH)4 + 3H2
(iv) Boron cannot expand \>Ctet due to absence of d-orbitals in the (iv) AlN + 3H20 ~ AI(OH)3 + NH3
valence shell. (v) Al4C 3 + 12H20 ~ 4Al(OHh + 3C~
(v) GaCl2 is actually Ga2CI~, i.e., Ga+[Ga3+C4J. Ga has thus +1 (vi) 2AI + 2Na:OH + 2H20 ----:-t 2NaAI02 + 3H2
and +3 oxidation states and not +2.
(i) The basic units are BO~-' ions which are linked tru:ough Na2B407 --,7 2NaB02 + B203
2
3. (vii) Na2B407 ·lOH20 -lOH 0)
hydrogen bonds. B203 + CoO ~ Co(B02h
(ii) There are two types of bonds in diborane two electron nOffi?al Cobalt metaborate
bonds and three centred two electron bonds. (viii) It melts and loses water of crystallisation upto200"C and·
(iii)'Boron ha)ides are electron deficient compounds. They act as white porous mass isob~ned on red heat. This white mass
Lewis acids. is known as burnt alum.
(iv) Boron atom being small in size is unable to accommodate four 200·C
K2S04 ·AI2(S04h . 24H20 ~ K2S0 4 . AI 2(S04h + 24H20
larg'e sized halogen atoms around it: " Red heat '
(v) In BCI3, boron 'attains an octet of electrons by means of K2S04 · A1i(S04h ) K2S04 + Al203 + 3S03
p1t-p1t bonding between B and CI atoms. Thus, it exists as a (ix) Be.ing more electropositive, it displaces copper from copper
monomeric gas. Due to large size of AI, efficient p1t-p1t bonding sulphate.
cannot occur. Thus, AlCl 3 dimerises to attain an, octet by 3CUS04 + 2Al ~ Al2 (S04)3 + 3Cu
forming adative bond between CI and AI atoms. Thus, it exists (x) Nitric acid whether dilute or concentrated hardly affects
as a solid. aluminium at all. Aluminium is rendered passive. A thin film
4. (a) of Al20 3 is formed on the surface of the metal.
(i) Ca2B6011·3H20, (ii) Na2B40?,4H20, 7. (i) Na2B407 + H2S04 + 5H20 ~ 4H3B03 + Na2S04
(iii) Na2B40?,5HzO,
(v) Na3AIF6,
(iv) KAISi308,
(vi) A1203, (ii) 2H3B03 s::zy) B20 3 + 3H20
(vii) K2S0!l·AI2(S04h-4Al(OHh,(viii) AlP04·AI(OHh·H20, (iii) B2~ + 3Mg ~.2B + 3MgO
(ix) Ca2B6011·5H20, (x} K20·3AI203·6Si02·2H20.
, (iv) Na2B4~ + 2NH4Cl ~ 2BN + Bi03 + 2NaCI + 4H20.
(b) Formulae of the compounds of boron and aluminium: BX3
and AlX3, B20 3 and Al203, B2S3 and Al2S3, BN and AlN, (v) B203 + 3C + 3Clz ~ 2BCl3 + 3CO
B 12C3 and A4C3•
8. (i) AlZOJ + 3H2S04 BOiled) A1 2(S04h + 3H20 (c) Hydrolysis of AlCI3 occurs into AI 20j.
Calculated quantity of K 2S04 is added to above solution. The 2AICi 3 + 3HzO ---7 Al 20 3 + 6HCl:
. solution is cooled when crystals of alum are obtained. (d) Aluminium dissolves in caustic alkalies.
A12(S04h + K2S04 + 24H 20 ---7 K ZS04·Al2(S04h·24H 20 (e) Duralumin is an alloy of aluminium (95%), Cu (4%), Mg (0.5%)
(ii) A1 2 0 3 +3C+3CI 2 JOOO'c) 2AICI 3 +3CO and Mn (0.5%). It is light and tough. It is resistant to corrosion.
(iii) Al 20 3 + 3C + N 2 ISOO'C) 2AIN + 3CO 19. (i) Pure Al20 3 20%; Cryolite Na3AIF6 60%; Fluorspar CaF2
20%.
(iv) . Al 20 3 + 6NaOH 2Na3AI03 + 3H 20
(ii) Reactions at electrodes.
9. (i) K2S04-A12(S04h·24H20 + 6NH40H
At cathode: A1 3+ + 3e ---7 Al
K2S04 + 3<NH4hS04 + 2Al(OHh + 24H 20
ppt:
At anode: 2F- ---7 F2 + 2e
Heat 2Al203 + 6F2 ---7 4AlF3 + 302
2AI(OHh ---;:---t'AI 20 3 + 3HzO
lOOO'C . . (iii) The component consumed during electrolysis, A1203'
Ah03 + 3C + 3CI 2 ~ 2AICI3 + 3CO (iv) The liberated metal in the molten state is taken out through
(ii) AICl 3 + 3NH40H ---7 AI(OHh+ 3NH4CI an outlet near the bottom of the electrolytic cell.
ppt.
(v) Carbon lining of the electrolytic cell acts as cathode and
AI(OHh + 3HBr ---7 AIBr3 + 3HzO carbon rods act as anode. .
or Al(OH)3 Al 20 3 + 3H 20 (vi) 950"C.
Alz03 + 3C + 3Br2 ---7 2AlBr3 + 3CO (vii) Molten cryolite acts as the solvent for Ah03' Fluorspar
decreases the viscosity of the mixture. Both decrea~e the
(iii) Potash alum + NH 40H ---7 Al(OHh
ppt.
fusion temperature from 2050°C to 9500C and make the mass
good conductor' of electricity.
2AI(OHh + 3H2S04 Al2(S04h + 6H20
(iv) Al H2S0 4 ) Al 2(SO) K2SO. soln.) K SO ·Ah(SO ) ·24H
43 SolutionIs 24_ 43 2
° Answers : Matching Type Questions
[A] (a-iii); (b-i); (c-iv); (d-v); (e-ii)
cooled
10. (a) Aluminium is rendered passive. [B] (a-iii); (b-i); (c-v); (d-iv); (e-ii)
(b)· AI(OHh dissolves in NaOH while Fe(OHh remains insoluble. [C] (a-v); (b-iii); (c-i); (d-ii); (e-iv)
Al(OHh + NaOH ---7 NaAlOz + 2H20 [D] (a-ii); (b-iii); (c-i); (d-v); (e-iv)
fUUSTRA1fONS OF. OBJECTIVE QUESTIONS

1. .Correct match is : [Hint: Cryolite-Na3AlF6; Feldspar-KAlSi30 s ;
(a) Ordinary form of borax Na2B40?,5H20 Mica K20·3AI203-6Si02-2H20 ; Fluorspar-CaF21
(b) Colemanite Ca2B6011,5H20 5. The function of fluorspar in the electrolytic reduction of
(c) Boronatrocalcite 2Mg3BgOlS,MgCl2 alumina dissolved in fused cryolite (Na3AIF6) is :
(d) Octahedral form of borax Na2B4~·lOH20 (a) as a catalyst
Ans. (b) (b) to lower the temperature of melt and to make the fused
2. Which of the following is correct? mixture very conducting
(a) The members of BnHn + 6 are less stable than BnHn + 4 (c) to decrease the rate of oxidation of carbon anode
series (d) none of the above '
(b) Dlborane is coloured and unstable at room temperature Ans. (b)
(c) The reaction of. diborane with oxygen is endothermic 6. A layer of coke is spread over bauxite during electrolytic
(d) All of the above' reduction of alumina by Hall Heroult process. This layer
,Ans. (a) . . acts as alan :
3. In which of the following, a salt of the type KM02 is (a) flux
obtained? . . I (b) slag to remove impurities
(a) B2~+KOH(aq.)~ (b) Al+KOH(aq.)~ (c) reducing agent •
(c) Both (d) None (d) insulation and does not allow heat to escape
Ans. (e) . Ans. (d) .
[Hint : B2H6 + 2KOH + 2H20 ~ 2KB02 + 6H2;
Pot. metaborate 7. Which of the following compounds is formed in borax bead
2AI + 2KOH + 2H20 ---7 2KAI0 2 + 3H2] test? [A.I.I.M.S.2004]
Pot. metaaluminale (a) Metaborate (b) Tetraborate .
4. Which of the following minerals does not contain alu- (c) Double oxide (d) Orthoborate
minium? Ans. (a)
(a) Cryolite (b) Mica [Hint: Borax on heating gives B2~ (transparent glassy mass).
(c) Feldspar (d) Fluorspar When hot B20 3 is brought in contact with a coloured salt,
Ans. (d) metaborates are formed. .
Elements of Group rnA or 13 (Boron and Aluminium) 395
Na2B407.10H20~ B20 3 co~oured)

su stance .
Metaborate 12. Al203 can be converted to anhydrous AlCl3 by heating: .
[C.B.S.E. 2006]
CUS04 + B 20 3 ---+ Cu(B02h + S03] (a) a mixture of .N203 and carbon in dry Cl2gas
8. Aluminium chloride exists as a dimer, Al 2C16, in solid state as (b) Al 20 3 with Cl2 gas
well as in solution of non-polar solvents such as benzene. (c) Al20 3 with HCI gas
When dissolved in water, it gives:' [A.I.E.E.E. 2004] (d) Al 20 3 with NaCl in solid state
(a) Al 3+ + 3CI- (b) [Al(H20)6]3+ + 3Cr Ans. (a)
(c) [AI(OH)6]3- + 3HCI (d) Al 20 3+ 6HCI [Hint : Alz0 3 + 3C + 3Clz ---+ 2AlCl3 + 3CO]
Ans. (b) 13. Boric acid is used in carrom boards for smooth gliding of
[Hint : The dimeric formula, Al2Cl6, is retained in non-polar pawns because: . .
solvent but is broken into [AI(HzO)6]CI3 on dissolution
(a) H3B03 molecules are loosely chemically bonded and
in water on account of high heat of hydration.]
hence soft
9. Inorganic graphite is : (b) its low density makes it fluffy
(a) B3N3fIQ (c) it is chemically inert with the plywood
(c) SiC (d) H-bonding in H3B03 gives it a layered structure
Ans. (b) \
ADS. (dj.
10. Hydrated AICl3 is used as : 14. Boric acid is polymeric due to:
(a) catalyst in cracking of petroleum (a) its monobasic nature
(b) catalyst in Friedel-Crafts reaction (b) its acidic nature
(c) mordant (c) the presence of hydrogen bonds
(d) all of the above (d) its geometry
Ans. (c) ADS. (c)
11. Borax is used as a cleansing agent because on dissolving in 15. The chemical formula of feldspar is:
water, it gives: [A.I.I.M.S. 2006] [E.A.M.C.E.T. (Engg.) 2007]
(a) alkaline solution (b) acidic solution (a) KAISi 30 g (b) Na3AIF6
(c) bleaching solution (d) neutral solution (c) NaAI02 (d) K2S04·Al2(S04hAAl(OHh
Ans. (~)
Ans. (a)
[Hint : Borax dissolves in water and gives an alkaline solution.
16. The chief impurity present in red bauxite is:
Na2B407 + 7H zO ~ 2NaOH + 4H3B03 ]
Strong Weak acid [D.CE. (Engg.) 2007]
base
(a) Si~ (b) Fe2~
(c) K2S04 (d) NaP
ADS. (b)
Set I : This set contains questions with one COtTeCt answer.
1. The fOnTIula of corundum is: 12. Which one is borax?
(a) Al20:3 0 (b) Al20 3·H20 o (a) Na2B4~·lOH20 0 (b) Na2B4~4H20 0
(c) Al2O:3·2H20 0 (d) Al20 3·3H20 o (c) Ca2B60 ll ·5H20 0 (d) CaB4~ . 0
2. Aluminium belongs to: 13. The electrolytic reduction method for extraction of aluminium
(a) s-block elements o (b) p-block elements o was discovered by:
(c) d-block elements o (d) i-blOCk elements o (a) Hoope o (b) Hall and Helvoult o
3. Aluminium fOnTIs:
(a) electrovalent compounds only o (c) Baeyer o (d) Serpeck o
14. Cryolite is:
(b) covalent compounds only o (a) sodium fluoride o
(c) electrovalent and covalent compounds both o (b) aluminium fluoride o
(d) coordinate compounds· only o (c) sodium aluminium fluoride o
4. Alumina is: (d) none of the above o
(a) acidic 0 (b) basic 0 15. Which one of the following is not ari C/re of aluminium?
(c) neutral 0 (d) amphoteric 0 (a) Bauxite 0 (b) Corundum' 0
5. The metal ~hich evolves hydrogen, when treated with (c) Epsomite 0 (d) Alum stone 0
caustic soda solution is:
16. When alumina is heated with carbon in nitrogen atmosphere,
(a) Cu 0 (b) Hg 0
the products are:
(c) Ni 0 ,(d) Al 0 (a) Al +CO . o
(b) AI+ CO2 0
6. When aluminium is heated in atmosphere of nitrogen fOnTIS (c) Al+CO+C02 0 (d) AlN +CO 0
a nitride offonTIula: 17. When alumina is electrolysed in presence of cryolite, the gas
(a) AlN 0 (b) Al3N 0
liberated at graphite anode is:
(c) AlN3 - o (d) Al2N3 . 0 (a) F2 0 (b) D.2 o
7. Which one of the following is most abundant in the earth's (c) CF4 0 (d) F20 o
crust?
18. Theelectrolysis of pure alumina is not feasible because:
(a) B 0 (b) Al 0
(a) iUs bad conductor of electricity and its fusion tempera-
(c) Ga 0 (d) In 0
ture is high 0
8. The major role of fluorspar (CaF2) which is added in small (b) it is volatile in nature 0
quantity in the electrolytic reduction of alumina dissolved in (c) it is decomposed when fused 0
fused cryolite, Na3AIF6, is : (d) it is amphoteric 0
(i) as a catalyst
19. In the extraction of aluminium, the. function of cryolite is to:
(ii) to make the fused' mixture very conducting.
. (a) lower the melting point ~f alumina 0
(iii) to lower the temperature of the melt
(b) increase the melting point of alumina 0
(iv) to decrease the rate of oxidation of carbon at the anode
(c) remove impurities from alumina 0
(a) (i) and (ii) 0 (b) (ii) and (iv) 0 (d) minimise the anodic effect 0
(c) (ii) and (iii) 0 (d) (i)and (iii) 0 20. Aluminium does not react with:
9. Al and Ga have nearly the same covalent radii because of:
(a) greater shielding effect of s electrons of Ga atoms 0
(a) NaOH 0 (b) HQ o
(b) poor shielding effect of s electrons of Ga atoms 0
(c) N2 0 (d) HN03 o
21. The common impurities present in bauxite ore are:
. (c) poor shielding effect of d electrons of Ga atoms 0 (a) Fe203 and CuO 0 (b) Fe203 and PbO o
. (d) greater shielding effect of d electrons of Ga atoms 0
10. Which of the following has the lowest melting point?
(c) FeZ03 and Si02 0 (d) SiOz and CuO o
22. In Hall's process, the ore is'mixed with:
(a) B 0 (b) Ga 0
(c) Al .0 (d) Tl 0
(a) coke 0 (b) calcium carbonate o
11. Which of the following is acidic in nature?[A.I.I.M.s~ 2004]
(c) sodium hydroxide 0 (d) sodium carbonate o
. 23. Borax is prepared by treating colemanite with:
(a) Be(OH)z 0 (b) Mg(OH)z 0 (a) NaN03 0 (b) NaCI 0
(c) AI(0H)3 0 (d) B(Offl3 0 (c) NaHC03 .0 (d) Na2C03 0
[Iiint: Mg(OH)z is a weak base and lle(OH)2 and A1(OH)3 are 24. On the addition of mineral acid to an aqueous solution of
amphoteric in nature. B(OH}J can accept one hydroxyl ion borax, the following compound is formed:
from water and proton is released. Thus, it acts as a Lewis (a) boron hydride 0 (b) orthoboric acid o
acid.] (c) metaboric acid 0 (d) pyroboric acid o
Elements of Group IiIA or 13 (Boron and Aluminium) 397
25. Which of the following compounds is formed when boron Therefore, it should not ,be stored in glass or metal
trichloride is treated with water? containers.]
(a) H3B03+HCI 0 (b)B2H6+HCl 0 38. Which one of the following is a correct statement?
[P.M.T. (M.P.) 1993]
(c) B20 3 +HCI 0 (d) None of these 0
(a) The hydroxide of aluminium is more acidic than that of
26. . ..... is the by-product obtained in the Serpek's process.
(a) Oxygen 0 (b) Ammonia ' 0 ~oo 0
(b) The hydroxide of boron is basic while that of aluminium
(c) Nitrogen dioxide 0 (d) Nitric oxide 0
is amphoteric 0
27. Aluminium metiu is purified by:
(c) The hydroxide of boron is acidic while thatof aluminium
(a) Hoopes process 0 (b) Hall's process o is amphoteric 0
(c) Serpek's process 0 (d) Baeyer's process o (d) The hydroxides of both boron and aluminium are
28. Which one of the statements is correct for Al metal?
amphoteric 0
(a) It is bad conductor of electricity 0
(b) It is malleable and ductile 0 39. B(OHh + NaOH~Na[B(OH)4]
(c) It is found free in nature 0 How can this reaction be made to proceed in forward
'(d) Alloys of aluminium are heavy b direction? ' [I.I.T.2006]
29. Which one of the following is not the alloy of aluminium? (a) Addition of cis-I,2-diol 0
(b) Addition of borax [J
(a) Magnalium 0 (b) Duralurnin 0
(c) Germansilver 0 (d)' Aluminium bronze 0 (c) Addition of trans-I,2-diol 0
30. In the alumino-therrnite process, Al ~cts as: (d) Addition of Na2HP04 [J
[Hint : Na[B(OH)4] is removed from the equilibrium due to the
(a) an oxidising agent 0 (b) afIux 0
formation, of chelate compound ,with cis-I,2-diol and the
(c) solder 0 (d) a reducing agent 0 reaction moves in the forward direction.
31. Alumina may' be converted into anhydrous aluminium
chloride by: CH 2-OH [HO" /OH]- [H 2C-O" O-'.CH2]-'
21 ,+ /B" 4 /B( 1 +4H2 0]
(a) heating it with conc. HCI 0 CH 2-OH HO OH H 2C-O O-CH2
(b) heating in a current of dry chlorine 0
(c) heating it with rock salt 0 40. Colemanite is a mineral of:
(d) mixing it with carbon and heating the mixture in a current (a) Ca 0 (b) B 0
of dry chlorine 0 (c) Al 0 (d) Mg 0
32. Which of the following statements about anhydrous 41. The correct order of atomic radii of group 13 elements is :
aluminium chloride is'correct ? (a) B < Al -, Ga > In 0 (b) B < Al < Ga <In 0
(a) It exists as AICl3 molecule o (c) B < Al < Ga - In 0 (d) B < Ga < Al - In 0
(b) It is a strong Lewis base o 42. When strongly heated, orthoboric acid leaves a residue of:
(c) It sublimes at 100°C under vacuum o (a) metaboric acid 0 (b)' tetraboric acid 0
(d) It is not easily hydrolysed o (c) boric anhydride 0 (d)boron 0
33. Which hydroxide is soluble in sodium hydroxide? 43. Boric acid is prepared from borax by the action of:
(a) Fe(OR)3 0 (b) Al(OR)3 o (a) hydrochloric ac~d 0 (b) sodium hydroxide 0 '
(c) Cr(OR)3 0 (d) All of these o (c) carbon dioxide 0 (d) sodium carbonate 0
34. The nature of the solution of potash alum is: ' 44. When a solution of sodium hydroxide is added in excess to
(a) acidic [J (b) basic o the solution of potash alum, we obtain:
(c) neutral 0 (d) uncertain o (a) a white precipitate 0
35. Which one of the following is alum? (b) bluish white preCipitate. 0
(a) NH4Fe.(S04h·12H20 o (c) a clear solution 0
(b) KCl-MgCI2·6H20 o (d) a crystalline mass 0
45; Borax bead test is responded by:
(c) ~hS04·FeS04·6H20 o (a) divalent metals 0 (b) heavy metals 0
(d) N~·S04 o (c) light metals 0
36. Alums are used for: (d) metals which form coloured metaborates 0
, (a) tanning of leather 0 (b) coagulation o 46. When Al is added to potassium hydroxide solution:
(c) purification of water 0 (d) all of these [J
(a) no reaction takes place 0
37. The liquefied metal expanding on solidification is: (b) oxygen is evolved' 0
[A.I.I.M.S. 2004] (c) wa.ter is produced 0
(a) Al o (b) Ga o (d) hydrogen is evolved 0
(c) Zn o (d) Cu o 47. Borazole, B3N3H6 is related to benzene as :
[Hilit : Ga is a soft silvery white metal and is liquid at room (a) isoelectronic '0 (b) isostructural 0
temperature. When it solidifies, it expands by 3.1 per cent.
(c) both (a) and (c) 0 (d) none of these 0
48. When excess of NaOH solution is added in potash alum, the (c) basic copper carbonate []
product is : (d) prussian blue 0
(a) A bluish precipitate 0 (b) Clear solution 0 57. Which of the following is most acidic?
(c) A white precipitate 0 (d) A greenish precipitate 0 (a) Na20 0 (b) MgO 0
"[Hint : Alum consists A}z(S04h which reacts with NaOH. (c) Al203 0 (d) Cao 0
Al2(S04h + 6NaOH ----0 2Al(OHh + 3Na2S04 58. Al 20 3 formation from aluminium and oxygen involves
Al(OHh + NaOH----o NaAl0 2 + 2H 20 evolution of a large quantity of heat, which makes aluminium
Soluble use in:
The other sulphates K2S04 and Na2S04 are also soluble in (a) deoxidiser 0 (b) confectionary 0
water. Thus, a clear solution is obtained.] (c) indoor photography 0 (d) thermite welding 0
49. Three centred bond is present in: 59. Anhydrous aluminium chloride is obtained when:
(a) NH3 0 (b) B2Ht; o (a) aluminium oxide reacts with HCI 0
(c) 003 0 (d) AlCl3 o (b) aluminium reacts with HCI 0
SO. In diborane: (c) aluminium is heated in a current of dry chlorine 0
(a) 4 bridged hydrogens and two terminal hydrogens are (d) aluminium hydroxide reacts with HCI 0
present 0 60. Alum is used by dyers of cloth:
(b) 2 bridged hydrogens and four terminal hydrogens· are (a) for fire proofing fabrics 0
present 0 (b) as first aid for cuts 0
(c) 3 bridged hydrogens and three terminal hydrogens are (c) for softening hard water 0
present 0 (d) as mordant 0
(d) none of the above 0 61. Aluminiumchloride exists as a dimer because aluminium has:
51. Aluminium vessels should not be washed with materials (a) greater LP. 0 (b) incomplete p-orbital 0
containing washing soda since: (c) larger radius 0 (d) high nuclear charge G
(a) washing soda reacts with aluminium to form soluble 62. Which of the following metals burns in air at high temperature
aluminate .0 with the evolution of much heat?
(b) washing soda is expensive 0 (a) Cu 0 (b) Hg 0
(c) washing soda is easily decomposed 0 (c) Pb 0 (d) Al 0
(d) washing soda reacts with aluminium to form insoluble 63. BC13 does not exist. as a dimer but BH3 exists as B2~
aluminium oxide 0 because:
52. Aluminium is more reactive than iron. But aluminium is less (a) Cl 2 is more electronegative than hydrogen 0
easily. corroded than iron because: (b) large size of chlorine atom does not fit between small
(a) oxygen forms a protective oxide layer on aluminium 0 sized boron atoms, while small sized hydrogen atoms
(b) aluminium is a noble metal 0 occupy the space between boron atoms 0
(c) iron undergoes reaction easily with water 0 (c) there is p1t-d1t back bonding in BCl 3 0
(d) iron forms mono and divalent ions 0 (d) both (b) and (c) 0
53. Alumina is: 64. Boron carbide, B4C, is widely used for:
(a) a bad conductor of electricity 0 Ca) making acetylene 0
(b) a good .conductor of electricity 0 (b) making plaster of Paris 0
(e)' a dehydrating agent 0 (c) as a hardest substance after diamond 0
(d) soluble in water 0 (d) making boric acid 0
54. .............. takes place in presence of anhydrous aluminium 65. Therrnite is a mixture of:
chloride. (a) 3 parts of powdered aluminium and 1 part of feme oxide
(a) Friedel-Crafts reaction 0 o
(b) Cannizzaro reaction 0 (b) 1 part of powdered aluminium and 3 parts of feme oxide
_ (c). Kolbe's reaction 0 o
(d) Hofmann's reaction 0 (c) I part of powdered aluminium and I part of ferric oxide
55. Alumina is not used as: o
(a) refractory material 0 (d) 2 parts of powdered aluminium and 3 parts of ferric oxide
.. 0
(b) a medium in chromatography
(c) abrasive
0
0
.
66. The most covalent aluminium halide is:
(d) a .white pigment 0 (a) AIF3 0 (b) Al0 3 0
56. The blue coloured mineral 'LapisLazuli' which is used as a (c) AlBr3 0 (d) AlI3 0
semi-precious stone is a mineral of the following class: 67. In the purification of bauxite by Baeyer's process, the
(a) sodium alumino silicate 0 chemical used is:
(b) zinc cobaltate 0 (a) Na2C03 0
Elements of Group lllA or 13 (Boron and Aluminium) 399
(b) cryolite 0 80. InB2~:
(c) NaOH 0 (a) there is direct boron-boron bond 0
(d) a mixture of NaOH and Na2C03 0 (b) the boron atoms are linked through hydrogen bridges
68. When aluminium is heated with cone. H2S04: o
(a) aluminium becomes passive 0 , (c) the structure is similar to C2~ o
(b) hydrogen is liberated 0 (d) all the atoms are in one plane o
(c) oxygen is liberated 0 81. The colour of ferric metaborate is:
(d) sulphur dioxide is liberated 0 (a) yellow 0 (b) blue o
69. When aluminium hydroxide dissolves in NaOH solution, the (c) green 0 (d) grey o
product is: 82. Therrnite is a mixture of iron oxide and:
(a) [Al(H20h(OHhl 0 (b) [Al(H20MOHht 0 (a) Al powder 0 (b) Zn powder o
(c) [Al(H20hCOH)4r 0 (d) [Al(H20)s(OH)]2+ 0 (c) K metal 0 (d) Na metal o
70. Which one of the following statements regarding BF3 is not 83. Inorganic graphite is:
correct? (a) B3N3~ 0 (b) B2~ 0
(a) It is a Lewis acid 0 (c) BN 0 (d) BF3 0
(b) It is an ionic compound 0 84. Which is used in high temperature thermometry?
(c) It is an electron deficient compound 0 (a) Na 0 (b) Ti 0
(d) It forms adducts ' 0 (c) Ga 0 (d) Hg 0,
71. Which one is not a borane? 85. LiAlH4 is obtained by reacting an excess of ...... with an
o ethereal solution of AICI3.
(a) B5H9 0 (bY B5HlO
(c) B5HIl 0 (d)B!#lO o (a) LiH 0 (b) Li 0
(c) LiCI 0 (d) LiOH 0
[Hint: General formulae of boranes are BIlHn+4 and B IlH/l+ 6']
86. Boron compounds behave as Lewis acids because of their:
72. In which of the following elements + I oxidation state is more
(a) acidic nature 0
stable than +3?
(b) covalent nature 0
(a) B o (b) Al o (c) ionisation property 0
(c) Ga o (d) TI o (d) electron deficient nature ' 0
73. Boron nitride isisoelectronic with: 87. Aluminium (III) chloride forms a dimer because aluminium:
(a) C2 0 (b) B2 o (a) cannot form a trimer 0
(c) N2 0 (d) ~ o (b) has high ionisation energy' 0
74. The number of OH units directly linked to boron atoms in (c) belongs to third group 0
Na2B4~·lOH20 is: (d) can have, higher co<?rdJnation number 0
(a) 2 o (b) 3 o 88. Which one of the following statements about H3B03 is not
(c) 4 o (d) 10 o correct?
75. From B2~' all the following can be prepared except: (a) It is a strong tribasic acid 0,
(a) B2~ 0 (b) H3BD3 0 (b) It is prepared by acidifying an aqueous solution of borax
(c) B2(CH3)6 0 (d) NaB~ 0 o
76. The halides of group llIA elements behave as Lewis acids. (c) It has a layer structure in which planar B03 units are
The acceptor ability is maximum for the halides of: joined by hydrogen bonds 0
(a) TI 0 (b) Ga 0 (d) It does not act as proton donor as it acts as a Lewis acid
(c) Al 0 (d) B D. by accepting hydroxyl ions ' 0
77. The power of halides of boron to act as Lewis acids 89. Which ofthe following is not a Lewis acid?
decreases in the order: [C.H.S.E. (P.M.T.) Pre!' 20101 ,(a) SiF4 0 (b) FeCI3 0
(a) BF3 > BCl 3 > BBr3 o (b) BBr3>.6CI3> BF3 0 (c) BF3 0 (d) C2~ 0
(c) BCl3 > BF3 > BBr3 ' o (d) BCl3 > BBr3 >BF3 0 90. Identify the statement that is not correct as far as structure
78. Silicon shows similarities with: of diborane is concerued: '
. (a) aluminium 0 (b) beryllium 0 (a) There are two bridging hydrogen atoms in diborane 0
(c) boron 0 (d) magnesium 0 (b) Each boron atom forms four bonds in diborane 0
(c) The hydrogen 'atoms are not in the same plane in
79. Which of the following is a false statement?
, diborane 0
(a) BH3 is not a stable compound 0
(d) All B-H bonds in diborane are similar 0
, (b) Boron hydrides are formed when dil. HCI reacts with
9]. Which of the following processes docs not involve a
,::"".Mg3B2 0 ' catalyst?
'Jc) All the B-H bond distances in B2H6 are equal 0 (a) Therrnite process o (b) Ostwald's process o
'f(d) <Th~oron hydrides are readily hydrolysed 0
~ '\ :": (c). Contact process o (d) Haber process o
92. AlC1 3 on hydrolysis gives: (a) Glycerol 0 (b) Acetic acid 0

(a) Al20:,·H20 [J (b) Al(OHh o (c) Ethyl alcohol 0 (d) Ethylene 0
(c) Al203 0 (d) AlC13·6H20 o 102. Specify the coordination geometry around and hybridiza-
93. Thallium shows different oxidation states because: tion of N and B atoms in 1 : 1 complex of BF3 and NH3 :
(a) of its high reactivity 0 [I.LT. (8) 2002]
(b) of inert pair of electrons 0 (a) N : tetrahedral, sp3 ;B : tetrahedral, sp3 . 0
(c) of its amphoteric nature 0 (b) N : pyramidal, sp3 ;B : pyramidal, sp3 0
(d) it is a transition metal 0 (c) N : pyramidal, sp3 ;B : planar, sp3 0
94. In the commercial electrochemical process for aluminium (d) N : pyramidal, sp3 ;B : tetrahedral, sp3 0
extraction, the electrolyte used is: 103. H3B03 is: [I.I.T. (S) 2003]
(a) Al(OHh inNaOH; solution 0 (a) monobasic and weak Lewis acid 0
(b) an aqueous solution of A12(S04h 0 (b) monobasic and weak Bronsted acid 0
(c) a molten mixture of Al203 and Na3AIF6 0 (c) monobasic acid and strong Lewis acid 0
(d) a molten mixture of AlO(OH) and Al(OHh 0 (d) tribasic acid and weak Bronsted acid 0
95. Electrolytic reduction of alumina to aluminium by Hall- 104. Which of the following compounds is known as inorganic
Heroult process is carried out: [U.T. (8) 2000] btmzene? [p.M.KT; 2003]
(a) in presence of NaCl 0
(a) BJ16 0 (b) CsHsB 0
(b) in presence of fluorite 0
(c) in the presence of cryolite which forms a melt with lower (c) C3N3H3 0 (d) B~3~ 0
melting temperature 0 1O~. Which one of the following is the correct statement?
(d) in the presence of cryolite which forms a melt with the [A~I.KKK 2008]
higher melting temperature 0 (a) B2H6' 2NH3 is known as 'inorganic benzene' 0
96. Aluminium oxide is not reduced by chemical reactions (b)Boric acid is a protonic acid 0
since: [KC.KT.2002] (c) Beryllium exhibits coordination number of six 0
(a) aluminium oxide is highly stable 0 (d) Chlorides of both beryllium and aluminium have bridged
(b) aluminium oxide is stable 0 chloride structures in solid phase 0
(c) reducing agent contaminates 0
106. The ion(s) that actls aS,oxidising agent in solution is/are:
(d) the process pollutes the environment 0
gy. Corundum is an ore of: [P.E.T. (Kerala) 2002]
(a) Te+ and A1 3+ .0 (b) B3+ and Al 3+ 0
(a) copper 0 (b) boron 0
(c) aluminium 0 (d) sodium D (c) Te3+ only 0 (d) B3+ only 0
(e) iron 0 107. H3P03 has ............ nonionisable P-H bonds:
98. A layer of coke is spread over bauxite during extraction of [J.KE. (Orissa) 2008]
aluminium. This acts as alan: [P.M.T. (Manipal) 2002] (a) none 0 (b) 1 0
(a) flux 0 (c) 2 0 (d) 3 0
(b) slag to remove impurities 0 108 The chemical formula of feldspar is: [P.M.T. (Punjab) 2008]
(c) reducing agent 0 (a) KA1Si30 g , 0
(d) insulation and does not allow heat to escape 0 (b) Na3AlF6 o
99. Alum helps in purifying water by: [A.I.E.KK 2002]
(a) formingSi complex with clay particles D
(c) NaAl02 o
. (b) sulphate part which combines with the dirt and (d) K 2S04·Al2(S04h4Al(OHh , o
removes it 0 109. Which of the following is not correct? [C.P.M.T; 2008]
(c) aluminium which coagulates the mud particles 0 (a) Al reacts with NaOH and liberates H2 0
(d) making the mud, water soluble 0 (0) AlC13 is a Lewis acid 0
100. BI;3 is used as catalyst in,several industrial processes due (c) Al is used in the manufacture of electrical cables' 0
to its: [C.KE. (Kerala) 2002] (d) NaOH is used during Hall's process of purification of
(a) strong (educing nature 0 bauxite 0
(b). weak reducing action 0 110. Boron halides behave .as Lewis acids because of their. . . .
(c) sp-ong Lewis acid nature 0 nature: . [KA.M.C.E.T. (Engg.) 2008]
(d),weak Lewis. acid character 0 (a) proton donor 0 . (b) covalent 0
10 l. Boric acid is a very weak acid but in presence of certain (c) electron deficient 0 (d) ionising 0
organic compounds, it acts as a strong acid. Which one of 111. A mixture of boron trichloride and hydrogen is subjected
the following organic compounds can affect such change? to silent electric discharge to form 'A' and HCl. 'A' is mixed
[S.C.R.A. 2001] with NH3 and heated to 200°C to form 'B'. The formula of
'B'is: [KA.M.C.E.T. (Med.) 2008]
Elements'of Group IDA or 13 (Boron and Aluminium) 401
(a) H~03 0 (b) B203 0 114. Which one of the following molecular hydrides acts as a
(c) B2~ 0 (d) B3N3~ 0 Lewis acid? [CoB.S.E. (P.M.T.) 2010]
112 The stability of +1 oxidation state increases in the (a) NH3 0 (b) Hz{) 0
sequence: {C.B.s.E. (p.M.T.) 2009] (c) B2~ 0 (d) C~ 0
(a) 'O<In<Ga<Al 0 (b) In<'O<Ga<Al 0 115. In which of the following molecu1es is hydrogen bridge
(c) Ga<ln<Al<Tl 0 (d) Al<Ga<In<TI O. bond present? lJ.E.E. (W.B.) 2010]
113. In aluminium extraction by the Baeyer's process, alumina is (a) Water 0 (b) Inorganic benzene 0
extracted from bauxite by sodium hydroxide at high (c) Diborane 0 (d) Methanol '0
temperature and pressure. 116. Which of the processes is used in thermite welding?
[A;M.U (Engg.) lOin]
A1203(S) +20H-(aq)~ 2AlOi(aq) + H20(l)
(a) Ti0 2 + 4Na~ Ti + 2Na20 . 0
Solid impurities such as Fe203 and Si02 are removed and (b) 2AI + Fe203 ~ Al20 3 + 2Fe 0
then Al(OHh is reprecipitaled. (c) Sn02 + 2C~ Sn + 2CO 0
2Al(OH)4" ~ A1203 ·3H20(S) +20H-(aq) (d) Cr203 + 2Al ~ 2Cr + Al203 0
117. Diborane reacts with ammonia under different conditions to
In the industrial world : [J.E.E. (\V.B.) 2009j
give a variety of products. Which one among the following
(a) carbon dioxide is added to precipitate the alumina 0
is not formed in these conditions?
(b) temperature and pressure are dropped and the super
{E.A.M.C.E:T. (Engg,~ 2010]
saturated solution seeded 0 o (b) B12H12 -o-'
(a) B2~·2NH3
(c) both, (a) and (b) are practised 0
(c) B~3~ o (d) (BN)1l 0
'" (d) the water is evaporated 01
118. Which of the following oxides are basic? (a) Ii white gelatinous precipitate 0
(a) B2O:3 0 (b) 1120 0 (b) insoluble in excess of NH40H 0
(c) In20:3 0 (d) Al20 3 0 (c) soluble in excess of NaOH 0
119. Stability of monovalent and trivalent cations of Ga, In, '0 (d) amphoteric in nature 0
lie in following sequence: 125. Which of the following metals are extracted by using Al as
(a) Ga3+ < In 3+ > Te+ 0 (b) Ga3+ > In3+ > T13+ 0 a reducing agent?
(c) '0+ > In+ > Ga+ 0 (d) Ga3+ > In+ > TI+ 0 (a) Na from Na20 0 (b) CrfromCrZ03 o
120. Which of the following elements do not form carbide? (c) W from W0 3 0 (d) Mg from MgO o
(a) B 0 (b) Al 0 126. Aluminium becomes passive in:
(c) In 0 (d) Ga 0 (a) cone. HN0 3 [] (b) Hz0 0 4 o
121. Orthoboric acid (H3B03) and metaboric acid (HBOz) differ (c) H004 0 (d) cone. HCl o
in respect of: 127. Which of the following statements are true for H3 B03?
(a) basicity 0 (b) structure 0 (a) It is mainly monobasic acid and a Lewis acid 0
(c) melting point 0 (d) oxidation 0 (b) It does not act as a proton donor but acts as an acid by
122. Select the correct statements about diborane: . accepting hydroxyl ions 0
(a) B2~ has three centred bond 0 (c) It has a layer. structure in which B0 3 units are joined by
(b) Each boron atom lies in sp3 hybrid state 0 hydrogen bonds 0
· 1220
(c) Hb .... B .... H b bond ang Ie IS 0 (d) It is obtained by treating borax with conc. H 2S04 0
(d) All hydrogens in B2~ lie in the same plane 0 128. In the reaction
123. Possible oxidation states of boron family elements are: 2X + B2H6~ [BH 2 X2t[BH4 r
(a) + 1 0 (b) + 2 0 the arnine(s) X is (are) : [LL'f. 2OD9~
(c) + 3 0 (d) +4 0 (a) NH3 0 (b) CH~2 0
124. Al2(S04h+~OH~X. Xis: (c) (CH3hNH 0 (d) (CH3hN 0
1. (a) 2. (b) 3. (c) 4. (d) 5. (d) 6. (a) 7. (b) 8. (c) 9. (c) 10. (b)
11. (d) 12. (a) 13. (b) 14. (c) 15. (c) 16. (d)- 17. (b) 18. (a) 19. (a) 20. (d)
21. (c) 22. (d) 23. (d) 24. (b) 25. (a) -26. (b) 27. (a) 28. (b) 29. (c) 30. (d)
31. (d) 32. (c) 33. (b) 34. (a) 35. (a) 36. (d) 37. (b) 38. (c) 39. (a) 40. (b)
41. (a) 42. (c) 43. (a) 44. (c) 45. (d) 46. (d) 47. (b) 48. (b) 49. (b) 50. (b)
51. (a) 52. (a) 53. (a) 54. (a) 55. (d) 56. (a) 57. (c) 58. (d) 59. (c) 60. (d)
61. (b) 62. (d) 63. (b) 64. (c) 65. (b) 66. (d) 67. (c) 68. (d) 69. (c) 70. (b)
71. (b) 72. (d) 73. (a) 74. (c) 75. (c) 76. (d) 77. (b) 78. (c) 79. (c) 80. (b)
81. (a) 82. (a) ·83. (c) 84. (c) 85. (a) 86. (d) 87. (d) 88. (a) 89. (d) 90. (d)
91. (a) 92. (b) 93. (b) 94. (c) 95. (c) 96. (a) 97. (c) 98. (d) 99. (c) 100. (c)
101. (a) 102. (a) 103. (a) 104. (d) 105. (d) 106. (c) 107. (b) 108. (a) 109. (d) 110. (c)
111. (d) 112. (d) 113. (c) 114. (c) 115. (c) 116. (b) 117. (b) 118. (b, c) 119. (b, c) 120. (c, d).
121. (a, b, c)122. (a, b, c) 123, (a, c) 124. (a,b,c,d) 125. (b, c) 126. (a,b,c) 127. (a,b,c,d) 128. (a,b,c)
~ Objective Questions for liT ASPIRANTS ~~'

1• H3BO 3~ lOO"C X 160"C
~
Y -Red hot B
---? 23, °. [Hint : Two oxides present in bauxite as impurity are Si0 2 and
Fe203' Si belongs to 3rd period and Fe belongs to IVth
X and Y respectively are :
period.'Si0 2 has three dimensional structure.]
=
(a) X Metaboric acid; Y Tetraboric acid
7. When an inorganic compound (X) having 3C~2e as well as
=
(b) X Borax; Y = Metaboric acid
2e-2e bonds reacts with ammonia gas at a certain tempera-
(c) X =Tetraboric acid; Y = Metaboric acid
(d) X = Tetraboric acid; Y = Borax ture, gives a compound (y), isostructural with benzene.
100°C ' 160'C Compound (X) with.ammonia at a high temperature produces
[Hint :H3B03 ~ HB02 (Metaboric acid) ; 4 HBOz ~ a substance (Z).
2 (X) (Xl 2
(a) (X) is B2~
H2B40 7 (Tetraboric acid)]
( Y) (b) (Z) is known as inorganic graphite
2. Which one of the following compounds does not exist ? (c) (Y) is B3N3H6
(a) B2~(CH3h (b) B2H3 (CH3h (d) (Z) is soft like graphite
(c) B2H2 (CH 3)4 (d) B2H(CH3)s [Hint : Diborane, B 2H 6, is a compound consisting 3C-2e and
[Hint : Not more than four hydrogen atoms can be substituted by
methyf groups' in
the moiecuie oCB'2H6:" Thehridge
2e-2e bonds. D2H6+ 2Nlf3 . Low temp'j' B 2Hfi:2NH3
200°C . .
hydrogen atoms are not to be substituted.] ~ B3N3H6' (Y) has structure similar to benzene. It
(Y)
3. A gas other than HCl is obtained in : .
IS caIIed'InOrganIc
. benZene. B2H6 + NH 3 Hightemp. ,
"'-:'~-"--7, (BN)x'.
(a) BCl3 + H2 Silent electric) (b) LiAIH4 + BF3 ----,? (Z)
discharge (Z) is a hard substance.]
(c) both (d) none of these
8. Gallium has smaller atomic radius than aluminium because
[Hint : 2BCl + 6H? Silent electric) B H + 6HCl ; of:
3 - dIscharge 2 6
(Gas) (a) poor shielding power of d electrons of Ga atom
. Ether (b) poor shielding power of s electrons of Ga atom
3LIAIH4 + 4BF3 - - - - ? 2B2H6 + 3LiF + 3AlF3] (c) greater shielding power of s electrons of Al atom
(Gas)
(d) greater shielding power of d electrons of Ga atom
4. AICl 3 is an electron deficient compound but AlF3 is not. This 9. Boron does not form B 3+ cation easily. It is due to:
is because: (a) energy required to form B3+ ion is very high which will
(a) atomic size ofF is smaller than CI which makes AIF3 more not be compensated by lattice energies or hydration
covalent energies of such ion
(b) AICl3 is a covalent compound while AlF3 is an ionic (b) boron is non-metal
compound (c) boron is semi-metal
(c) AICl 3 exists as a dimer but AlF3 does not (d) none of the above
(d) Al in AICl3 is in sp3 hybrid state but Al in AlF3 is in sp2 10. Na2B401'lOH20 is correctly represented as:
state
(a) 2NaB02·Na2B2~·lOH20 (b) Na2[B40S(OH)4] ·8H20
5. Hydride of boron occurs asB2~ but B 2CI6 does not exist.
(c) Na2[B4(H20)407} 6H20 (d) all of the above
This is because :
(a) prc-d1C back bonding is possible in B2H6 but not in B2Cl6 [Hint : Borax molecule is actually made of two tetrahedra and two
(b) boron and hydrogen have almost equal values of triangular units joined as shown below.]
electronegativity OH
(c) boron and chlorine have almost equal atomic sizes I
<
I
(d) small hydrogen atoms can easily fit in between boron O-B~O
atoms' but large chlorine atoms do not
6. Bauxite ore is generally contaminated with impurity of oxides
Na2 'HO-B /0 >B~OH
O-B - 0 .
of two elements E I and E 2 • Which of the following state- I
ments is correct ? OH .
(a) E[ is a non-metal and belongs to 3rd period while E2 is a 11. Orthoboric acid behaves as a weak monobasic acid giving
metal and belong to fourth period H 30+ and:
(b) One of the two oxides has three dim_,lsional polymeric
structure
(a) [B(OH)4t (b) H2 J302
(c) Both (a) and (b) are correct (c) [B(OH)4r (d) H2Bb'2
(d) None of the above
12. Amorphous boron is extracted from borax by following steps:
Borax
(A)·
----'--7 H3B03 B203
(8)
~ Boron. x H
I I
(A) and (B) are :
(a) H 2S04,Al (b) HCI, carbon
H- W~~?' B ""'N - H X _N/B""'N_ X
(c) H 2S04, Mg (d) HCI,Fe I 11 1 11

[Hint : Na2B407 + H 2S04 + 5H20 ~ Na2S04 + 4H3B03 ; H - B ' N /B- H H - B ' N / B- H
2H3B03 ~ B203 + 3H20; I I
B203 + 3Mg ~ 2B + 3MgO] X H
13. Aqueous solution of borax acts as a buffer because : (iii) (iv)
(a) it contains weak acid and its salt with strong base
(b) it contains tribasic acid and strong base 16. X~Y+LiBH4
(c) it contains number of neutral water molecules Heat
[Hint : Na2B407 + 7H20 ~ 2Na [B(OH)4] + 2H3B03] Which of the statement is true for the above sequence of
Salt with strong Weak acid reactions?
base
(a) Z is hydrogen (b) X is B2~
14, _G_t::nt;.ral fomlUla of all!-winium alums is.: (c) Z and Yare Fz and B2~ respectively
(a) [M(H20)61 [AI(H20)61 [S04h (d) Z is potassium hydroxide
(b) [M(H20 )41 [Al(H20)41 [S0414 [Hint : B + F.2 ~ B~ ;
(c) [M(H20)4] [Al(H20)61 [S04h (Z) (X)
(d) [M(H20)61 [AI(H 20)6] [S04h 8B~+ 6LiH B2H6 + 6LiBF4 ]

(Y)
15. 'The number of isomers possible for disubstituted borazine,
17. The stnicture of diborane (B2H6) contains: [A.LE..!E.E.2005~
B3N3H4X2 is:
(a) four 2c-2e bonds and two 3c-2e bonds
003 ~4 ~6 W5
[Hint:
(b) two 2c-2e bonds and four 3c-2e bonds
x X (c) two 2c-2e bonds and two 3c-3e bonds
I I
(d) four 2c-2e bonds and four 3c-2e bonds
H- N'~;::~. B ""'N-X H-N~B""'N-H
I ~ I 11
H-B~W,/B-H H-B~N/B-X
I I
H H
(i) (ii)
1. (a) 2. (d) 3. (c) 4. (b) 5. (d) 6. (c) 7. (a,b,c) 8. (a) 9. (a) 10. (b) n. (c) 12. (c)
13. (a) 14. (d) 15. (b) 16. (c) 17. (a)

In each of the following questions two statements are given 1. (A) Borax bead test is not suitable for Al (III).
as Assertion (A) and Reason (R). Of the statements, mark the (R) Al 20 3 is insoluble in water.
correct answer as : 2. (A) Thallium exhibits oxidation states of +1 and +3.
(a) If both (A) and (R) are true and (R) is the correct (R) Thallium exhibits inert pair effect.
explanation of (A). 3. (A) Boric acid is a tribasic acid.
(b) If both (A) and (R) are true but (R) is not the correct (R) Boric acid contains three hydroxyl groups.
explanation of (A). 4. (A) BF3 is a weaker Lewis acid than BCI3.
(c) If (A) is true but (R) is false. (R) BF3 molecule is stabilized to a greater extent than BCl3
(d) If both (A) and (R) are false. by B-F n:-bonding.
(e) If (A) is false but (R) is true.
5. (A) AlCl 3 forms dimer AlzCl6 butit dissolves in water forming 7. (A)· In water, orthoboric acid behaves as a weak monobasic
[Al(H ZO)6]3+ and Cl- ions. acid.
(R) Aqueous solution of AICh is acidic due to hydrolysis. (R) In water, orthoboric acid acts as a proton donor,
6. (A) Aluminium is used as a reducing agent in thermite I1Lt1'~ .2OO1Il
process. 8. (A) Boron always forms covalent bond.
3
(R) The small size of B + favours formation of covalent
(R) Aluminium can reduce NazO to sodium.
bond. nU.lJ. ZW7Ji
1. (b) 2. (a) 3. (e) 4. (a) 5. (b) 6. (c) 7. (c) 8. (a)

5. Which _one. of the. following metals cannotbeextracted.J:!-)l--.
using Al as a reducing agent ?
Aluminium is stable in air and water inspite of the fact that it is
(a) NafromNazO (b) CrfromCrz03
reactive metal. The reason is that a thin film of its oxide is (ormed
(c) W from W0 3 (d) Mn from Mn304
on its surface which makes it passive for further attack. The layer 6. Aluminium becomes passive in :
is . so useful that in industry, it is purposely deposited by an
(a) conc. HN0 3 (b) H:zCr04
electrolytic process called anodising. (c) HCl04 (d) all of these
Reaction of aluminium with oxygen is highly exothermic and is
called thermite reaction.
THOUGHT 2,
3
2Al(s) + 20z (g) ~ Alz03(S); AH = 1670 kJ (A) + (8) + CaC03
Thermite reaction finds applications in the metallurgical extraction
(A) + COz ~ (8) + NaZC03
of many metals from their oxides and for welding of metals. The Solution
drawback is that to start the reaction, high temperature is required
for which an ignition mixture is used. (8) + Conc. HCI ~ NaCl + Acid
1. Anodising can be done by electrolysing dilute HZS04 with J,I H 20
aluminium as anode. This results in : (C) Strongly) (D) Acid (C)
(a) the formation of AlZ(S04)3 on. the surface of aluminium heated
anode (D) + CuSO Heated) Blue coloured (E)
(b) the formation of oxide film (Alz~) on the surface of 4 inflame compound
aluminium anode
(c) the formation of polymeric aluminium hydride film on the 1. Compound (A) is :
surface of aluminium anode (a) NaBOz (b) NazB4~
(d) none of the above (c) Na~~ (d) NaOH
2. The reaction which is not involved in thermite process : 2. . Compound (8) is :
(a) 3Mn304 + 8Al ~ 9Mn + 4Alz0 3 (a) NaBOz (b) Na2B4~
(c) Na3B~ (d) NaOH
(b) Crz03+2Al~ 2Cr+Alz03
3. Compound (C) is :
(c) 2Fe + Al Z0 3 ~ FeZ03 + 2AI
(a) HzB4~ (b) HBOz
(d) B 20 3 + 2Al ~ 2B + Alz0 3 (c) H3B03 (d) HB30S
3. Thermite a mixture used for welding is : 4. Compound (D) is :
(a) Fe and Al (b) BaO and Mg powder
(a) H~03 (b) BA
(c) Cu and Al (d) FeZ03 and Al powder (c) B (d) none of these
4. Anodised aluminium is : 5. Compound (E) is :
(a) Al obtained at anode
(a) CuzO (b) CuS
(b) Al prepared electrolytically
(c) CUS03 (d) Cu(BOzh
(c) alloy of Al containing 95% Al
(d) AI electrolytically coated with aluminium oxide
(c) has zero dipole moment

(d) is a Lewis base
(i) Boron + 02 (X) [Hint : BCl3-B in s/ state, triangular planar structure and zero
dipole moment being symmetrical molecule. It is a Lewis
(n) (X) + C (carbon) + Cl 2 (Y)+ CO
acid.]
(iii) (y) + LiAIH4 ---7_ (Z) + LiCI + AICl 3
(iv)(Z) + NH3---7 (A)---'? (8) THOUGHT 4
(v) (Z) + NaH ---7 (D) Boron forms a number of hydrides having the general formulae
1. Compound (Z) is : BnHn+4 and BnHn+6' These hydrides are called boranes.The
(a) an ionic compound simplest hydride of boron is diborane, B2~' Boranes contain
(b) an electron deficient compound special types of bonds known as multicentre bonds. Boraneshave
(c) 3C-2e compound high heat of combustion.
(d) having ethane like structure 1. The type of hybridization of boron in diborane is :
2. Compounds (X) and (Y) are : (a) sp (b) s/ (c) si "(d) dsp2
(a) (X) = B02 , (Y) = BCl2 (b) (X) = B03 ,(y) = BCl4 2. Three centre two electron bond is present in :
(a) BF3 (b) B4HlO (c) H3B03 (d) B2~
= =
(c) (X) B20 3 , (y) BCl 3 (d) (X):::: B03, (y) = B4C
3. Which of the following is electron deficient compound?
3. Compound (8) is :
(a) C2H6 (b) Sil:4
(a)--borazole--(b) inorganic benzene
(c) PH3 (d) B4HlO
(c) borazon (d) boron nitride
4. Which hydride does not exist?
4. Compound (D) is used as alan:
(a) oxidising agent (b) complexing agent
(a) BH3 (b) H2F2
(c) SbH3 (d) N2tLt
(c) buffer agent (d) reducing agent
5. From B2H6, all the following can be prepared except:
[Hint : B2H6 + 2NaH 2NaBH4 (sodium borohydride). It is
used as a reducing agent.]
(a) H3B~ (b) B2(CH3)4H2
(c) B2(CH3)6 (d) NaBtLt
5. Compound Y : 6. InB2H6:
(a) has boron in sp2 hybridized state (a) there is direct boron-boron bond
(b) is a planar molecule (b) the boron atoms are linked through hydrogen bridges
(c) all the B-H bond distances are equal
(d) all the atoms are in one plane
Thought 1 1. (b) 2. (c) 3. Cd) 4. Cd) 5. (a) 6. (d)

Thought 2 1. (a) 2. (b) 3. (c) 4. (b) 5. (d)
Thought 3 1. (b, c) 2. (c) 3. (a, b) 4. (d) 5. (a,b, c)
Thought 4 1. (c) 2. (b, d) 3. (d) 4. (a) 5. (c) 6. (b)
1. What are special features of structure of boron? 4. Can we prepare anhydrous AICl 3 by heating AICI 3·6H20?
[Hint : It is a symmetrical solid with icosahedral shape. There are [ADS. When AlCI 3·3H20 is heated, hydrolysis takes place.
20 faces (eq~ilateral triangle). The faces meet at 12 comers.
2AICI3·6HzO - 7 2AI(OH)3 + 6HCl
Each icosahedron consist of 12 boron atoms; six of them
are bonded to another icosahedron by two centre bond 2AI(OHh - 7 Al20 3 + 3HzO ]
( I. 71 A); each of other six is bonded by a three centre bond 5. When finely powdered aluminium is suddenly exposedto air,
(2.02 A) in separated icosahedra.] it catches fire, explain why?
2. Which alloy of aluminium is used in air-craft industry? [Ans. Aluminium powder undergo exothermic oxidation, there-
[ADS. Duralumin] fore, it catches fIre and becomes hazardous.
3. Aluminium vessels should not be cleaned by washing soda, 3
2AI +"2°2 ~ A1203; dH -ve (-310 kJlmol)]
explain why?
6. Boric acid is weak, it cannot be titrated directly with NaOH.
[ADS. Na2C03 undergo hydrolysis to give NaOH. Sodium
hydroxide react with aluminium vessels. Give the precautions taken in the titration of boric acid with
caustic soda.
2AI + 2NaOH + 2H20 - 7 2NaAI02 + 3H2]
[Ans. When catechol is added to boric acid, stable compound 9. What is the chemical composition of Emery Paper?
(strong acid) is formed, which can be titrated with caustic [Ans. Impure form of corundum (AI 20 3 ) containing impurity of
soda using methyl orange indicator.} Fe203 and silica is called Emery and it is used in the
7. What do you understand by? manufacture of emery paper or sand paper. This paper is
(a) Ammonal (b) BentonIte used to polish metals.]
(c) Rubies and Sapphire (d) Lapis Lazuli 10. Discuss the structure of trica1cium aluminate, which is
[Hint: important constituent of portland cement.
(a) Ammonal : It is mixture of {AI + NH4N03 }, used in bombs. [Hint : General formula = Cli9[AI6018]' It contains twelve
(b) Bentonite: Alumina-silica clay called 'bentonite' is dropped membered rings of Si-O-Si-O bonds made by joining
from aeroplanes in the slury form for spreading water over fires. six AI04 tetrahedra.]
(c) Rubies and sapphire are chemically A1 20 3. These are gems. 11. Complete the following reactions:
(d) Lapis Lazuli is sodium alumino silicate, which is used as
semiprecious stone.] (i) BCI 3 +(C 2HS)4j!jCl-CHCI 3 )?
8. Give the name and structural formula of a boron compound
which is optically active. (ii) NH4CI + Na2B407 Red hot) ?
[Ans. Boro salicylic acid is optically active.] (iii) BCl3 + NH4CI 140"C) fl NaBH 4 )?
[Hint: C6 HsCI '
,
[Ansdi) BCI3 + (C2HSkNCI- CHCI ) [(C2Hs)4N]BCI4
Boio salicylic acid

(Optically active)
The allswer to each of the followillg questions is a sillgle 4. Borax is represented as Na2[B40S(OH)4}8HzO. How many
digit illteger, rallg;"g from 0 to 9. tetrahedral boron atoms are present in the structure of borax?
1. How many orbitals of boron are involved in hybridisation in 5. How many isomers of disubstituted borazine are possible?
diboralle? 6. How much nitrogen is evolved when one gram of ammonium
2. How many moles of methane are obtained by hydrolysis of chloride is heated with borax strongly?
one mole of aluminium carbide? 7. The mass of carbon anode consumed (giving only CO2) in
3. Colemanite is an important mineral of boron. It is represented the production of 27 kg of aluminium metal from bauxite by
Ca2BxOll·6H20. What is the value of x? electrolytic method is:
1. (4) Each boron atom in B2H6 is in si-hybridised state. Thus, four 5. (4) Four isomers are possible.
orbitals are involved in hybridisation. [See Q. No. 15 on page 404 ]
2. (3) A1 4C 3 + l2H20~ 4AI(OHh + 3CH4 6. (0) No nitrogen is evolved in this reaction.
1 mole 3 moles 2NH4CI + Na2B4~·lOH20 ~ 2NaCI + 2BN + B 20 3
3. (6) Ca2B601l,5H20 + 14H20
4. (2) Borax has two tetrahedral and two triangular units joined 7. (9) 2AI 20 3 + 3C ~ 4AI +3C0 2
together, 3x12 4x27
Group
IVA or 14
6
CHAPTER 9
, C
Carbon
2s 22rJ
'~"14'
,-, " ,
~ :S-,[
."
,Elements of Group IVA or 14
Silicon
3IfsrJ (Elements of Carbon Family, ns2np2)
32
Ge
Germanium
,.w-4rJ
50
~il POSITION IN PERIODIC TABLE
Snlln ,-
Group IVA or 14 of long fonn of periodic table consists of six elements-<::arbon
(C),-silicon (Si), gennanium (Ge), tin (Sn), lead (Pb) andununquadium*. These-----
5s'SrJ
82 six elements constitute a family known as carbon family. These are p-block
elements as the last differentiating electron' is accommodated in np shell. These
Pb
Lead elements have four electrons in their valency shell and thus placed in the IVth
6s"6rJ group. The elements of this group show similarities as well as gradation in
114
properties with rise of atomic number and thus their inclusion in the same group
Uuq
Ununquadium
is justified on the basis of electronic configuration and physical and chemical
7s"6rJ properties which are described below:
Group lllA IVA VA
Contents: i Period 13 14 15
9.1 Position in Periodic Table
B C N
9.2 Comparison of Carbon and Silicon 2 (5) (6) (7)
9.3. Comparison of Tin and Lead
Al Si p
9.4 Carbon 3 (13) (14) (15)
9.5 Compounds of Carbon
Ga Ge As
9.6 Silicon 4 (31) (32) (33)
9.7 Compounds of Silicon
9.8 Tin Sn Sb
5 (50) (51)
9.9 Compounds of Tin
9.tO Lead or Plumbum Tl Pb Bi
6 (81) (82) (83)
,9.11 Compounds of Lead
Uut Uuq
7
(113) (114)
1. Electronic configuration: The ~lectronic configuration of the members of this group are:
Element At. No. Electronic configuration Inert gas core
Carbon 6 2,4 Ii, 2i 2l [He] 2i 2p2

Silicon 14 2,8,4 Ii, 2i 2i, 3i 3l [Ne] 3i 3l
Germanium 32 2,8, 18,4 2 lO
Ii, 2s 2i, 3i 3i 3d , 4i 4l [Ar] 3d 10, 4i 4p2
Tin 50 2, 8, 18, 18, 4 2
Ii; 2s 2p6, 3i 3i 3d lO
,
lO
4i 4p6 4d , 5i 5l [Kr] 4dIO, 5s2 5p2
2, 8, 18, 32, 18,4 Ii, 2i 2p6, 3i 3i 3d lO 1o
4i 4i 4d 4f 14, 5i 5i 5d , 6i 6l [Xel 4/,4, 5d lO, 6i 6l
lO
Lead 82 ,
Ununquadium 114 2, 8, 18, 32, 32, 18, 4 Il 2s 2

2p6, 3i 3i 3d iO
, 4i 4i 4d iO 4f 14, 5i 5p6 5dlO 5f 14, [Rnl 5/,4, 6d 1O, 7s2 7l
6i 6i 6dIO, 7i 7l
*Recently a new element of this group with atomic number 114 (IUPAC name ununquadiuml has been discovered.
Elements of Group IVA or 14 (Elements of Carbon Family) 409
The configurations show that these elements have same C Si Ge Sn Pb
. number of electrons in the valency shell, i.e., 4 electrons in the Atomic radius (pm) 77 118 122 140 146
valency shell, two of which are in s-orbital while remaining At. volume (mL) 3.4 11.4 13.6 16.3 18.27
two in p-orbitals. Thus, they have ni n/ configuration, i.e.,
It is observed that there is large increase in atomic radius
s-orbital is paired while two p-orbitals are unpaired.
from carbon to silicon but from silicon onwards, the increase
ns is comparatively small from member to member. This is due
to the fact that shielding effect of i p 6 electrons of the
penultimate shell in silicon isJarge while the shielding effect of
The penultimate shell . of carbon contains 2 electrons
d lO e1ectrons III
. Ge and S n and d10 ,J14 electrons .m Pb.IS less.
(saturated), of silicon contains 8 electrons (saturated), of
germanium contains 18 electrons (saturated) while Sn and Pb In the same period, the atomic radii of group 14 elements
contain 18 electrons (unsaturated) each. This shows why are smaller than the corresponding elements of group 13. This
carbon differs from silicon in some respects and these two is due to fact that effective nuclear charge increases when we
differ from rest of the members of this group. The close remove from group 13 to group 14. This brings contraction in
semblance between the elements is quite striking in the case of size.
elements of the first and second groups, but this becomes less C < B ~ < M ~ < ~
evident in the elements of third group and stjJlless evident in (77 pm) (85 pm) (118 pm) (143 pm) (122 pm) (135 pm)
the fourth group. It shall be clear from thefoUowing discussion. 5. Ionisation poten·lial: the ionisation potentials- "",-_._-
2. Occurrence of the elern.Elrn.: Carbon is extremely decrease gradually from carbon to lead but not systematically
wide spread in nature. It is an essential constituent of all living as in groups I and II. The value of lead is slightly higher than
matter as proteins, carbohydrates and fats. Carbon is the expecteci. due to lanthanide contraction.
seventeenth and silicon the second most abundant element by
C Si Ge Sn Pb
mass in the earth's crust. Carbon is found both in native and
Ionisation t1;H, 1086 786 761 708 715
combined states. Silicon occurs very widely as silica and a wide
enthalpy t1;H2 2352 1577 1537 141l 1450
variety of silicate minerals and clays. Germanium is only found
(kJ moC I ) t1;H3 4620 3228 3300 2942 3081
in traces in some silver and zinc ores, and in some types of coal.
t1;H4 6220 4354 4409 3929 4082
No doubt that the abundance of tin and lead is comparatively
low, .but they occur as concentrated ores. Tin is mined as Large decrease in ionisation potential from C to Si is due to
cassiterite, Sn02 and lead is found as galena ore, PbS. In the increase in size of the atom. Decrease in ionisation potential
fusion reactions occurring on stars and sun, carbon acts as from silicon onwards is comparatively smaller due to less
catalyst. The energy released in the process is called stellar energy. screening effect of dlO electrons in Ge and Sn and due to
4
The last member, ununquadium (114) is recently discovered d lO/ electrons in Pb.
element. It is synthetic, radioactive and unstable element. Not The slight increase in the iO)1isation energy from Sn to Pb
much is known about its properties. is due' to lanthanide contraction and increase of 32 units of
3. Non-metallic and metallic character: The change nuclear charge in Pb over Sn, i.e. valency electrons are more
from non-metallic to metallic character with the increase of tightly held in Pb. .
atomic number is best illustrated by this group; Carbon, the The fIrst ionisation energies of group 14 are higher than the
first element, is a non-metal, silicon, the second element has corresponding elements of group 13 in the same period.
most of the properties of a non-metal but its electrical properties C > B , ~ > M
and some of the physical properties are those of a (1086 kJ morl) (800 kJ mol-I) (786 kJ mcir l) (577 kJ mol-I)
semi-metal (metalloid). Germanium is a metalloid (properties
The increase is due to decrease in size and increase in charge
are mixed, i.e., of a metal and a non-metal) while last two
on nucleus of group 14 elements in the same period.
members Sn and Pb are distinctly metals.
6. Melting and boiling points: Carbon has an extre-
C Si Ge Sn Pb mely high melting point (41 OO°C). Silicon melts appreciably lower
'-.;------' '-----v---'
Non-metals Metalloid Metals than carbon but the values of silicon and germanium are still
high. (Si = 1420°C; Ge = 945°C). They have the very stable dia-
The change from non-metallic to metallic character is due'
mond like structure in which smaller atoms are closely packed.
to less effective nuclear charge and increased number of
Tin and lead are rnetallic and have much lower melting points (Sn
available orbitals with increase in the size of the atom. = 232°C; Pb = 327°C) because the M....;"M bonds are weaker.
4. Atomic radii and atomic volume:· Atomic radii They do not use all the four outer electrons for metallic bonding.
and atomic volume increase gradually on moving down the The boiling point of carbon is exceedingly high. It decreases
group. The size increases due to the effect of extra shell being
in silicon and then increases in germanium. However, the boiling
added from member to member.
point decreases from germanium to lead.
7. Electronegativity: The electronegativity values do 10. Multiple bonding: Carbon, the first member of group
not decrease in a regular manner. Carbon is the most 14, possesses a pronounced ability to form stable prt-prt multiple
electronegative element while Si, Ge, Sn and Pb possess nearly bonds (double and triple bonds) with itself and with other first
the same values. This is due to filling of d-orbitals in Sn and row elements such as nitrogen and oxygen. The compounds
Ge and also i-orbitals in lead.
containing )C=C<, -C=C-, -C=N, )C=O, and
C Si Ge Sn Pb
)C=S bonds are common. Graphite, an allotropic form of
Electronegativity 2.5 1.8 1.8 1.8 1.9
carbon, is also an example of prt-prt bonding. Silicon and other
8. Allotropy: Except lead, all other elements of this elements of this group show their reluctance in forming
group show allotropy. For example, carbon exists as diamond, prt-prt multiple bonding due to their large atomic sizes. However,
graphite, coal, charcoal and lampblack; silicon exists in two silicon and other elements of this group have vacant d~brbitals
forms, crystalline and amorphous; germanium exists. in in their valence shell. These elements can fomi drt-prt double
two crystalline forms and tin exists in three forms; grey tin, bonds with nitrogen and oxygen. This bond is formed by the
white tin and rhombic tin. donation of an electron pair from filled 2p-orbitals of N or 0
9. Valency: All these elements show a coval~ncy of 4. to the vacant 3d-orbitals of silicon or other elements of group
The tetravalency is explained on the basis of the shifting of one 14. The existence of drt'-prt bonding explains the structures of
of the paired ns electrons to the vacant np orbital in the same trimethylamine, (CH 3hN, and trisilylamine N(SiH 3 h and their
shell. basic' 'nature:" ,,- - - -, ", , ' - .- .-.._-
ns np In trimethylami~e, the N atom undergoes sl-hybridisation
Ground state [ill Ii Ii] I
giving tetrahedral configuration. The geometry of the QIolecule
is pyramidal as one of the tetrahedral positions is occ~pied by .\
Exci ted state [1J Ii Ii Ii I a lone pair. prt-drt bonding cannot occur in thi~. molecule as
carbon does not have d-orbitals. This lone pair, N(CH 3 h, can
Sp3 hybridization
be donated to Lewis acids and thus it shows a basic nature. In
These four half filled orbitals mix together to give four sl trisilylamine, si -hybridisation occurs giving trigonal planar
hybrid orbitals resulting in a tetrahedral structure and each geometry to the molecule. The lone pair of electrons is present
having one unpaired electron. in unhybridised p-orbital. This overlaps with empty d-orbital of
2
When ns electrons of outermost shell do not participate in anyone of the silicon atoms forming prt-drt back bonding. Due
bonding it is called inert pair and the effect is called inert pair to non-availability of lone pair, this molecule does not show
., 2+
effect. The last three elements have a tendency to lorm M basic nature.
ions as well as M 4+ ions. Since, the inert pair effect increases 11. Catenation: The linking of identical atoms with
from Ge to Pb, the stability of M4+ ions decreases and that each other to form long chains is called catenation. All the
of M2+ ions increases. Thus, the stability of these ions follows elements of this group have the property of catenation. However,
the following order: this property decreases from carbon to lead. Thus, carbon has
Ge2+ < Sn2+ < Pb 2+ the maximum property of catenation, silicon has much lesser
Ge4+ > Sn4+ > Pb4+ tendency, germanium has still lesser tendency whereas tin and
2+ . lead hardly show this property; The decrease of this property
The compounds of Ge are unstable while compounds of
2 is associated with M-M bond energy which decreases from
Ge4+ are stable. Thus,the compounds of Ge + get oxidised into
4 carbon to lead.
Ge + easily and act as reducing agents.
-2e C-C 83 kcaUmol
~ Ge4+ Si-Si 54 kcaUmol
Less stable More stable
(Reducing agent)
Ge-Ge 40 kcaUmol
Sn-Sn 37 kcaUmo1
The compounds of Sn + are less stable than Sn4+. Thus,
2
2 The reason for greater tendency of carbon for catenation
Sn + compounds also act as reducing agents. In the case of
2 than other elements may further be explained by the fact that
lead, Pb + compounds are more stable than Pb4+ compounds.
The Pb4+ compounds, thus, act as oxidising agents. C-C bond energy is approximately of the same value as the
energies of bonds between carbon and other elements. On the
Pb4+ + 2e~ Pb2+ other' hand Si-Si bond is weaker than the bonds between
Less stable More stable
(Oxidising agent) silicon and other elements.
2 C-C 83 kcaUmol Si-Si 54 kcaUmol
.
Smce M 4+ IOns
. are .sma11'
er th an M +Ions, 1 M4+
. .m genera,
compounds behave as covalent due to high polarisation

c-o 86 kcal/mol Si-O 88 kcaUmol
C-O 81 kcaUmol Si-C 186 kcaUmol
(small size and high charge) and M 2+ compound s are'IOmc.
.
Thus, carbon forms a number of compounds in which a Tin dissolves slowly in dilute HCI but readily in concentrated
large number of carbon atoms are linked together in the form HO.
of straight chains, branched chains or closed· rings. The Sn + 2HCI ~ SnCh + H2
property of catenation is responsible for a very large number Lead also dissolves in dilute HCL
of compounds of carbon. Lead dissolves in concentrated HCI forming chloroplumbous.
12. Maximum covalency: Carbon has only two energy acid, but the reaction stops after sometime due to deposition
shells, K and L L shell (outermost shell) has four orbitals 2s, of PbCI 2.
2px, 2py and 2pz. These four orbitals can accommodate a Pb + 2HCl ~ PbC12 + Hz
maximum of 8 electrons forming four covalent bonds. Thus,
PbCl 2 + 2HCl ~ H2PbC4
maximum covalency of carbon is four because it has no
d-orbitals or vacant orbitals which can be used to accommodate Tin dissolves in dilute H2S04, conc. H2S04, dil. HN0 3 and
more electrons. conc. HN0 3.
The remaining elements, however, have vacant d-orbitals. Sn + H2S04 (dil.) ~ SnS04 + H2
These permit the formation of coordinate bonds with other Sn + 4H 2S04 (cone.) ~ Sn(S04h + 2S02 + 4Ht O
atoms or ions having lone pairs of electrons. For example, SiF4 4Sn + IORN03 (dB.) ~ 4Sn(N03h + NH~03 + 3H20
can combine with 2P- ions. Sn + 4HN0 3 (cone.) ~ H2Sn03 + 4N02 + H20
Sif4 + 2F- ~ [SiF6 f- Metastannic
add
Thus, the maximum covalency of silicon can be 6. Similarly, Lead is not affected by dU. H2S04. Hot conc. H2S04
other members can show maximum covalency of six involving dissolves lead but the reaction becomes slower due to formation
sp3d 2 hybn'd'lzatlOn.
. of insoluble PbS04.
Since all these elements except carbon satisfy the following
Pb + 2H2S04 ~ PbS0 4 + S02+ 2HzO
three conditions for the formation of complexes, they have the
HN03 is the best solvent for lead.
tendency to form complexes using .d-orbitals.
(i) small size of the atom or ion 3Pb + 8RN03 (dil.) ~ 3Pb(N03h + 2NO + 4H20
. (ii) high charge Pb + 4HN0 3 (conc.) ~ Pb(N03h + 2N02 + 2H20
(iii) availability of vacant orbitals. of appropriate energy. Organic acids dissolve lead in presence of oxygen.
13. Reactivity: The elements of this group are relatively Pb + 2CH3COOH + I12 O2 ~ Pb(CH 3COO)z + H20
less reactive but reactivity increases down the group. Lead
often appears more unreactive than expected. This is partly (iv) Reactivity towards alkalies: Carbon is unaffected
due to surface coating of the. oxide and partly due to the high by alkalies. Silicon reacts slowly with cold aqueous NaOH and
overpotential for the reduction of H+ to H2 at a lead surface. readily with hot soiution giving solution of silicate.
(i) Reactivity towards air: These elements react with Si + 2NaOH + H20 ~ Na2Si03 + 2H2
the oxygen of the air on strong heating when their oxides are .Sn and Pb are slowly attacked by cold alkali but readily by
formed. hot alkali giving stalmates and plumbates. Thus, Sn and Pb are
C+02~C02; Si+02~SiOz somewhat amphoteric.
Ge + 02~ Ge02; 2Pb + Oz ~ 2PbO Sn + 2NaOH + H20 ~ Na2Sn03 + 2H2
Mono-oxides CO, SiO, GeO are also known. SiO is unstable. Pb + 2NaOH + H20 ~ Na2Pb03 + 2H2
(ii) Reactivity towards water: C, Si and Ge are unaffected 14. Compounds:
by water. However, on red heating, these elements except lead (i) Hydrides: All the members of this group form covalent
decompose steam. hydrides directly or indirectly. The number of hydrides, their
C+H20 ~CO+H2
stability and the case of formation decreases as we move
down from carbon to lead. However, all the members form
Si + 2H zO ~ Si02 + 2H2
hydrides of the type M H 4. Besides M 14, carbon forms a large
Sn + 2H20 ~ Sn02 + 2H2 number of hydrides, saturated as well as unsaturated. Silicon
Lead is unaffected by water, probably, because of a protective forms only limited number of saturated hydrides. Germanium
oxide film. gives a still smaller number of hydrides while Sn and Pb give
(iii) Reactivity towards acids: Non-oxidising acids do only one hydride each.
not attack carbon and silicon. Germanium is not attacked by The hydrides of MH4 type are gaseous and their thermal
dilute HCI. However, when metal is heated in a stream of HCI stability decreases and consequently the reducing nature
gas, germanium chloroform is formed. increases from top to bottom. However, among the hydrides,
Ge + 3HCl ~ GeHC13 + H2 silicon hydrides are least stable to hydrolysis.
Hydrides CH 4 SiHa·· GeH4 SnH4 PbH4 [Non-existence of PbBr4 and Pb4 can be explained on the
Decomposition temp.eC) 800 450 285 150 0 basis of strong oxidising nature of Pb 4+. The ions Br- and 1-
are reducing agents, i.e., in presence of these ions, Pb4+ ions
[The hydrides of silicon (silanes) are much more reactive
are reduced to Pb2+ ions.
than the alkanes. The difference in behaviour is attributed to
various factors: Pb4+ + 2Br- ~ Pb2+ + Br2
(a) Electronegativity values are: C 2.5, Si = 1.8 and Pb4+ + 2r ~ Pb2+ + 12 ]
H = 2.1. Thus, the bonding electrons between C and H or Si Except carbon halides, other halides are readily hydrolysed
and H are not equally shared and silicon is vulnerable to attack by water. The trend towards hydrolysis, however, decreases
by nuc1eophilicreagents. down the group. The hydrolysis is due to utilisation of
0:0+ 0+ 0- d-orbitals to which water molecules can get attached.
C-H Si-H The tetrahalides of Si, Ge, Sn and Pb can form hexahalo
(b) The larger size of Si is easier. to be attacked. complexes like [SiF6f-, [GeF6]2-, [GeCI6f-, [SnCI6]2- and
(c) Si has low energy d-orbitals which may be used to fomi [PbCI6f- with the corresponding halide ions. Thus, tetrahalides
an intermediate compound and thus lower the activation of Si, Ge, Sn and Pb act as strong Lewis acids ..
energy of the process. Carbon does not form dihalides. All tM other elements do
form dihalides. There is a steady increase in'the stability of
SiH4 + 2NaOH + IhO ~ Na2Si03 + 4H2
dihalides .
. SiH4 + 3H20 ~ H2Si03 + 4H2
SiX2 < GeX2 < SnX2 < PbX2
SiH4 + 4AgN03 ~ Si +- 4Ag + 4HN0 3
(iii) Oxides: All the elements of this, group form oxides
SiH4 + 2Cl 2 ~ Si + 4HCI ] of the type M02 .
The low stability of GeH 4, SnH4 and PbH4 is due to. weak
C02 Si02 Ge02 Sn.02 Pb0 2
M-H bond. It is due to large difference in the size of M and
hydrogen atom leading to poor overlapping and weak covalent The acidic nature decreases with increase of atomic number.
bond. CO2 and Si02 are acidic while Ge020 Sn02 and Pb0 2 are
[Note : Extremely pure silicon can be obtained by pyrolysis of amphoteric. All these dissolve in alkalies giving carbonates,
monosilane, SiH 4, in absence of air. The pure silicon is used as silicates, germanates, stannates and plumbates, respectively.
a semiconductor. M02 + 2NaOH ~ Na2M03 + H20
SiCl LiAlH4 )SiH Healin. )Si(Pure)] The dioxides of Ge, Sn and Pb also dissolve in acids.
4 4. absence of air
(ii) Halides: The members of this group form tetrahalides Ge0 2 + 4HCI ~ GeCl 4 + 2H20
of the type MX4 except PbBr4 and Pb4. The halides are Sn02 + 4HCI ~ SnCl4 + 2H20
covalent and formed by sp3 hybridization. The thermal stability Pb02 + 4HCI ~ PbCl2 + Cl2 + 2H20
of . halides of different elements with a common halogen
They also form oxides of the type MO. SiO is unstable. CO
decreases with increasing atomic number. The thermal stability
is neutral while SnO and PbO are amphoteric. Basic character
of tetrahalides of the same element decreases with increase in
of both mono and dioxide increases down the group.
molecular mass of the tetrahalide.
CX4 > SiX4 > GeX4 > SnX4 > PbX4 ~_ COMPARISON OF CARBON AND
CF4> CC4 > CBr4> CI4 SILICON
fcflf: Carbon and silicon,'the first two elements of group 14 have a
CI --I -l- number of similarities in their properties as both have same
I ",O-H
number of electrons in the outermost shell. They show many
CI-~i-Cl + 2H20~ ~l oSli-·CI .
dissimilarities in properties also because the number of
CI . I , electrons in the penultimate· shells are different.
r.---'"
~I.L<;;U
H OH Points of Similarities
OH ,I I
If~ I- . OH (a) Electronic configuration: Both the elements have 4
2
. I I I -- electrons, i.e., i p grouping in their valence shell.
CI-Si--CI +2H20)~Cl-+--Si~ CI~ HO-Si-OH
I -- I'cg..H : I C; 2, 4 Si; 2, 8, 4
OH I '-- OH (b) Occurrence: Both are widely distributed in nature.
HOH Carbon is the essential constituent of vegetable and animal
kingdom while silicon is an essential constituent of mineral

kingdom.
(c) Non-metallic: Both are typical non-metals. They form (Silane) (Disilane) (Trisilane) (Tetrasilane)
oxides of type M02 which are acidic in nature. Their monoxides ,These are all colourless gases and bum in air to form oxides.
CO and SiO are neutral, SiO is comparatively unstable. Cf4 + 202 ---? CO2 + 2H20
(d) Valency: Both show tetravalency. Both form covalent SiH4 + 202 ---? Si02 + 2H20
compounds by sharing of electrons. Both show tetravalency
(iii) Formation of halides: Both form covalent halides
on account of sp3 hybridization. .
of same formula.
(e) Allotropy: Both show allotropy.
CC4
(f) Catenation: Both carbon and silicon possess the
SiC4
property of catenation. Their atoms join with one another in
large numbers forming the long chains and rings. (iv) Formation of acids: Both form similar types of
(g) Similar compounds :
acids.
(i) Formation of -oxides: Both bum in oxygen to form H2C03 H2Si03
Carbonic acid Silicic acid
acidic oxides.
COz + 2NaOH ---? Na2C03 + H20 COOH SiOOH
Si02 + 2NaOH ---? Na2Si03 + H20 I I
(ii) Formation of hydrides: Both form a number of COOH
. - -.- ,. ~ - ,SiQQfL
Oxalic acid Silico-oxalic acid
similar hydrides.
~ Points of Difference (Dissimilarities)
Carbon Silicon
1. It has 2 electrons in the penultimate shelL It has 8 electrons in the penultimate shell.
, C:[2J,4 Si: 2, []J, 4
2. It is black solid. It does not melt It is reddish brown solid. It melts at 1410°C.
3. Some allotropic forms of carbon. e.g., graphite are good conductors It is bad conductor of heat and electricity.
of electricity.
4. Caustic alkalies have no action on carbon. It reacts with alkalies to evolve hydrogen.
Si + 2NaOH + H20 ---7 Na2Si03 + 2H2
5. The dioxide, carbon dioxide, is a gas. It has a linear structure. Carbon The dioxide, silica, is a solid. It has a giant structure. The silicon atom is
atom is linked to two oxygen atoms by double covalent bonds. linked with oxygen atoms by single covalent bonds.
Carbon is sp hybridized. These hybrid orbitals overlap with the p- I I
orbital of each oxygen atom. The remaining 2p-orbital of each o 0
oxygen atom form 1t-bonds with p-orbitals of carbon atom.
I I
-O-Si-O-Si-O-
p-p p-p I I
o p-sp C sp-p 0 o 0
I I
CO2 molecules are held together by weak van der Waals' forces ' Silica has a three dimensional infinite, structure in which silicon is tetra-
hence it exists as a gas at ordinary temperatures. hedrally bonded to four oxygen atoms and each oxygen atom is bonded to
Carbon dioxide dissolves in water and behaves as weak acid. two silicon atoms by covalent bonds. Hence, silica has high melting point
CO 2 + H20 ~ H2C03 and is a solid.
Carbonic acid Silica is insoluble in water and acts as a very weak acid.
2NaOH + C02 ---7 Na2C03 + H20 2NaOH ± Si~ ---7 Na2Si03 + H 20
6. The lower oxide. carbon monoxide, is known. It is stable and The SiO is unstable.
neutral in nature.
7. It forms a large number of hydrides known as hydrocarbons which It forms Jesser number of hydrides which are not very stable. These act
are stable. These are not hydrolysed by water. i as reducing agents. These are hydrolysed by water with evolution of
hydrogen.
8. It does not directly react with Cl2 or Br2' It reacts with Cl2 or Br2 at 500°C.
Si+ 2Cl 2 500°C) Si04
9. Co,. is a stable compound and it is not hydrolysed by water. The SiC4 is less stable and it is hydrolysed by water. The hydrolysis is due to
hydrolysis does not occur because water molecules cannot be the fact that water molecules can be coordinated to Si as its maximum
coordinated' to carbon as its maximum covalency is four. covalency is six.
'10. The oxyacid. H2C03. is unstable. It is best known in the form of The oxyacid, H2Si03• is stable. It is also known in the form of salts.
salts, carbonates. silicates. .
11. It does not form complex ions as d-orbitals are not present and It forms a number of complex ions as d-orbitals are present and maximum
maximum covalency is four. covalency is six.
(v) Structure of trimethyl ammonia and trisilyl SnO + 2NaOH ~ Na2Sn02 + H 20

ammonia: Trimethyl ammonia is pyramidal whereas trisilyl (Sodium stannite)
ammonia is a planar molecule. In silicon atom, there is vacant SnO + H2S04 ~ SnS04 + H 20
d-orbital hence electron pair of nitrogen is donated to silicon PbO + 2NaOH ~ Na2Pb02 + H 20
by p1t-d:Tt overlapping in trisilyl anunonia. Thus, trisilyl anunonia (Sodium plumbite)
has planar structure. PbO + H 2S04 ~ PbS0 4 + H 20
6. Both form tetrachlorides of the type MCI 4. These are
hydrolysed by water.
H3S/N\SiH3 H3s/N~SiH3 H3Si~N""'SiH3 SnCl4 + 4H 20 ~ Sn(OH)4 + 4HCI

PbC14 + 2H20 ~ Pb0 2 + 4HCI
Trimethyl ammonia haS pyramidal shape due to presence of. These tetrachlorides combine with HCl to form chloro acids.
lone pair of electron at nitrogen. H 2SnCl6 H2PbCl6
{2 Chlorostannic acid ChloC9plumbic acid
CH3 <J>
N
CH3
CH3 (Pyramidal Shape)
Tetrachlorides decompose on heating.
SnCl4 ~ SnCl2 + Cl 2
PbCl 4 ~ PbCl2 + Cl 2
7. Sulphides of both are precipitated by passing H2S through
9~ COMPARISON OF TIN AND LEAD their -s-alt 801l1tions. --_.
Tin and lead are the last two members of group 14. Both PbClz + H2S ~ PbS + 2HCl
Black ppt.
resemble each other in many respects but lead being the last
member having higher atomic mass differs in some respects SnCl2 + H 2S ~ SnS + 2HCI
Yellow ppt.
with tin.
8. Both form tetrahydrides which are unstable.
Points of Similarities 9. Both form organometallic compounds.
Sn(C 2Hs)4 Pb(C 2H s)4
1. Electronic configuration: Both have same electronic Tin tetraethyl Lead tetraethyl
configuration having 4 electrons in the outermost shell and 18
electrons in the penultimate shell. Points of Difference (Dissimilarities)
Sn (50) 2, 8, 18, 18, 4 Tin Lead
1. Tin shows allQtropy. Lead does not show allotropy.
Pb (82) 2, 8, 18, 32, 18, 4
2. Tin does not leave any mark Lead leaves a mark on paper.
2. Metallic nature: Both of them are metals.They have on paper.
low melting and boiling points. 3. Ductile. Not very ductile.
Element m.pt. (0C) b.pt. eC) 4. Tin is a metalloid. Lead is a metal.
5. SnO does not combine with PbO combines with silica showing
Sn 232 2275 silica. PbO is more basic than SnO.
Pb 327 1620 PbO + Si02 ~ PbSi03
Both are malleable in nature. 6. SnCI 2 is soluble in both dil. and PbC1 2 is insoluble in diL HCI but
colic. HCI. soluble in cone. HCI forming
3. Valency: Both show valency of 4 and 2 in their
complex H[PbCI3], ~[PbCI4]'
compounds. It is based on the fact that either 4 or 2 electrons 7. SnS is soluble in yellow ammo- PbS is insoluble in yellow ammo-
from the outermost shell act as valency electrons. The lower . nium sulphide showing its acidic nium sulphide showing its basic
valency, i.e., 2 is shown on account of the inertness of ns pair nature. nature.
of electrons. The compounds having divalency are electrovalent 8. Stannic compounds are stable. Plumbous compounds are stable.
while compounds having tetravalency show covalent nature. Stannous compounds act as Plumbic compounds act as oxidis-
Both are electropositive metals but also exhibit an electronegative reducing agents. ingagents.
9. Tin is not attacked by organic Lead dissolves in orgapic acids.
character in some of their compounds. Similar to silicates, the
acids. The reaction is not The reaction with sulphuric acid is
stannates and plumbates are known. retarded with sulphuric acid as retil1'ded by the formation of
4. Action of alkalies: Both react with hot alkali solutions sulphates of tin are soluble. Sn insoluble PbS04. Pb forms lead ni-
and liberate hydrogen. forms metastannic acid with trate with concentrated nitric acid.
Sn + 2NaOH + H 20 ~ Na2Sn03 + 2H2 concentrated nitric acid.
10. Tin combines with sulphur to Lead combines with sulphur to
Pb + 2NaOH + H 20 ~ Na2Pb03 + 2H2 form stannic sulphide. form lead sulphide.
5. Both form amphoteric oxides of the type MO and M02• Sn +2S~ SnS2 Pb+S~PbS
Elements of Group IVA or 14 (Elements of Carbon Famity) 415
(a) Diamond: (i) It is the purest form of carbon.

(ii) It is found naturally as well as obtained artificially.
(iii) It is the hardest natural substance known.
1. Unique properties of carbon in the group
(iv) It is transparent and has a specific gravity 3.52.
1. Carbon has the smallest atomic radius and lowest atomic (v) It is a bad conductor of heat and electricity. It is
volume amongst all the elements of group 14. transparent to X-rays and glows in ultraviolet rays with bluish
2. It is most compact. It is the hardest and has highest green colour. '
melting and boiling points amongst the elements of group 14. (vi) Its refractive index is high (2.45) and when properly
3. It has the highest ionisation energy and is most cut, it produces maximum total internal reflection which is
electronegative element of group 14. responsible for its brilliance.
4. Its maximum covalency is 4 as d electrons are absent in (vii) It is chemically inert. It is not attacked by acids,
the valency shell. alkalies and salts. It burns in air on heating at 900°C to form
5. It has maximum property of catenation. It can form CO2, It reacts with fluorine at 700°C to form CF4.
multiple bonds. As a result, carbon forms a large number of
C + 02 900°C) CO 2
compounds. (Diamond)
6. Carbon dioxide, CO 2, is a gas while the dioxides of other
elements are solids.
7. CCl 4 does not undergo hydro!y~is v.:hile t:l1etetrllhalid~s,_ 1.SlJ-A:-
1.1)(4, of other elements undergo hydrolysis.
1.54A
2. Occurrence
Carbon is one of the most widely. distributed elements in
nature. It occurs free as well as in the combined state. It
occurs free in crystalline form as diamond, graphite, and in the
amorphous form as coal. It is present in all living organisms,
plants and animals, in the combined state in the form of
proteins, carbohydrates, fats and other complicated compounds.
It is present as hydrocarbons in natural gas and petroleum. It
Fig. 9.1 Structure of diamond
occurs as carbon dioxide and carbon monoxid~ in atmosphere.
In mineral world, it occurs in the form of carbonates such as
limestone, CaC03; magnesite, MgC03; calamine, ZriC03; C + 2F2~CF4
dolomite, MgC0 3·CaC0 3; siderite, FeC0 3 ; cerusl)ite, PbC03 ; The important properties of diamond are related to its struc-
etc. ture. In diamond, each carbon atom is in sp3 hybridized state
and linked to four other carbon atoms tetrahedrally by covalent
3. Allotropic forms of carbon bonds. This gives a giant three dimensional polymeric structure
The property due to which an element exists in two or more in which C-C .distance is 1.54 A and bond angle is 109S.
forms which differ in their physical and some of the chemical As the atoms are held firmly by strong covalent bonds,
properties is known as allotropy and the various forms are diamond is the hardest substance, possesses very high melting
called allotropes or allotropic modifications. This phenomenon point (3600°C) and chemically inert. Since there is no mobile
is due to the difference either in the number of atoms in the electron present, diamond is non-conductor of electricity.
molecules [as in the case of oxygen (02) and ozone (03)J or Uses : Diamond is used as a gem stone on account of
arrangement of atoms in the molecules (as in the case of reflection and refraction of light. Impure diamonds (black) are
various forms of carbon). used in knives for cutting glass, "Diamond studded saws" in
Carbon exists in two allotropic forms: drill bits, as rock borers and is also used as polishers.
(a) Crystalline and (b) amorphous. The crystalline forms (b) Graphite: (i) It is found in nature and also
are diamond and graphite while the amorphous forms are coal, manufactured by Acheson process. Anthracite is heated with
charcoal, lampblack, etc. sand in an electric furnace of the resistance type. It is fitted
with two carbon electrodes joined by a thin carbon rod through
Carbon
I which an alternating current is passed (Fig. 9.2).
I I The charge is heated at 3000°C for 24-30 hours. Silicon
Crystalline Amorphous (micro crystalline)
I carbide is formed first which decomposes at high temperature
I
Diamond
I
Graphite
I
Coal
I
Charcoal
I
Lampblack
into graphite and silicon. Silicon volatilizes away leaving behind
graphite.
free to· move throughout the entire layers, graphite is good

conductor of electricity. The adjacent layers are held by weak
van der Waals' forces and the distance between two layers is
sufficiently large (3.4 A). Thus, two adjacent layers can easily
slide over each other and hence graphite is soft and possesses
low density. The more reactivity of graphite is due to the
presence of mobile electrons. Graphite is of two forms: a.
Fig. 9.2 and ~. . .
In a.-graphite layers are arranged in sequence ABAB, with
Si02 + 3C ~ SiC + 2CO the third layer exactly above first layer. In ~-graphite, the
.t layers are arranged as ABCABC . . . . . . . . . The two forms
C + Si are interconvertible.
(Graphite)
Graphite is thermodynamically more stable than diamond
(ii) It is a soft, greasy, dark greyish coloured crystalline and its free energy of formation is 1.9 kJ less than diamond.
solid. 16oo°C •
(iii) Its density is 2.5 g mL-1. Graphite 50000-60000 atm.) DIamOnd
(iv) It is good conductor of electricity and its conductivity When graphite is heated with vapours of K, Rb, Cs at
increases with temperature .. 300°C, it forms CsM. Graphite is diamagnetic but Cs~
(v) It leaves a black mark on paper and is called black lead paramagnetic.
or plumbago. Uses: Graphite is used:
(vi) It is chemically more active than diamond. It ignites in (i) for lining and making electrodes of electric furnaces.
air or oxygen at 700°C to form C02. It is not at.tacked by (ii) in making refractory crucibles.
alkalies and dilute acids. However, when treated with (iii) in making lead pencils.
concentrated HN03 or concentrated H2S04, it is oxidised to (iv) as a moderator in nuclear reactor.
insoluble yellowish green substance known as graphitic acid, (v) as a lubricant in machinery.
C ll H40 S' With alkaline potassium permanganate, it is oxidised (c) Coal: It is the crude form of carbon. It has been
to mellitic acid [C6(COOH)6] and oxalic acid. It forms C02 formed in nature as a result of slow decomposition of vegetable
with chromic acid. matter under the influence of heat, pressure and limited supply
-
..-
" ....
.....
~
~
~
.....
=t
of air. It is found in various forms which represent the different
stages of transformation of vegetable matter. The successive
stages of transformation are: peat, lignite, bituminous, steam
coal and anthracite. The carbon contents of these forms along
~
... -, -~ .LA with calorific values are given below:
Peat Lignite Bituminous Steam Anthracite
coal
r"\ ~
""""' ,.....t-:=;.
f-
~ ["'!; Carbon content %. 60 67 88 93 95
r"" Calorific value .9900 11,700 14,950 15,720 16,200
(B.Th.U. per Ib)
- ....
...a.
~
~ [1 B.Th.U. == 252 calories or 397 B.Th,U. 1 kcal.]
The common variety of coal is bituminous. It is hard like
stone and burns with smoky flame. The superior quality is
--I1.42A I-- anthracite which burns with non-smoky flame.
When coal is subjected to destructive distillation by heating
Fig. 9.3 Structure of graphite in the absence of air, it loses volatile constituents such as coal
gas, ammonia, benzene, phenol and tar, the residue left behind
It has a two dimensional sheet structure. Each carbon atom is coke. Thus, coke is an artificial product. It is coal minus
is in si hybridized state and is .linked to three other carbon volatile matter.
atoms in a hexagonal planar structure. As there are four UseS: Coal is mainly used: (i) as a fuel. (ii) for the manu-
valence electrons in each carbon atom, after forming three facture of coal gas, coal tar and coke. (iii)' in the manufacture
C-C bonds, each carbon atoin is left with one spare electron of synthetic petrol. .
in its p-orbital. This electron then overlaps with each other to Coke is used : (i) as a reducing agent in iron and steel
form a 1t-bond. Hence, the C-C distance in graphite is shorter industry. (ii) as a fuel. (It burns without smoke) (iii) for making
(1.42 A) than that of diamond (1.54 A). The 1t-electrons are fuel gases and graphite.
Elements of Group NA or 14 (Elements of Carbon Family) 417
(d) Charcoal: This form of carbon is obtained by burning is C60. It was given the name of buckminster fullerene. It
wood, cellulose or any other carbonous matter in a limited is made from interlocking hexagonal and pentagonal rings of
supply of air. Charcoal is of various forms such as wood carbon atoms. The· C60 molecule structure is shown in Fig.
charcoal, sugar charcoal, coconut charcoal, animal charcoal, 9.4. Such molecules are now thought to exist even in chimney
etc. These forms contain varying amounts of carbon content. soot or candle soot. Each carbon is si
hybridised. The average
A very pure form of carbon is obtained from sugar. Wood C-e distance is 144 pm.
charcoal is porous and has a very large surface area per unit
weight. It is, therefore, used as an adsorbent. When charcoal
is given a special treatment in order to increase its absorption
capacity, the resulting material is known as activated charcoal
and the process of treatment is called activation. Activation is
carried out by heating the charcoal in retOlis at 800--850°C in
a current of superheated steam. This removes the impurities
sticking on the surface and blocking the capillary pores.
Charcoal is the most active form of carbon. It easily burns
in air to form CO 2 , It reacts with many oxidising agents. It is
affected by conc. HN0 3 and conc. H2S04'
C + 4HN03-~-C02 + 4N0 2-+ 2H 20
C + 2H2S04 ~ CO2 + 2S02 + 2H20 (a) (b)
Uses: Charcoal is used : Fig.9.4 (a) Structure of Cso. buckminsterfullerene a "buckyball"
(i) in removing offensive odour from air in the air- (b) The buckminsterfullerene molecule is often called
conditioning processes. "buckyball" because of its football appearance
(ii) in making filters in cigarettes as to remove vapours of
nicotine. Another molecule C70 has been recently discovered. These
(iii) in removing fused oil from crude spirit. and similar large carbon molecules are sometimes referred as
(iv) in decolourising sugar syrup and refining oils, fats, bucky balls. This allotrope family was named after R. Buck-
glycerine, etc. minster Fuller, a genius architect of the twentieth century.
(v) in treatment of drinking water after chlorination as it One method of manufacturing the fullerenes is to use an
adsorbs excess of chlorine. intense laser beam to heat graphite to temperatures of over
(vi) in gas masks as it adsorbs poisonous gases. 1O,OOOOC. At these temperatures, sections of the hexagonal
(e) lampblack or carbon· black or soot: It is planes of carbon atoms peel off the surface and wrap
obtained by burning substances rich in carbon content such as themselves into balls.
kerosene, petroleum, turpentine oil, acetylene, etc., in a limited Diamond and graphite are insoluble in all solvents but
supply of air. These substances yield a large amount of smoke fullerenes are highly soluble in nonpolar solvents such as hexane
which is passed into chambers having wet blankets. The soot and toluene. Although black in solid phase, fullerenes display
collected on these blankets is called lampblack. a wide range of colours in solution. All the fullerenes sublime
It is almost pure carbon. The carbon content is as high as when heated. The C 60 molecules pack together in the same
98-99% with a small impurity of hydrocarbon. Lampblack is way as metal atoms do, fonning a face centred cubic arrange-
a soft black powder. It is used for making printing inks, black ment. The fullerenes have low densities (about 1.5 g cm-3)
paints, Indian ink, boot polishes and ribbons of typewriters. The and they are non-conductors of electricity. All the carbon atoms
main application, at present, is as a filler in making rubber tyres. in buckminster fullerene are si hybridized because all carbon
atoms are equivalent, the strain caused by distortion of the
• 4. Fullerenes or Bucky balls bonds from coplanarity is equally distributed among all the
carbon atoms. Thus, this molecule is quite stable.
Chemistry is full of surprises and the discovery of a new The fullerenes are easily reduced to anions by reaction with
series of allotropes of carbon must rank as one of the most alkali and alkaline earth metals. For example, rubidium fits within
unexpected findings of all. the interstices in the C 60 lattice to give Rb3C60' This compound
fullerenes constitute a family of structures in which carbon is a super conductor at temperatures below 28K. Chemical
atoms are arranged in. a spherical or elliptical structure. To reaction with the surface of the fullerenes is also possible; thus
make such a structure, the carbon atoms form five or six- reaction with fluorine results in the formation of CooFoo.
membered rings, similar to the pattern of lines on a soccer ball. Besides Coo and C 70, even-numbered fullerenes from C 70 to
One of the most interesting carbon molecules, made in 1985, CIOO are known. Only recently, a fullerene C 36 has been estab-
as a result of action of a laser beam on a sample of graphite lished. It is a black solid and gives a golden-yellow solution.
Various carbides are formed when carbon is heated with

certain oxides.
2000°C
CaO + 3C~ CaC2 + CO
Calcium carbide
Si0 2 + 3C 2000°C) SiC + 2CO

Silica Carborundum
2000°C
2Al20 3 + 9C ~ Al 4C3 + 6CO
(d) Reactivity towards acids: Charcoal dissolves slowly
in hot dilute HN03 forming a brown coloured substance,
artificial tannin. Conc. HN0 3 oxidises carbon to carbon
dioxide.
Fig. 9.5 The American Pavilion at the Montreal Expo in 1967 C + 4HN03 ---7 CO2 + 4N02 + 2HzO
was geodesic dome designed by R. Buckminster Fuller. The
Hot and conc. H 2S04 also oxidises it to carbon dioxide. A
dome.is a three-quarter sphere, 200 feet high and 250 feet
in diameter.
small quantity of mellitic acid (benzene hexacarboxylic acid) is
also formed.
C 'F2H zS04 ---'-?C02 + 2S02 -+ 2H20 .
5. Chemical properties of carbon.
12C + 9H2S04 ---7 C6(COOH)6 + 6H20 + 9S02
Charcoal has the enormous surface area and hence, it is the
most reactive form of carbon. The other forms such as diamond, 9~1 COMPOUNDS OF CARBON
graphite, coal, etc., which are denser, are less reactive in
nature.
(a) Combustion: All the allotropic forms of carbon burn 1. Oxides of Carbon
in air or oxygen forming carbon dioxide (when oxygen supply Two oxides of carbon, carbon monoxide and carbon dioxide
is sufficient) and carbon monoxide (when oxygen supply is are important and described below:
insufficient).
C + O2 ---7 CO 2 (Carbon dioxide) (a) Carbon Monoxide, CO
2C + O2 ---7 2CO (Carbon monoxide) It is found in small amounts in volcanic gases, chimney
This property shows that all the allotropic forms are chemically gases, exhaust gases of internal combustion engines and coal
identical. gas.
(b) Reducing agent: Carbon is a strong reducing agent. Preparation: The following methods can be applied for
It reduces many metallic oxides to corresponding metals, the preparation of carbon monoxide:
sulphates into sulphides and water to hydrogen. These (i) By heating oxalic acid with concentrated sulphuric
reactions occur at high temperatures. acid: A mixture of CO and CO2 is obtained. Sulphuric acid
ZnO + C ---7 Zn + CO acts as a dehydrating agent. CO2 is removed by passing the
PbO + C ---7 Pb + CO gaseous mixture through caustic soda or caustic potash
PbS04 + 4C ---7 PbS + 4CO solution.
BaS04 + 4C ---7 BaS + 4CO COOH
C CO + H I
+ H 20 Red hot)
steam. 2 COOH
(C) Combination with other elements: It combines with Similarly by heating formic acid with concentrated H 2S04,
sulphur when the vapours of sulphur are passed over red hot only CO is obtained.
carbon forming carbon disulphide.
HCOOH
C + 2S ---7 CS 2
When electric arc is struck between carbon electrodes in (ii) By the reduction of oxides of heavy metals with
presence of hydrogen, acetylene is formed. carbon: On heating oxides of heavy metals with carbon,
CO is formed.
2C + H2 ---7 C2H 2
Fe203 + 3C ---7 2Fe + 3CO
Beryllium when heated with carbon fomls carbide
ZnO + C ---7 Zn + CO
2Be + C ---7 Be::C
(iii) By reduction of carbon dioxide: CO 2 can be reduced (vii) It is neutral to litmus.
with carbon or zinc at high temperatures. CO2 when passed (viii) It bums with blue flame to form C02. This is an
over red hot zinc, a mixture of CO and C02 is obtained. exothermic process.
2CO + O 2 ~ 2C0 2 + Heat
ZnO + CO
(ix) It is a good reducing agent as it takes up oxygen and
Similarly, when CO 2 is passed over red hot charcoal, the converted into CO2, This property is utilised for the extraction
reduction of C02 into CO occurs with the formation of a of metals from their oxides.
mixture of CO 2 and CO. The gaseous mixture is passed through
NaOH or KOH solution as to remove CO2, 2Fe + 3C02
(iv) By heating carbonates of calcium, barium or
magnesium with zinc, CO is obtained.
Zno + CO~ Zn + CO2
PbO + CO~ Pb + CO 2
MgC03 + Zn ~ MgO + ZnO + CO
It reduces Fehling'S solution also.
(v) By beating potassium ferrocyanide with conc.
H2S04 : When potassium ferrocyanide in powdered state is 2Cu(OHh + CO ~ CU20 + 2H20 + C02
heated with concentrated H 2S04, CO is evolved. Dilute H 2S04 It reduces 120 5 into iodine.
should never be used because it shall evolve highly poisono~s 120 5 + seo ~ 12 + ~C02
gas; HCN.
(x) The bonding in carbon monoxide is represented as,
K4Fe(CN)6 + 3H2S04 ~ 2K2S04 + FeS04 + 6HCN
6HCN + l2H 20 ~ 6HCOOH + 6NH3
:c:::o: or :Cf-O:
Formic acid Thus, all the four valencies of carbon are not satisfied. It
behaves as unsaturated compound and forms addition products
with a number of substances.
CO + 2H2 l50-400°C) CH OH
ZnO 3
Methyl alcohol
~Fe(CN)6 + 6H 2S04 + 6H20 ~ 2K 2S04 + FeS04 + 6CO Sunlight) COCl
+ 3(NH4hS04 or camphor 2
Phosgene
Manufacture: Carbon monoxide is obtained in the form
of water gas and producer gas when air (moist) is passed over CO+S-~ COS
a bed of white hot coke. The following reactions may occur. Carbonyl sulphide
2C + 02~ 2CO CO + NaOH---':=~ HCOONa
Sodium formate
C + 02~C02
High
C + H20~ CO+H2 cuel + CO pressure) CuCl'CO
~ (Ammonkal Addition
Water gas soln.) product
Carbon dioxide is reduced by passing the mixture over It combines with metals like Cr, Ni, Fe, etc. The
heated charcoal. compounds thus formed are called carbonyls.
CO 2 + C~ 2CO Ni + 4CO -=~ Ni(CO)4
The CO produced, always consists of N2, H 2, CO2, etc. Fe + SCO -='-..::::4 Fe(CO)s
Properties: (i) It is a colourless and odourless gas.
These reactions are used in the extraction and purification
(ii) It is slightly soluble in water.
of metals.
(iii) It is a combustible gas but does not support combustion.
(iv) Its density is nearly equal to the density of air.
·Uses: (i) It is used as a fuel in the form of water gas
(CO + H2) and producer gas (CO + N2).
(v) It is highly poisonous in nature. One part in 100 parts
of air causes death in few minutes. The poisonous nature of (ii) CO is used in the manufacture of methanol, synthetic
CO i~ due to the fact that it combines with haemoglobin (a red petrol, formic acid and phosgene gas (highly poisonous gas).
(,;olouring matter of blood which is absorber of oxygen) to (iii) It is used as a reducing agent in the extraction of iron.
form carboxy-haemoglobin which is !lO(' }ble to absorb (iv) It is used in the extraction of nickel (Mond's process).
oxygen and as a result of this, suffocatioi, _,:; ~:s place. This Structure: The electronic stmcture of carbon monoxide
phenomenon is known as ASPHYXIA. may be represented as follows:
+
(vi) It is not decomposed by heat. :C- ::: 0:
+
or 0: or :C 0:
Carbon atom is sp hybridized. One sp-orbital is being used Bicarbonates of all the metals decompose on heating with
to form a single bond with oxygen atom while the other sp- evolution of CO 2.
orbital which points away from the C-O bond contains a lone 2NaHC0 3 ----7 Na2C03' + H20 + CO 2
pair of electrons. The remaining two unhybridized p-orbitals Ca(HC0 3h ----7 CaC0 3 + H20 + CO2
form two 1t-bonds with two p-orbitals of oxygen atoms. The Manufacture: (i) Fro~ fuel gases: The fuel gases
presence of a triple bond is evidenced by the following facts: produced during the combustion of coal or coke contain large
(i) The bond length between carbon and oxygen is 1.13 A amounts of carbon dioxide mixed with nitrogen, carbon
which corresponds to carbon-oxygen triple bond. . monoxide, oxygen, etc. These gases are passed through K2C03
(ii) The value of dipole moment is small. solution which absorbs C02.
(iii) Due to presence of lone pair of electrons on carbon, K2C03 + CO2 + H20 ----7 2KHC03
carbon monoxide molecule acts as a ligand and can form a
This solution is then boiled when C02 is liberated.
coordinate bond with certain metals (Mf-C f - 0).
2KHC03 ----7 K2C03 + H20 + CO2
(b) Carbon Dioxide, CO2 (ii) From lime kilns: When lime is manufactUred by the
calcination of lime stone, (CaC03), carbon dioxide is obtained
Occurrence: It is present in atmosphere to the extent as a by-product.
of 0.03-0.05 per cent. It comes to the atmosphere from animal CaC03 ----7 CaO + CO2
breathing, decay ~f vegetagle matter, burning of carbon and
(iii) From fermentation: During fermentation," wherr--
carbonous matter, etc. It is also utilised by plants in photo-
molasses are changed into alcohol, a large amount of CO 2 is
synthesis. Thus, a carbon dioxide cycle is operating in nature
obtained as a by-product. .
and the proportion of CO 2 in the atmosphere remains about the
same. It is found in combined state in the form of carbonates. Sugar ----7 C 6H 120 6 ----7 2C 2HsOH + 2C02
Glucose
Preparation: The following methods are used for its
preparation : Properties: (i) It is a colourless, odourless and taste-
(i) By the complete combustion of carbon: Carbon is less gas.
burnt in free supply of air. (ii) It is slightly soluble in water under ordinary pressure
C + O 2 ----7 CO 2 but at high pressures, the solubility is high.
If CO is formed, it also bums with pale blue flame forming (iii) It is heavier than air.
carbon dioxide. (iv) It is easily liquefied under pressure into a colourless
mobile liquid. If CO2 under pressure is allowed to escape
2C + O2 ----7 2CO
through a nozzle, a white solid, i.e., dry ice is obtained. Solid
2CO + 02 ----7 2C0 2
CO 2 is a soft, white, snow like substance; It sublimes and
(ii) By the action of dil. mineral acids on carbonates
leaves no residue. Solid C02 is used as a refrigerant under the
and bicarbonates: Mineral acids react with carbonates and
commercial name drikold. It is used in the transport of
bicarbonates and evolve carbon dioxide.
perishable food materials. It provides cold as well as the inert
CaC03 + 2HCI----7 CaCl2 + H20 + CO2 atmosphere which helps in killing the undesirable bacteria.
Na2C03 + 2HCI----7 2NaCI + H20 + CO 2 (v) It is neither combustible nor a supporter of combustion.
NaHC0 3 + HCI ----7 NaCI + H20 + CO2 However, burning magnesium, sodium or potassium continues
burning in the gas.
This method is used in the laboratory for the formation of
.carbon dioxide. Marble pieces (CaC0 3) are taken in Woulfebottle CO2 + 2Mg ----7 2MgO + C
which is fitted with a thistle funnel and a delivery tube. The C02 + 4Na ----7 2Na20 + C
other end of the delivery tube is kept into a dry cylinder through
a card board disc. Pieces of marble are first covered with water
leo2
and then concentrated HCI is added through the funnel. C02 Na2C03
is formed which is collected by upward displacement of air. [Note : CO 2 is used as fire extinguisher but it cannot be used in the case
Sulphuric acid is not used for the preparation because of active metal fires which have affinity for oxygen.]
calcium sulphate formed gets deposited on the pieces of marble. (vi) CO2 acts as an oxidising agent. When heated with Zn,
This prevents the further action of H2S04 on marble pieces. iron or carbon, these are oxidised.
(iii) By heating carbonates and bicarbonates: The Zn + CO2 ----7 ZnO + CO
carbonates ofless electropositive metals on heating decompose CO2 + C ----7 2CO
evolving carbon dioxide. (vii) CO 2 is. an acidic oxide. It dissolves in water forming
ZnC0 3 ----7 ZnO + CO 2 unstable carbonic acid.
CuC0 3 ----7 CuO + CO 2 H 20 + CO 2 ~ H2C0 3
It combines with alkalies to form two series of salts, (vi) CO2 is used by plants in the form of food.
carbonates and bicarbonates. Stmcture : CO2 has a linear structure since its dipole
2NaOH + CO 2 ~ Na2C03 + H 20 moment is zero. Both the oxygen atoms are linked by double
With excess of CO2, carbonate is converted into bicarbonate. bonds.
O=C=O
Na2C03 + H 20 + CO2 ~ 2NaHC03
The C-O bond length is 1.15 A which is less than
Lime water, Ca(OHh, is turned milky on passing CO2 with
the formation of insoluble calcium carbonate. calculated value of double bond C=O. Thus, it is believed
that CO2 molecule is a resonance hybrid of the following
Ca(OHh + CO 2 ~ CaC03 + H 20 structures :
Insoluble
The milkiness disappears on passing more of CO 2 with the
conversion of calcium carbonate into soluble calcium
bicarbonate. The formation of the molecule can be explained on the basis
CaC03 + H20 + CO 2 ~ Ca(HC0 3h of hybridization. Carbon is sp- hybridized. The hybrid orbitals
Soluble form sigma bonds with p-orbitals of each oxygen atoms. The
(viii) CO2 reacts with basic oxides like Na20, K 20, etc.,to unhybridized two p-orbitals of carbon atom form two
form corresponding carbonates. 1t-bonds with two oxygen atoms.
K20' + CO2 ~ K2C0 3 2s
Na20 + CO 2 ~ Na2C03 Oxygen atom
(ix) CO2 is converted by plants in the presence of sunlight
and chlorophyll into glucose and higher carbohydrates. This ··0 0··
Carbon atom ' O=C=O
•• 1t 1t ••
process is known as photosynthesis.
6C02 + 6H20 ~ C6H1206 + 602
UseS: (i) It is used in the manufacture of aerated water. Oxygen atom
(ii) Solid CO 2 (dry ice) is used in refrigeration. It is superior Carbon forms some less stable oxides, e.g., C302, C S0 2
refrigerant than common ice because it can produce very low and C 120 9 . Graphite oxides are C20 and C203 which are still
temperatures and does not form liquid on melting. A mixture less stable. Carbon suboxide is formed by dehydration of malonic
of solid CO2 and ether'is used to produce low temperature of acid.
<
the order of -80°C to -100°C. ' COOH
P4 0 10
(iii) Carbogen is a mixture of O 2 and CO 2 (5-10%). It is CH2 ~ ) O=C=c=c=O + 2H20
used for artificial respiration in the case of pneumonia patients . COOH
and victims of CO poisoning.
(iv) It is used in the manufacture of white lead and sodium Some important reactions of carbon suboxide are:
<
carbonate (Solvay process). COOH
(v) CO2 is used as fire extinguisher. The use of common C30 2 + 2H20 ~ CH2
fire extinguisher is based on the production of C02. A soda COOH
Malonic acid
acid fire extinguisher contains a concentrated solution of sodium
coa
bicarbonate and a bottle containing concentrated sulphuric acid.
When the apparatus is turned upside down the acid flows out
of the bottle and reacts with sodium bicarbonate to produce
CO 2 ,
C30 2 + 2HC} ~ CH2
< COC}
Malonyl chloride
<
CONH 2
Aluminium sulphate in place of conc.H2S04 is used in foam C 30 2 + 2NH3 ~ CH2
type fire extinguishers. When solution of NaHC0 3 and
CONH2
aluminium sulphate react, C02 is liberated along with the Malonyl amide
hydrolysis of aluminium sulphate producing aluminium hydro-
xide in the form of foam.
AIz(S04h + 6NaHC03 ~ 2A1(OHh + 3Na2S04 + 6C02
II 2. Carbonic Acld, Carbonates
and Bicarbonates
Al2(S04h + 6H20 ~ 2AI(OHh + 3H2S04
Carbon dioxide is an acidic oxide. The solution of CO2 in
AI(OHh deposits on the burning articles and thus cuts off
water shows feeble acidic nature. This is believed due to the
their contact with the air.
formation of carbonic acid.
COz + HzO ~ HZC03 (C02 is called carbonic anhydride.) NaZC03 + 2HCl--7 2NaCl + H 20 + C02
Carbonic acid is known only in solution and has never been NaHC03 + HCI--7 NaCI + H20 + CO 2
isolated in free state. ZnC03 + H2S04 --7 ZnS04 + HzO + CO 2
The carbonic acid is a dibasic acid and it forms two series
(iv) Action of MgS04 : This is the reagent with which
of salts by replacement of one or both the hydrogen atoms.
carbonates and bicarbonates can be distinguished and tested.
H2C03 ~ W + HC03 ~ 2W + COr- Soluble carbonates form an insoluble white precipitate with
(a) Acid salts, are also called bicarbonates or hydrogen magnesium sulphate in cold.
carbonates. These contain HC0 3- ions. Na2C03 + MgS04 --7 MgC03 + Na2S04
(b) Normal salts, are also called carbonates. These contain White ppt.
coj-,- ions. Bicarbonates do not form any white precipitate with
The metallic carbonates or bicarbonates are prepared by magnesium sulphate in cold. However, when such solution is
following methods: heated, a white precipitate appears.
(i) By passing CO 2 through the solution of base:
2NaHC03 + MgS04 --7 Mg(HC03)z + Na2S04
2NaOH + CO2 --7 Na2C03 + HzO
1CO2 + H 20
(Soluble)
1 Heat
NaHC03 MgC03 + H2 0 + CO2
Ca(0H)2 + CO2 --7CaC03 + H 20 White ppt.
1C02 + H 20 (v) Effect of phenolphthalein: Soluble carbonates
produce pink colour with phenolphthalein showing higher pH
Ca(HC03h
value while bicarbonates do not give pink colour with
(ii) By reacting basic oxides and CO2 :
phenolphthalein.
K20 + C02 --7 K2C03
Na20 + CO2 --7 Na2C03 i~ 3. Gaseous Fuels
(iii) By double decomposition, i.e., by using sodium
Fuels are the substances which undergo combustion. As a
carbonate:
result of their burning, they produce heat energy. During com-
CaCl2 + Na2C03 --7 CaC0 3 + 2NaCI bustion, no undesirable product should be formed. The heat
BaCl2 + Na2C03 --7 BaC03 + 2NaCI energy production depends on the presence of combustible
Properties: (i) Solubility: (a) Except alkali metals substances such as carbon, carbon monoxide, carbonous matter,
carbonates, all other carbonates are insoluble in water. hydrogen, etc., in the fuels. Most common fuels are :
(b) The bicarbonates are soluble in water. The bicarbonates (a) Solid fuels: . Wood, Jignite, peat, coke, charcoal, etc.
of alkali metals are known in solid state while the bicarbonates (b) Liquid fuels: Petroleum products such as petrol,
of alkaline earth metals are only known in solutions. kerosene, spirits, etc.
(ii) Action of heat: (a) All bicarbonates decompose on (c) Gaseous fuels: Water gas, producer gas, coal gas,
heating evolving carbon dioxide. The carbonate formed may oil gas, natural gas, etc.
further decompose except alkali metal carbonates. Characteristics of good fuel: (i) It should have high
calorific value.
Ca(HC03)z -----7 CaC03 + H 20 + CO 2
(ii) It should yield very little ash content.
2NaHC03 --7 Na2C03 + H20 + CO2 (iii) It should not give any offensive odour or any undesirable
(b) Alkali metal carbonates except LhC03 do not decom- product during burning.
pose on heating. (iv) It's cost of production should be low and it should be
(c) All other carbonates decompose on heating with easily available.
evolution of carbon dioxide. (v) The combustion should be of moderate speed.
ZnC03 --7 ZnO + CO2 Superiority of gaseous fuels: Gaseous· fuels are the
CaC03 --7CaO + C02 best fuels. The following are the advantages of gaseous fuels
over solid and liquid fuels:
CuC03 --7 CuO + CO 2
(i) Gaseous fuels leave no ash and there is lesser loss of heat
Ag2C03 --7 2Ag + CO 2 + ~ 02 during their combustion.
(iii) Action of acids: Both carbonates and bicarbonates (ii) Gaseous fuels do not produce smoke.
are decomposed by the action of acids with evolution of CO2 (iii) They have high calorific value.
(effervescences ). (iv) No special devices are required for their combustion.
Elements of Group NA or 14 (Elements of Carbon Family) 423
(v) Gaseous fuels can flow through pipes and can be ignited oxygen. It is a good gaseous fuel as it contains about 95%
at the moment's notice at any place where a burner is placed. combustible gases. The calorific value of coal gas is 450-650
Some of the important gaseous fuels are discussed below : B.Th.V. per cubic ft. The average composition of coal gas by
volume is:
(i) Producer Gas Hydrogen 56% , Ethylene, acetylene 2.5%
Producer gas is mainly a mixture of carbon monoxide and Methane 22.8% : Carbon dioxide 1.3%
nitrogen. It is prepared by the incomplete combustion of coal, Carbon monoxide 10.9% ; Oxygen 0.5%
coke or charcoal. The combustion is done in restricted supply Nitrogen 5.0%
of air.
Hydrogen, methane and carbon monoxide are non-illumi-
C + O2 ----> CO2 + 97.7 kcal
nating but heat producing constituents. The unsaturated hydro-
CO 2 + C ----> 2CO - 38.3 kcal
carbons produce illumination. Nitrogen, carbon dioxide and
2C + O 2 ----> 2CO + 59.4 kcal oxygen are present as impurities.
Initially, carbon dioxide is the main product but when it rises Coal gas is obtained by destmctive distillation of coal
through the bed of coal, it combines with carbon, provided the at about 1000°C. For this plllpose, coal is heated at 1000-
temperature is 1000°C, forming carbon monoxide. Thus, heat 1100°C in a large fire-clay retorts. The products of decom-
is generated ducing its preparation. This heat can also be position are: {i).coaLg~s (li) coke (ili).coaltar{iv.)ammonic~
utilised if producer gas is generated on the spot and used while liquor. One ton of bituminous coal gives about 13000 cubic ft
still hot. of coal gas.
Producer gas is poisonous, heavier than air and insoluble in Uses: It is used :
water. It has a low calorific value. The CO bums and converted (i) as a fuel in the household and in metallurgical
into CO2 in air producing heat energy. The low calorific value operations.
(103 B.Th.V. per cubic ft) is due to the presence of large (ii) in providing. inert atmosphere in certain chemical
proportion of nitrogen in it. It is mainly used as a gaseous fuel processes.
in open hearth furnace in the manufacture of steel and glass. (iii) in smelting of metals and alloys.
It is also used to heat coke ovens for the manufacture of coal (iv) as a reducing agent.
gas. (v) as an illuminating gas.
(ii) Water Gas (iv) Oil Gas

Water gas is mainly a mixture of CO and Hz. It is made Oil gas is obtained by cracking of kerosene. It is a mixture
by blowing steam through the layers of incandescent (red hot) of lower hydrocarbons, mainly CH4, C2H4, C2H2, etc.
coal. The efficient working temperature is 1000-1 400°C. A thin stream of oil is allowed to drop on the red hot surface
C + HzO ----> CO + H2 - 28 kcal of an iron retort. The kerosene is broken down into gaseous
hydrocarbons.
Due to endothermic nature of this reaction, the coal cools
down after sometime and the formation of carbon dioxide C 16H34 ----> 6CH4 + 2C 2H4 + C2H2 + 4C
starts at low temperature. To check this formation, the The gas mixture is passed through hydraulic main to
current of steam is replaced by a blast of air. This raises the remove tar and soluble impurities and then collected in
temperature of coal and steam is readmitted. In general, water gas holder.
gas consists of 40 volumes of CO, 50 volumes of Hz, 5 Oil gas is generally used in laboratories.
volumes of CO2 and 4-5 volumes of nitrogen. Petrol gas is a mixture of petrol vapours and air. It is
The calorific value of water gas is fairly high (310 B.Th.V. obtained by passing air through petrol (solvent oil). Nowadays,
per cubic ft). The calorific value of water gas is increased by petrol gas is used in the laboratories instead of oil gas.
carburetting, i.e., adding gaseous hydrocarbons obtained by
cracking of petroleum oils. (v) Natural Gas
Water gas is used as a fuel and for the manufacture of
Natural gas is found in regions rich in petroleum. The gas
hydrogen. It is also used for lighting purposes and in the
consists of chiefly methane. The approximate composition of
manufacture of methyl alcohol. The flame of water gas is
a sample of natural gas is given below:
short and hot, it is thus used for welding purposes.
CH4 C2H6 C3HS C4H 10 N2
85% 9% 3% 1% 2%
(iii) Coal Gas
The composition may vary from place to place. Natural gas
Coal gas is a mixture of hydrogen, methane, carbon from certain regions has been found to have sufficient pro-
monoxide, ethylene, acetylene, carbon dioxide, nitrogen and portion of helium.
Chief use of natural gas is as a fuel. It is also used for the (iii) In case of smel1 of gas inside the kitchen, no flame should
production of hydrogen, carbon black and various petro- be produced and no electIic switch be touched.
chemicals. (iv) The LPG cylinder should never be stored in cupboard.
(v) Kitchen should be airy.
(vi) Liquefied Petroleum Gas (LPG) (vi) After cooking is over, the pressure regulator should be
Liquid or liquefied petroleum gas (LPG) is a clean burning turned off.
gaseous fuel which contains C 3 and C4 hydrocarbons of the LPG is an ideal fuel in modern living. The main
alkane and alkene series. LPG contains hydrocarbons of such advantages of LPG are :
volatility that can exist as gases under normal temperature and (a) It gives instant flame by just lighting a match box or lighter.
atmospheric pressure, but can be easily liquefied under high (b) It gives instant heat, there is no need to wait for appliances
pressure, i.e., the critical temperature of the gaseous mixture to warm up.
(LMP) is nearly equal to room temperature. The main con- (c) It gives correct amount of heat required, as the size of the
stituents of LPG are n-butane, isobutane, butene and propane. flame can be adjusted.
LPG is generally isolated either from natural gas or from (d) It gives comfort because cooking is quicker and the kitchen
the cracking units of petroleum refineries. During fractional does not get heated or get dirty like other fuels.
distillation of crude petroleum, the gases collected at the top of (e) It is much cheaper than other fuels.
the fractionating tower . which do not condense at all (hydro- (f) It is easy to store. The cylinder Qccupies very little space. LPG.
carbons having low boiling points such as methane, ethane, connections can be transferred from one place to another.
propane, butanes, etc.) are used for making LPG The mixture
of lower hydrocarbons is condensed under high pressure in (vii) Gobar Gas or Blo-gas
refrigeration units. However, traces of sulphur containing The mixture of gases that can burn and produce heat energy,
compounds such as ethyl mercaptan (C 2H sSH) or methyl which is emitted from places where organic wastes (like animal
mercaptan (CH 3SH) are deliberately added in order to detect dung, human excreta, vegetable waste, leaves, etc.) decay out
any dangerous leakage from the gas cylinder. of contact of air is called bio-gas or gobar gas.
The density of LPG is about 0.55 g mL-I and is colourless, Its main constituent is methane (60-70%). Other gases
ta~teless, odourless and non-toxic in nature. However, life is present are CO, H 2• COz, H 2S, N 2 , etc. Bio-gas is combustible.
not possible in its gaseous atmosphere due to lack of oxygen, It gives a blue flame with a lot of heat which may be used for
i.e., it is suffocating in nature. In gaseous state it is twice cooking, lighting and as a fuel for petrol and diesel engines.
heavy as air. It is highly inflammable and produces heat energy Organic waste is made to decay out of contact of air when
on combustion in air. bio-gas is produced. This process is called anaerobic fermen-
C 3Hg + 50 2 ~ 3C02 + 4H 20 + Heat tation. The waste that remains after fermentation called slurry
is a very good fertilizer as the bacteria add a lot of nitrogen to
C4H IO +Ci) O2 ~ 4C02 + 5H20 + Heat the waste during fermentation, thus improving the quality of
the fertilizer.
The average calorific value of LPG is 55 kJg-lor 29780
Bio-gas has become a very practical alternative energy
kcallm3. LPG is used as a domestic fuel, direct motor fuel,
resource in several rural areas of the country.
laboratory gas and a source of petrochemicals. About 80%
LPG is used nowadays in India as a domestic fuel (Cooking
gas). Domestic installation consists of a LPG cylinder, pressure.
4. Carbides
regulator, rubber tubing and a hot plate. On opening the cylinder ·Carbides are binary compounds of carbon with elements of
valve with the help of pressure regulator, the pressure inside lower or about equal electronegativity. Carbides are classified
the cylinder is reduced causing LPG liquid to vaporise into gas. into three types on the basis of chemical bonding. These are
The gas through rubber tube reaches the burner of the hot salt-like carbides, covalent carbides and interstitial or alloy
plate where it is mixed with air and burnt. like carbides. Carbides are generally prepared by heating the
LPG is the safest fuel but requires certain simple pre- element or its oxide with carbon or hydrocarbon at very high
cautions in day to day use. temperatures.
(i) As LPG is heavier than air and as such, it travels towards Ba + 2C~ BaC2
floor, so it is important that the flame should be at higher 2Li + 2C ~ Li2C2
level than cylinder. Thus, it is recommended that hot plate CaO + 3C ~ CaC 2 + CO
level should be above cylinder height. 4Li + C2H 2 ~ Li2C2 + 2LiH
(ii) There should be no electrical appliances like fridge in the
kitchen which can cause electric spark during switch on
Salt·like carbides: These carbides are formed by the
metals of groups lA, IIA and IlIA (except boron), coinage
or off.
metals, zinc, cadmium and some lanthanides. Depending on
the nature of the hydrocarbon formed during hydrolysis by SILICON
water or dilute HCI, the ionic carbides can be further classified
Silicon is the second most abundant element occurring in the
into the following types :
earth's crust (about 28% by weight). Silicon and oxygen make
(i) Acetylides: These are the ionic carbides which yield
up 75% of the crust of the earth. Unlike carbon, it is never
acetylene on hydrolysis. These are regarded as derivatives of
found in free state but always in combined state. It is an
acetylene and are thus called acetylides. The alkali metals and
important constituent of igneous rocks which' consists of
copper, silver and. gold form M2C2 type compounds. The
silicates of magnesium, aluminium, potassium or iron. Silicon
alkaline earth metals, zinc and cadmium give MC2 type carbides.
is widely present as silica (Si02) in various forms such as
These carbides are believed to contain [C=C]2- groups. Two
sand, quartz, flint, etc. Silicon dioxide, Si02 has a melting
types of crystal structures characterise these carbides. Both point of 1710°C.
are tetragonal and are derived from sodium chloride structure Silicon is obtained by the reduction of silica. It exists in two
by replacement of. Cl- ions by c:~- ions. allotropic forms: (a) amorphous and (b) crystalline. The
(ii) Methanides: These carbides evolve methane on amorphous variety is obtained by heating dry pOWdered silica
hydrolysis. These are· regarded as derivatives of methane with magnesium.
and are called methanides. A1 4C3, Be2C, Mn3C,etc., are some Si02 + 2Mg ----'7 Si + 2MgO
examples of methanides. These contain C4- groups. The crystalline variety is obtained by heating a finely
,(iii) AUylldes: These, carbides evolve ..allylene.(methyl powdered sand or quartz with carbon in an electric furn~~ .
acetylene) on hydrolysis. The only example of this type is A small amount of iron is added to prevent the formation of
Mg2C 3. It contains c t discrete groups. carborundum (SiC).
Si02 + 2C ----'7 Si + 2CO
Mg2C3 + 4H20 ----'7 2Mg(OHh + CH3-C=CH
Propyne High purity silicon can be prepared by reducing SiCl 4 with
(Iv) Mixed carbides: These carbides yield a mixture of magnesium.
hydrocarbons on hydrolysis. Carbides of iron group, UC 2 and SiC4 + 2Mg ----'7 Si + 2MgCl2
ThC2 belong to this class. The magnesium chloride, being water solub~e, is then washed
Covalent carbides: The only true covalent carbides are away from the silicon. The final purification of silicon takes
those of silicon (SiC carborundum) and boron (B4C and B13C2).' place by zone-refining.
These are chemically inert and extremely hard materials.On Amorphous silicon is chemically more reactive than
account of hardness, these carbides are used as abrasives. crystalline silicon. Amorphous smcon is a brownish powder. It
Silicon carbide is produced by heating quartz or sand with burns brilliantly in oxygen and ignites spontaneously in fluorine.
an excess of coke in an electric arc furnace. Si + O 2 ----'7 Si02
Si + 2F2 -----7 SiF4
Si02 + 3C 2000-2500°C) SiC + 2coi It decomposes steam at red heat. It dissolves in the mixture
of HN03 and HCI. However, it dissolves readily in alkalies.
Metallic or interstitial carbides: In these carbides, Si + 2H 20 -----7 Si02 + 2H2
small carbon atoms occupy interstitial positions in the crystal Si + 2KOH + H 20 ----'7 K2Si03 + 2H2
lattices of the metals. These are of two types: MC (M = Ti, Zr, Na2C03 + Si -----7 Na2Si03 + C
Hf, V, Nb, Ta, Mo, W) and M 2C (M = V, Mo and W). These It combines with certain metals forming silicides.
carbides possess metallic lustre, high electrical conductivity 2Mg + Si -----7 Mg2Si
and are chemically inert. These are extremely hard like diamond When amorphous silicon is strongly heated, it fuses and on
and possess very high melting points. cooling solidifies to the crystalline form. It is very hard
UseS: (i) Calcium carbide is used to prepare acetylene. crystalline silicon, does not burn in oxygen but it readily
Acetylene is the starting material for many organic compounds. combines with fluorine. It dissolves in mixture of HN03 and
It is also used for production of oxy-acetylene flame employed HE When fused with alkali, it gives a silicate.
for welding purposes. Na2C03 + Si -----7 Na2Si03 + C
(ii) SiC, being hard substance, is used as abrasive. Boron Silicon is used in the manufacture of certain alloys such as
carbide is also used as abrasive and shield from radiations. It ferrosilicon, silicon bronze, manganese silicon bronze, etc.
is used for the construction of atomic reactors. These alloys possess high strength and hardness and resistant
(iii) Carbides which can withstand high temperature are to the attack of acids.
used widely in furnace lining. One outstanding property of silicon in a high state of purity
is its electrical conductivity. It acts as a semiconductor, i.e.,
(iv) Tungsten carbide, WC, is used for the manufacture of
it does not conduct electricity until a cartain electric voltage is
high speed tools.
applied, but beyond that it conducts moderately. Its conductivity
properties can be changed by a process known as doping, i.e., sulphate, copper sulphate, etc., are placed and whole solution
placing other atoms in a crystal of pure silicon. is left as such for a night, beautiful hollow tubes of metallic
The excesses (n-type) and deficiencies (p-type) of electrons silicate gels possessing different colours shoot up from these
result from inserting arsenic and boron atoms respectively in crystals and look like plants. This is called silica garden or
the place of silicon atoms in the crystalline structure. In 1947, chemical garden.
an electrical device called the transistor was invented. The Uses:. It is used:
simplest device used layers of n-p-n or p-n-p-doped sili.con. (a) in fire proofing of wood and textiles.
The most revolutionary application of silicon's semiconductor (b) as a preservative for eggs.
properties has been in the design of integrated circnits, (c) as an adhesive cement for joining pieces of china clay.
computer memories and even whole computers called (d) in the soap industry as a filler for a cheaper variety of soap.
microprocessors on tiny chips of silicon. These are used in (e) in paint industry and calico printing.
calculators, cameras, watches, toys, cardiac pacemakers and (f) for making silica gel, Si02·xH20. When a solution of
many other products. Na2Si03 is acidified with HCI, a gelatinous precipitate of siliCic
9:1 COMPOUNDS OF SILICON (H2Si03) acid is slowly formed.

Na2Si03 + 2HCI ~ 2NaCI + H2Sio3
1. Carborundum (Silicon Carbide), SiC· If most of the water 1s carefully removed, the jelly like
precipitate-ofH2Si03-is converted intoasolid:product which
It is obtained 'whena fuixtllre· of sand,··carbon; coimrion· sait is called silica gel. It possesses excellent absorption. property
and saw qust is strongly heated in an electric furnace.
of gases and vapours.
Si0:2 + 3C ~ SiC + 2CO
Salt is added to act as flux and saw dust makes the mass 3. Silicones
porous. Two carbon rods connected by a thin carbon core act
as electrodes in the furnace. Carborundum is formed round the These are organosilicon polymers containing Si--O-Si
central core of carbon. It is crushed, washed with H 2S04, linkages. These are formed by the hydrolysis of alkyl or aryl
NaOH, H20 and then dried. substituted chlorosilanes and their subsequent polymerisation.
Properties: (i) Pure carborundum is colourless but The alkyl or aryl substituted chlorosilanes are prepared by the
commercial samples possess yellow, green or blue colour. reaction of Grignard reagent and silicon tetrachloride.
(ii) It is very hard mass. However, its hardness is less than RMgCl + SiCl4 ~ R-SiCl3 + MgC12
diamond. Grignard reagent
(iii) It is chemically inert and resists the attack of almost all 2RMgCI + SiC4 ~ R2SiCl2 + 2MgCl2
the reagents except fused caustic soda. The fused alkali
dissolves it in presence of air. 3RMgCI + SiC4 ~ R3SiCI + 3MgCl2
4NaOH + SiC + 202 ~ Na2Si03 + Na2C03 + 2H20 R stands for .:.-...cH3, -C2HS or -CJI5 groups.
Its structure is similar to diamond. Hydrolysis of substituted chlorosilanes yield corresponding
Uses: It is used as an abrasive instead of emery. It is silanols which undergo polymerisation.
used to make grind-stones, knife sharpeners, etc.
2. Sodium Silicate, Na2Si03 (Water Glass)

R). <[Cf.ft:OH
Si + -2HC1) R)Si<OH
R . [CCH:OH R OH
It is commercially called water glass. Chemically it is Dialkyl silandiol
sodium metasilicate containing an excess of silica. Its com-
Polymerisation of dialkyl silandiol yields linear thermo-
position may vary from Na2Si03·Si02 to Na2Si03·3Si02' plastic polymer.
It is obtained by fusing soda ash (Na2C03) with pure sand
at a high temperature. R R ·R R
Na2C03 + Si02 ~ Na2Si03 + CO2i I I I I
The resulting mass is extracted with water and the solution HO-Si-:9H: ± H::O-Si-OH ~ HO-Si-O-Si-OH
is evaporated to get a syrupy rnass known as water glass. I I I I
Properties: It is soluble in water. The solution is alkaline R R R R
due to hydrolysis. Polymerisation continues on both the ends and thus chain
Na2Si03 + 2H20 ~ 2NaOH + H2Si03 increases in length.
If in a solution of sodium silicate of density 1.1, some RSiCl 3 on hydrolysis gives a cross linked silicone.The
coloured salts like cobalt nitrate, nickel chloride, ferrous formation can be explained in three steps:
CI OR Properties: (i) The lower silicones are oily liquids but
I 3H 2O I
(i) R-Si-CI -3HCI ) R-Si-OR higher members containing long chains or ring structures are
I I waxy and rubber like solids.
CI OR (ii) Silicones are stable towards heat.
R R R (iii) Chemical reagents have no action on silicones.
I I I (iv) These are non-toxic.
(ii) RO-Si-:9H ±H: O-Si----19H ±H: O-Si-OR ~ (v) Viscosity of silicone oils remains the same at different
I I I temperatures.
OR OR OR (vi) Silicones are good electrical insulators.
(vii) These are water repellants.
R R R Uses: (i) Silicone oils are used for high temperature oil
I I I baths, high vacuum pumps and low temperature lubrication.
RO-Si-O-Si-O-Si-OR (ii) These are used in making water-proof cloth and paper
I I I by exposing cloth or paper to the silicone vapour.
OR OR OR (iii) These are used as insulating materials for electric
R R R motors and other electrical appliances.
I I I (iv) These are mixed with paints and enamels to make them
(iii] -.--. H0==Si=0c=Si=-c.=O=Si==OH--- ... '-.- -0 ~., - , --~. resistant to the effects of high temperature, sunlight, chemicals---..
I I
1----1
I and damp.
:OR: (v) These are used in making vaseline like greases which
--iIJJ 0 are used as lubricants in aeroplanes.
(vi) Silicone-rubbers are useful as they retain their elasticity
RO-Si-O-Si-O-Si-OR over a range of temperatures.
I I I
R R R 'ij 4. Silicates
Silicates are metal derivatives of silicic acid, R 4Si04 or
R R R·
Si(ORk Silicates are formed by heating metal oxide or metal
I I I carbonates with sand, e.g.,
-O-Si-O-Si-O-Si-O-
I I I Na CO
2 3
Fused with sand) Na4Si04, Na2(Si03)n, etc.
Si0 2
o o o
I I I
-O-Si-O-Si-O-Si-~
I I I
R R R -Ot"---+---",O- -0 - Oxygen
Cross linked silicone -0 0- 0 - Silicon
Cyclic (ring) silicones are formed when water is eliminated Plane projection of
silicate ion
from the terminal -OR groups of linear silicones.
0-
Silicates have basic unit of SiOt, each silicon atom is
bonded with four oxide ions tetrahedrally.
There are following types of silicates:
(i) Orthosilicates: These silicates contain single discrete
unit of SiO!- tetrahedra,
e.g., Zircon ZrSi04; Forsterite or Olivine Mg 2Si04
Phenacite Be2Si04; Willemite Zn2Si04
(ii) Pyrosilicates: These silicates contain two units of
siof joined along a comer containing oxygen atom. These
Cyclic silicone are also called as island silicates.
R3SiCI on hydrolysis forms only a dimer
R3Si 0 :B:; J:>H: SiR3 ~ R3Si-O-SiR3
e.g., Synthetic silicates Li2Si0 3, Na2Si03;

Spodumene LiAl(Si03h;
Jadeite NaAl(Si0 3)2;
Enstatite MgSi0 3 ;
Diopside CaMg(Si0 3h;
Tremolite Ca2Mgs(Si4011 h(OHh
-0
0- (v) Two dimensional sheet sllicates: In such silicates,
three oxygen atoms of each tetrahedra are shared with adjacent
\ I SiOt tetrahedra, such sharing "forms two dimensional sheet
structure with general formula (Si20S)~n-.
co/"!'------o/"\'------o-
0- -0
e.g., Thortveitite SC2(Si 20 7);
Hemimorphite Zn3(SiZ07)Zn(OHhH20
(iii) CycUc structure: Cyclic or ring silicates have
g~neral JQI1U~la (SiQ~-)n Qr(Sj03)~Il-.
Structure and example of cyclic silicates containing
Si30t and Si60i~- ions are given below:
e.g., Talc Mg(Si 20shMg(OHh

Kaolin AI2(OHMSi20S)
(vi) Three dimensional sheet silicates: These silicates
involve all four oxygen atoms in sharing with adjacent SiO:t-
tetrahedra.
e.g., Beryl Be3Al2Si6018 ; Benitoite BaTiSi30 9 e.g., Quartz, Tridymite, Crystobalite, Feldspars, Zeolites
Wollastonite Ca3Si309; Catapleite Na2ZrSi309·2H20 and Ultramarines.
(iv) Chain sllicates: Chain silicates are formed by sharing Zeolites are a class of three dimensional aluminosilicates.
two oxygen atoms by each tetrahedra. Anions of chain silicate They carry a negative charge on aluminosilicate framework
have two general formulae, which is compensated by neighbouring alkali-metal or alkaline-
(a) (Si03)~"- (b) (Si4011)~n- earth cations." They possess open structures consisting of
polyhedra cavities of uniform size and shape. Most zeolites
(natural or synthetic) accommodate water molecules in their
(a) cavities, where they provide a mobile phase for the migration
of the charge-compensating cations. This enables zeolites to
serve as ion - exchange materials and is the key to their ability
to soften water.
When hard water is passed through a column packed with a
zeolite, the calcium and magnesium ions exchange with the
sodium ions,
(b) 2NaZ(s) + Ca2+(aq.) ~ caZ2(s) + 2Na+(aq.)

When the ion exchange capacity of the zeolite is exhausted,
this reaction can be reversed by passing a concentrated solution
of sodium chloride through the zeolite to regenerate it in the
sodium form.
• 5. Glass Manufacture: The raw materials used in the manufacture
of glass depend on the variety of glass. For ordinary glass, the
Glass is a transparent or translucent amorphous supercooled
raw materials are sand, washing soda and limestone. These are
solid solution of silicates and borates.The most common
ground separately and mixed in the proper proportion, i.e., in.
silicates present are those of potassium, calcium and lead. Its
the ratio of 100 : 35 : 15. The mixture is known as "batch".
composition is variable as it is not a true compound. ,
Broken glass pieces known as "cullet" are added to the mixtUre
An approximate formula for ordinary glass may be given as,
of raw materials. Cullet melts at low temperature and helps in
R20·MO·6Si0 2
melting the rest of charge at low temperature.
where R = Na or K and M = Ca, Ba, Zn or Pb.
The charge is fused now either in a pot or tank furnace at
Si02 may be replaced by AlZ0 3, B203, P20 S' When glass
about 1400°C. This temperature is obtained by burning
is heated, it does not melt at a fixed temperature. However, it
producer gas. Both the furnaces work on the regenerative
gradually softens and can be moulded into any desired shape.
system of heat economy. A tank furnace is used where the
It is the property of glass which makes it a useful material for
output expected is large but where the highest quality of
making articles of different shapes. Glass melts into a li~uid at
glass is desired, the pot furnace is used. In tank furnace, the
a very high temperature. ,
process is continuous while in pot furnace the process is
Raw materials: Following are the main raw materials discontinuous.
used in the manufacture of glass :
Pot furnace: A pot is a large monkey shaped crucible
_(a) Acidic oxides: A numb~r of acidic oxides are, use.~t. The ofthetypegiveninFig,9.6;In-apot furnace a-number ofsueh-- .,
choice depends upon the quality of glass to be manufactured.
pots are arranged in a circle. These are heated by burning
(i) Silica: Sand of uniform size is used, i.e., neither too
producer gas.
fine nor too coarse. Fine variety makes the reaction violent
while coarse variety slows down the reaction. It should be free
~ Burning fuel gas ~
from iron oxide and organic matter.
(ii) Boron trioxide, B203: This is introduced in the form
of boric acid or borax. It is used when a glass of low
cOefficient of expansion is required.
(iii) Phosphorus pentoxide, P20S: It is introduced in Melting Pot
the form of calcium phosphate. It is used when opalescent
glass is required.
(b) Basic oxides: One or more of the following basic +• + + t t t t
Air + Fuel Fuel gases
oxides are used: gases
Lithium, sodium, potassium, calcium, barium, magnesium,
Fig. 9.6 Pot furnace
lead and zinc oxides. Sodium is introduced in the form of
sodium carbonate (NaZC03), sodium nitrate (NaN03) or sodium Tank furnace: It is a large rectangular clay tank in
sulphate (NaZS04) and carbon mixture. Potassium is added as which raw materials are fused. It is also heated by producer
potassium carbonate (K2C03) or potassium nitrate (KN03). gas (Fig. 9.7).
Calcium is added as CaC03 or CaO. Barium is put in as BaC03.
Magnesium is added as MgC03' Lead oxides are put in as such.
Zinc oxide is used when heat resistant glass is to be obtained.
(c) Colouring materials: Coloured glasses are obtained
by adding certain metallic oxides or salts in the fused mass.
The following is the list of various substances used for
imparting a particular colour to the glass.
Substance Colour imparted
Ferric oxide Yellow
Chromic oxide Green
Cobalt oxide Blue
Selenium metal Red
Manganese oxide Purple
Cuprous oxide Red
Cadmium sulphide Yellow
Nickel oxide, }
Fig. 9.7 Tank furnace
Cobalt oxide, Black
Manganese oxide
The free silica decomposes the carbonates, setting the Etching of glass:
evolution of C02.
Glass is attacked by hydrofluoric acid. This property is
Na2C03 + Si02 ~ Na2Si03 + CO2 used in the etching of glass.
CaC0 3 + Si02 ~ CaSi03 + CO2 The glass to be etched is coated with a thin layer of wax and
the design to be produced is scratched with a needle or stylus.
At 1400°C silica also dissolves in the silicates of sodium and An aqueous solution of hydrofluoric acid is applied to the
calcium. exposed part. After sometime it is placed in water and wax is
Na2Si03 + CaSi03 + 4Si02~ ~a2Si03·C~Si03-4Si02, removed from the surface. The marks are engraved on the
Glass exposed parts.
The heating is continued till bubbles of C02 no longer rise
and the mass melts to a clear liquid. The clear viscous liquid TIN
is then poured into moulds or stamped with dies to produce Occurrence: Tin does not occur free in nature. The most
desired mticles. impOltant ore is cassiteIite, Sn02, which is also known as tin
Annealing: The glass if cooled rapidly becomes brittle stone. The ore is usually associated with siliceous matter,
and fragile. The articles of glass are cooled neither very slowly tungstates of iron (FeW04) and manganese (MnW04). It also
nor very rapidly. These are made to pass through a long tunnel exists along with the pyrites of copper, iron and zinc.
likefurnace. .which is very hotatthe mouthend.and.verycold, Extraction: Tin is extracted from cassiterite ore4trc:
at the tail end, i.e., the articles are cooled gradually during extraction involves the following steps:
passage through the tunnel. This process is termed as (a) Concentration: The ore is crushed and powdered. It
annealing and takes several days for completion. is washed with running water which removes lighter siliceous
The articles so cooled require some finishing such as matter. Iron tungstate is removed by electromagnetic separator.
cutting, grinding, polishing, etc. Only the finished products are The ore is now roasted in a current of air to remove sulphur
sold in the market. and arsenic as S02 and AS 20 3, respectively.
(b) Smelting: The roasted ore is mixed with about one
Varieties of glass: fifth its ma<;s of powdered anthracite (carbon) and a little
By varying the composition of batch, several varieties of limestone (flux). The mixture is subjected to heat in a
glass are obtained. Some of the varieties are the following: reverberatory furnace when tin' oxide is reduced to tin metaL
(i) Soda glass or soft glass: It is a mixture of sodium The liquid metal is drawn off from the furnace.
and calcium silicates. It is a cheap variety. It softens at a Sn02 + 2C ~ Sn + 2CO
comparatively low temperature and can be easily shaped into The crude tin metal contains a number of impurities. It is
different forms. It is used in making glass tubes, window further purified by liquation and poling. The crude metal is
panes, bottles, dishes, etc. heated gently on the sloping hearth of reverberatory furnace.
(ii) Potash glass or hard glass: It is a mixture of Tb;~ tin metal flows down leaving behind iron, copper,
potassium and calcium silicates. It fuses with difficulty. It is tungsten. ,,~tc. The molten metal is now stirred with a green
more resistant to the action of water and acids. It is used for wood pole whereby impurities like S, As are oxidised, and any
making hard glass apparatus. tin oxide formed is reduced by the hydrocarbons of wood.
(iii) Flint glass: It is a mixture of potassium and lead Properties: (i) Tin is a silvery white metal. It melts at
silicates. It has a very high refractive index and is used for 232°C and boils at 2270°C. It is not affected by air.
making electric bulbs and optical instruments. (ii) It is malleable and ductile but at 200 D C, it becomes brittle
(iv) Jena glass: It is a mixture of zinc and barium and can be powdered.
borosilicates. It is resistant to heat, shock and common (iii) It produces a peculiar sound whenever it is bent. The
reagents. It is used for making good quality of glass wares. cracking sound is known as tinery.
(v) Pyre,x glass: It is a mixture of zinc, barium (iv) It exists in three allotropic forms. White tin is the
borosilicates and alumino silicates. It is similar to jena glass in common and most stable.
properties. It can withstand sudden changes in temperature
18"C
and is highly suitable for laboratory glassware and oven Grey ~ White Rhombic
glassware. Its approximate composition is : silica 80%, Na20 Density 5.74 • 7.32 6.55
4%, CaO 0.5%, K20 0.5%, B20 3 12%, Al203 3%. The conversion of white tin to grey tin in .cold countries is
(vi) Crooke'S glass: It is a special type of glass containing accompanied by decrease in density, i.e., increase in volume.
cerium oxide. It does not allow the passage of ultraviolet rays. It is very brittle and easily comes into powdered form. This is
It is used for making lenses. termed as tin disease or tin pest or tin plague.
(v) Tin is much less reactive than the metals of group lA, Name Composition Uses
IIA and IlIA. When heated in presence of oxygen at 1500-1600°C, (i) Solder Sn 67%, Pb 33% in soldering
it bums with bright flame forming stannic oxide, Sn02. (ii) Rose metal Sn 28%, Pb 22%, Bi 50% for electric fuses
Heat (iii) Bronze Cu 75-90%, Sn 25-10% for utensils, statues
Sn + 02 --t Sn02
and coils
It is not attacked by water. Molten tin decomposes steam (iv) Bell metal Cu 80%, Sn 20% bells and gongs
with liberation of hydrogen. (v) Type metal Sn 3%, Pb 82%, Sb 15% printing types
(vi) Tin is not attacked by organic acids. This property is (vi) Britannia metal Sn 86%, Sb 12%, eu 2% cheap table ware
utilised for tinning cooking utensils made of copper or brass.
It dissolves slowly in dil. HCI but readily in conc. HCl. 9.1 COMPOUNDS· OF TIN
Sn + 2HCI ---; SnCl2 + H2 1. Stannous Oxide, SnO
It dissolves in dil. H 2S04as well as in conc. H 2S04 , Preparation: (a) It is prepared from stannous chloride
Sn + H 2S04(dil.) ---; SnS04 + H2 by following methods.
Sn + 4H 2S04(conc.) ---; Sn(S04)2 + 2S02 + 4H 20 (i) Sodium hydroxide is added· to stannous chloride. The
stannous hydroxide thus formed is heated in an atmosphere of
Dilute HN0 3 dissolves tin with the formation of ammonium C02 when stannous oxide is formed.
nitrate.
SnCl2 + 2NaOH ---; Sn(OHh + 2NaCI
4[Sn + 2HN03 ---; Sn(N03h + 2H]
Sn(OHh co2SnO + H20
)
HN0 3 + 8H ---; NH3 + 3H 20
(ii) A mixture of solid stannous chloride and sodium
NH3 + HN0 3 ---; NH 4N0 3 carbonate is heated in atmosphere of CO2, when stannous
4Sn + lOHN0 3 ---; 4Sn(N0 3h + NH4N0 3 + 3H20 oxide is formed. .
SnCl2 + Na2C03 ---; SnO + CO2 + 2NaCI
Conc. HN03 oxidises Sn into metastannic acid.
(b) It may also be prepared by heating stannous oxalate in
2[2HN03 ---; H 20 + 2N02 + 0] absence of air.
Sn + 20 + H 20 ---; H2Sn03 Sn(COOh ---; SnO + CO + CO 2
Properties: (i) It is a dark grey or black powder. It is
Sn + 4HN03 ---; H2Sn03 + 4N02 + H 20
insoluble in water.
(vii) Tin dissolves in hot alkali solutions forming stannates. (ii) It bums in air with incandescence forming stannic
Sn + 2NaOH + H 20 ---; Na2Sn03 + 2H2 oxide, Sn02. .
(viii) Tin directly combines with halogens and sulphur. 2SnO + 02 ---; 2Sn02
Sn + 2Cl2 ---; SnCl 4 (Stannic chloride) (iii) It is an amphoteric oxide. It dissolves both in acids and
alkalies.
Sn + 2S ---; SnS2 (Stannic sulphide)
SnO + 2HCI ---; SnCl2 + H 20
Uses: (i) The metal is extensively used in tinning brass Stannous
. chloride
utensils. Organic acids present in the food stuff attack the
utensils which are made of copper, brass, etc. This may cause SnO + 2NaOH ---; Na2Sn02 + H20
Sod. stannite
food poisoning. The utensils are protected by tinning, i.e.,
depositing a thin layer of tin on the surface of utensils. The Stannites are known only in aqueous solutions. Stannites
vessel to be tinned is perfectly cleaned and heated. A pinch of absorb oxygen from air and oxidised to stannates which are
NH4Cl is sprinkled to remove the oxide film. A little tin is now stable in nature.
fused on the clean surface and then rubbed over with the help 2Na2Sn02 + O 2 ---; 2Na2Sn03
Sod. stannate
of cotton rag to have a uniform layer.
Oi) It is largely used in forming a protective coating over
iron. The process of depositing tin over the sheets of iron or " 2. Stannic Oxide, Sn02
steel is called tin plating. Tin plating is done either mechanically It is found in nature as cassiterite or tin stone.
or elecuically. Preparation: It may be prepared by heating tin in air or
(iii) Tin in the form of tin foil is used for wrapping cigarettes, by heating metastannic acid which is obtained h" rc:acting tin
confectionary and for making the tooth-paste tubes. with concentrated nitric acid.
(iv) Tin amalgam is used in making min·ors. Sn + O2 -----t SnOz
(v) It is used for making useful alloys.
Sn + 4HN03 ----7 H2Sn03 + 4N0 2 + H 20
H2Sn03 ~ Sn02 + H20 (v) It is a strong reducing agent Few examples are given
Metastannic acid below: .
Properties: It is a white powder, insoluble in water. It (a) It reduces mercuric chloride to mercurous chloride
is somewhat unreactive. However, it dissolves in conc. H2S04 (white ppt.) and finally to metallic mercury (dark grey or black).
forming stannic sulphate. 2HgCl2 + SnCl2 ~ Hg2Cl2 + SnCl4 .
Sn02 + 2H2S04 ~ Sn(S04h +. 2H20 Mercurous cmoride
When the solution is diluted, stannic oxide is reprecipitated. Hg2Cl2 + SnCl2 ~ 2Hg +' SnCl4
Sn(S04h + 2H20 ~ Sn02 + 2H2S04 (b) It reduces ferric salts to ferrous salts and cupric salts
into cuprous salts.
It readily dissolves in alkalies forming stannates.
2FeCl3 + SnC12 ~ 2FeCl2 + SnCl4
Sn02 + 2KOH ~ K2Sn03 + H 20
2CuCl2 + SnCl2 ~ 2CuCI + SnCl4
Stannates are used as mordants in dyeing. It is used in the
manufacture of pottery and glass in the form of white glazes. (c) It decolourises iodine and thus can be titrated with it.
SnCl2 + 2HCl + 12 ~ SnCl4 + 2HI
~ 3. Stannous Chloride, SnClz (d) Organic nitro compounds are reduced to amino
Preparation: (i) Hydrated stannous chloride SnC12·2H20 compounds.
is prepared "y.
dissolying tin in hot' concentrated hydrochloric C6HSN02 + 6HCl + 3SnCl2 ~ C6HSNH2 +~SnC14+2~
acid and subjecting the solution to crystallisation. Nitrobenzene Aniline
Sn + 2HCl ~ SnCl2 + H2 (e) It reduces gold chloride to metallic gold.

Hydrated stannous chloride consists of two molecules of 2AuCl 3 + 3SnCh ~ 2Au + 3SnCl4
Colloidal gold
water as water of crystallisation, i.e., SnCI2·2H20.
Anhydrous salt cannot be obtained by heating the hydrated SnCl4 undergoes hydrolysis forming stannic acid which
salt as it undergoes hydrolysis and a white solid of tin hydroxy absorbs colloidal particles of gold and thus forms purple of
chloride is formed. cassius.
Uses: It is used: (i) as a reducing agent.
SnC12·2H20 ~ Sn(OH)Cl + HCl + H 20 (ii) for making purple of cassius. Purple of cassius is used
(ii) Anhydrous stannous chloride is formed when dry HCl for colouring glass and pottery.
gas is passed over hot tin. . (iii)' as a mordant in dyeing.
Sn + 2HCl (gas) ~ SnCl 2 + H2
It can also be obtained when a mixture of Sn and calculated 4. Stannic Chloride, SnCI4
quantity of mercuric chloride is heated. It is prepared by passing dry chlorine over fused tin in a
Sn + HgCh ~ SnCl2 + Hg retort. The vapours of stannic chloride are condensed in water
cooled receiver.
Properties: (i) It is a white crystalline solid. It is soluble
Sn + 2Cl2 ~ SnCl 4
in water, alcohol and ether.
(ii) In water, it is soon hydrolysed. However in presence of Properties: (i) It is a colourless fuming liquid having
HCI (acid), hydrolysis is reversed. disagreeable smell.
(iii) It forms ·a white precipitate with alkalies. The (ii) It. is hygroscopic and forms crystalline hydrates
precipitate of stannous hydroxide, however, dissolves in containing 3, 5, 6 and 8 molecules of water as water of
excess of alkali. crystallisation. The pentahydrate SnCI4·5H20, is known as
"'butter of tin" or "oxymuriate of tin".
SnCl2 + 2NaOH ~ Sn(OHh + 2NaCl
(iii) It is soluble in water in which it undergoes hydrolysis.
Sn(OHh + 2NaOH ~ Na2Sn02 + 2H20 SnCl4 + 4H20 ~ Sn(0H)4 + 4HCl
Sodium stannite
(iv) It forms a dark brown precipitate of stannous sulphide It is also soluble in organic solvents showing that it is a
on passing H2S through its solution. The precipitate dissolves covalent compound. .
in yellow ammonium sulphide. (iv) It dissolves in conc. HCl forming chlorostannic acid. In
presence of ammonium chloride, it forms ammonium salt of
SnCl2 + H2S ~ SnS + 2HCl this acid.
SnS + (N~hS2 ~ (NH4hSnS3 SnCl4 + 2HCI ~ H2SnCl6
Yellow ammonium Ammonium thio- Chlorostannic acid
sulphide stannate
SnCl4 + 2NH4CI ~ (NH4hSnCI6
Ammonium chlorostannate
Uses: It is used :
(i) in pentahydrate form as a mordant and in ammonium
chlorostannate form as a mordant for pink dyes.
(ii) for fire-proofing cotton.
(iii) for increasing the weight of silk.
LEAD OR PLUMBUM
Occurrence: Lead is mainly found. in the form of sulpb.ide.
The are is called the galena, PbS. It is usually associated with
zinc blende, iron pyrites and traces of silver (up to 0.1 %). The Fig. 9.9 Reverberatory furnace
lead content in galena are varies from 6 to 8%. The other less
important ores of lead are : The temperature of the furnace is raised and air s~pply is
(a) anglesite, PbS0 4 (b) cerussite., PbC03, (c) lanarkite, reduced. Some more concentrated galena ore is added. PbS
PbO·PbS04· . reacts with PbO and PbS04 forming lead metal.
Extraction: Lead is mainly extracted, from galena ore. 2PbO + PbS ---'; 3Pb + S02
The extraction involves the following steps: PbS04 + PbS ---'; 2Pb + 2S02
(i) Concenu'ation of the ore Thus, roasting and smelting are done in the same furnace
(ii) Reduction at different· tempeFatmes.
(iii) Purification Molten lead is drawn off
(i) Concentration: The ore is crushed and sieved. It is from the lower part of the
submitted to the froth floatation process for concentration. furnace.
(b) Carbon reduction
process: The concen-
trated are is mixed with
some lime and it is then
roasted in a sinterer (Fig.
9.10). It is mounted on
trunnions for charging and
discharging. It is provided
with a grating at the bottom
and a hood at the top. The
air is introduced through
grating and is circulated
through the charge by Air blast
applying suction at the top
of the hood. PbS is Fig. 9.10 Sinterer
oxidised to lead oxide .
.Fig. 9.8 Froth floatation process 2PbS + 302 ---'; 2PbO + 2S02
Lime serves two purposes:
The are is introduced in a large tank containing water to which
(i) It prevents the formation of PbS0 4.
some pine oil has been added. The mixture is agitated by
(ii) It prevents the formation of PbSi0 3.
passing compressed air. The froth is produced which carries
[PbSi03 + CaO ---'; PbO + CaSi03]
away along with it to the surface the are particles while the
gangue settles down at the bottom. The sintered are is crushed into small pieces and mixed with
coke and lime. It is fed into a small blast furnace (15-20 feet
(ii) Reduction: Two processes are used.
in height and 3-5 feet in 'aiameter). The following reactions
(a) Air reduction process for ores rich in lead content,
occur in the blast furnace,
(b) Carbon reduction process for ores poor in lead content.
PbO + C ---'; Pb + CO
(a) Air reduction process: The concentrated are is
PbO + CO ---'; Pb + CO2
roasted in the reverberatory furnace. The are is partially oxidised
by adjusting the supply of air. CaO + Si0 2 ---'; CaSi03 (slag)
2PbS + 302 ---'; 2PbO + 2S02 PbSi0 3 + CaO ---'; PbO + CaSi03
(if formed)
PbS + 202 ---'; PbS0 4
The slag and molten metal are drawn out from the furnace. (vii) It is not affected by pure water except at the boiling
(iii) Purification: The lead obtained by any ofthe above point. It dissolves slowly in water contaffi.ing dissolved oxygen.
two processes cont£rins Bi, Sb, Cu, Fe, Ag, etc., as impurities. 2Pb + 2H 20 + O2 ----? 2Pb(OHh
The removal of these impurities is done by the following The dissolution of lead in water is known as plumbo-
processes: solvency. The value of plumbosolvency increases if the water
(i) Softening PfO- \ contains nitrates, organic acids and ammonium salts.The
cess: This process Charging pipe
presence of soluble sulphates, phosphates, carbonates, etc.,
removes the base decrease the dissolution of lead due to formation of a protective
metals. The impure thin layer of insolubIe'lead salts. Lead pipes are often used for
metal is melted on the conveying drinking water. In order to minimise the dissolution
shallow hearth of the of lead in the form of lead salts which are poisonous, hard
reverberatory furnace water is first passed through lead pipes as to deposit the
and a current of air is protective film on the inner surface of the pipes.
circulated. The base (viii) Reaction with acids: Dilute HCI and H2S04 have
metals are oxidised and practically no action on lead. Lead dissolv~s in hot cone. HCI
come on the surface with evolution of hydrogen. .
of the molten mass as 3[Pb + 2HN0 3(dil.) ----? 2Pb(N0 3h + 2H]
scum which is 2[HN03 + 3H ----? NO + 2H20]
removed. . ~
(ii) Desilverisa- 3Pb + 8HN03(dil.) ----? 3Pb(N03h + 2NO + 4H20

tion: The removal Pb + 2HN0 3(conc.) Pb(N03h + 2H
of silver is done by 2[HN0 3 + H ~ N0 2 + H20]
Parke's process or Pb + 4HN0 3(conc.) ----? Pb(N0 3)2 + 2N02 + 2H20
Pattinson's process. Organic acids dissolve lead in presence of oxygen.
(iii) Electrolytic Fig. 9.11 Blast fumace
re6ning : Desilverised Pb + 2CH3COOH +402 ----?Pb(CH3COOh + H 20
lead is further purified by Bett's electrolytic method. It consists Hot cone. H 2S0 4 dissolves lead with evolution of S02 butthe
of impure lead as anode and pure lead as cathode while lead reaction becomes slower due to forniation of insoluble PbS0 4.
silico fluoride, PbSiF6, acts as an electrolyte. This contains
Pb + 2H 2S04 ----? PbS04 + S02 + 2H 20
8 to 12% hydrofluosilicic acid (H2SiF6) and a little gelatin.
On passing current, pure lead is deposited on the cathode, HN0 3 is the best solvent for lead. With dil. HN0 3, NO is
the less electropositive impurities like Ag, Au, Sb, etc., collect evolved while with cone. HN0 3, NOi is liberated.
below anode as anodic mud while more electropositive (ix) Reaction. with NaOB: Lead dissolves in NaOH
impurities like Fe, Zn, Ni, etc., go into the solution. forming sodium plumbite with evolution of hydrogen.
Properties: . (i) It is a bluish grey metal. It has bright Pb + 2NaOH ----? Na2Pb02 + H2
metallic lustre when freshly cut. It is soft in nature and can be <;:ut (x) Reaction witb non-metals: Lead directly combines
with knife. It is a heavy metal (sp. gr. 11.35). It melts at 327°C. with sulphur and halogens.
(ii) It leaves a black mark on paper. Pb + S ----? PbS
(iii) It is malleable but not ductile.
(iv) It is poor conductor of electricity. Pb + 2Cl 2 ~ PbCl4
(v) It is not attacked by dry air but affected by moist air Uses: Lead is used:
with the formation of a. thin film of basic carbonate on its (i) for making chambers used in the manufacture of H2S04,
surface which prevents the further action. (ii) for making pipes for carrying water.
(vi) When heated in air or oxygen, it forms lead monoxide (iii) for making telegraph and telephone wires which are to
which changes to red lead; be buried in earth.
2Pb + O 2 ~ 2PbO
(iv) in making bullets and lead accumulators.
(Litharge)
(v) in the preparation of lead pigments.
6PbO + O High temp- ) 2Pb 0 (Red lead) (vi) in making useful alloys such as solder, type metal,
2 3 4
pewter, etc.
. ,
. FLOW SHEET FOR TH~ EXTRACTION OF LEAD AND FORMATION OF VARIOUS COMPOUNDS
d
Galena ore
~ Concentration by froth floatation process
Reduction
l
Air reduction process Carbon reduction process
~ ~
Fused in reverberatory furnace The ore· is mixed with lime and
in presence of air heated in Sinterer
PbS ~ PbO and PbS04 PbS~ PbO
~ ~
Mixed with more of galena and Mixed with C and CaO
heated at higher temperature and smelted in blast furnace
~ ~
PbO and PbS04 are reduced by Crude lead
PbS into lead metal
t
Crude metal
High temp. Heat in

Pb304 ~(--=:..__~- PbO ~(- . . , . . - - - - - Purified - - - ' - - - - 7 PbS
:t-. 1~~
400-500°C air or oxygen Pure Lead Metal
CH,COOHl
t.' (CH3COO)zPb §
::t:
,,i
el 2
. 7
0
'"
'f-,.
'"
0
~~x "'x
;,'0 °0
Qo
P
c,"
+'"
PbCr04
o
PbCl2
PbCl 4 .,s:.
Pb(N03h
2PbC03,Pb(OH)z
White lead
(Chrome yellow) Na2Pb02
lNaoH
PbCr04·PbO
Chrome red
Pb + 2HCI ~ PbCl2 + H2
PbCl2 + 2HCI ~ H2PbCl4
Chloroplumbous acid
COMPOUNDS OF LEAD Properties: It is insoluble in water. It is an amphoteric

oxide. It dissolves in acids and alkalies both.
1. Lead Monoxide, PbO
PbO + 2HN03 ~ Pb(N03h· + H20
It is known in two forms: PbO + 2NaOH ----" Na2Pb02 + H20
(i) a yellow powder commonly known as massicot and On heating in air at 470°C, it forms red lead.
(ii) a buff coloured crystalline form known as· litharge. 6PbO + O2 ~ 2Pb30 4 (red lead)
p,.paration: It is obtained by heating lead or lead Uses: It is used for making glass, paints and varnishes.
sulphide in air at 300°C (massicot form). When the tempemture The mixture of massicot and glycerine is used as a cement for
of oxidation kept 900, litharge is formed. glass and pottery. PbO is used for making other lead compounds.
2Pb + O 2 ----" 2PbO
2PbS + 302 ----" 2PbO + 2S0z 2. Red Lead (Minium or Sindhur), P~04
It is also formed by heating lead nitrate or lead carbonate. Preparation: It is obtained by heating litharge at 470°C
2Pb(N03h ----" 2PbO + 4NOz + 02 in air.
PbC03 ----" PbO + CO2
Properties: It is a red powder, insoluble in water. When (v) A black precipitate is obtained when H 2S is passed
heated, it becomes almost black but it again becomes red on through its solution.
cooling. On heating above 470°C, it decomposes into PbO and (CH 3COO)zPb + H 2S -----7 PbS + 2CH 3COOH
O2 . Lead sulphide
2Pb30 4 -----7 6PbO + 02 (black)
When treated with conc. HN0 3, lead nitrate and brownish (vi) A yellow precipitate of lead chromate is formed when
black insoluble oxide, Pb02, are formed. This indicates that potassium chromate solution is added.
Pb 30 4 is a compound oxide containing both Pb02 and PbO in
(CH 3COO)zPb + K2Cr04 -----7 PbCr04 + 2CH 3COOK
the ratio of I : 2.
Pb30 4 + 4HN03 -----7 2Pb(N03)z + Pb0 2 + 2HiO (vii) On addition of dil. HCI to a cold solution of lead
acetate, a white precipitate of lead chloride appears. This
With H 2S04, it evolves oxygen.
precipitate is soluble in hot water.
2Pb30 4 + 6H 2S04 -----7 6PbS04 + 6H 20 + O 2
(CH3COO)zPb + 2HCl -----7 PbCl 2 + 2CH 3COOH
It acts as an oxidising agent.
(viii) The solution of lead acetate on boiling with litharge
Pb 30 4 + 8HCl -----7 3PbCl 2 + 4H 20 + Cl2
(PbO) forms basic lead acetate.
Pb304 + 4C -----7 3Pb + 4CO
(CH 3COO)zPb + PbO + H20 -----7 Pb(OH)zPb(CH3COO)z
Pb30 4 + 4CO -----7 3Pb + 4C02 Basic lead acetate - -
Uses: It is used: Uses: It is used:
(i) as a red pigment. (i) in the manufacture of chrome yellow and chrome red
(ii) in glass industry. employed as lead pigments.
(iii) for making protective paint for iron and steel. (ii) as a mordant in dyeing and calicoprinting.
(iv) in match industry as an oxidising agent. (iii) for the manufacture of white lead.
(iv) as a laboratory reagent for the test of sulphide and
~ 3. Lead Acetate (Sugar of Lead), chloride ions.
(CH 3COOhPb (v) in medicine for curing skin diseases.
Preparation: It is prepared by dissolving lead oxide i¥i 4. Basic Lead Carbonate (White Lead)
(litharge) or lead carbonate or basic lead carbonate in acetic 2PbC03 ·Pb(OHh
acid (45%) and crystallising the solution.
White lead is manufactured by the application of the
PbO + 2CH 3COOH -----7 (CH 3COO)zPb + H 20 following three methods:
PbC0 3 + 2CH3COOH -----7 (CH3COO)zPb + C02 + H20 (i) Dutch process, (ii) Carter's process, (iii) Electrolytic
2PbC03·Pb(OH)z + 6CH 3COOH -----7 process.
3(CH 3COO)zPb + 2C0 2 + 4H 20
1. Dutch process: This is the oldest method but
it produces the best quality of white lead. It is a very slow
Properties: (i) It is a white crystalline solid. It is soluble method and takes about 6 to 8 weeks for the conversion of
in water. Its solution has sweet taste and known as sugar of lead metal into white lead in the presence of acetic acid, carbon
lead but it is poisonous in'nature. dioxide and moist air.
(ii) On heating, it decomposes to give acetone. Lead is melted and cast into the form of peIforated discs,
(CH 3COO)zPb -----7 PbO + CO2 + CH 3COCH3 called buckles. A number of earthenware pots with shelves are
Acetone taken in which vinegar or dilute acetic acid (3%) is placed at
(iii) It forms a white precipitate of lead carbonate when their bottom. Buckles are kept at the shelves of these earthenware
treated with sodium bicarbonate. . pots. These pots are then arranged in rows. These are partly
covered with wooden planks and the space in between the
(CH 3COO)z·Pb + 2NaHC0 3 -----7 PbC03 + 2CH 3COONa
rows is fled by spent tanbark and horse dung (Fig. 9.12).
+ CO 2 + H 20 The pots are allowed to remain in this position for about 6
(iv) It forms a white precipitate of basic lead carbonate to 8 weeks. D4ring this period, fermentation of tanbark and
when treated with a solution of sodium carbonate. horse dung occurs. This produces CO 2 and heat energy which
3(CH 3COOhPb + 3Na2C03 + H 20 -----7 helps in the evaporation of acetic acid:' The' combined- action
2PbC03·Pb(OH)z + 6CH3COONa + CO2 of acetic acid vapours, carbon dioxide, air and mois,ture converts
Basic lead carbonate lead into white lead. The following chemical changes are
supposed to take place.
Buckles Molten lead is first atomised by a jet of superheated steam or
. ~:~~~~:t~"%g
compressed air and brought in the wooden cylinders. A spray
of acetic acid, carbon dioxide and air is blown into the cylinders
(Fig. 9.13).
The same chemical changes occur as in the Dutch process.
~ lead buckles The conversion takes place in 5-12 days.
3. Electrolytic process: The electrolytic cell is divided
Dilute acetic acid
into two compartments with the help of a porous diaphragm.
The anodic compartment is filled with sodium acetate solution
and contains anodes of lead plates, while cathodic compartment
consists of cathodes of steel dipped into a solution of sodium
carbonate. On passing electricity, lead of anode starts dissolvil1g
in the form of.lead acetate, which meets with sodium carbonate
Fig. 9.12 Dutch process to form white lead.
2Pb + 2H20 + O2 ~ 2Pb(OHh CH3COONa ~ CH3COO- + Na+
Anode .
Pb(OH)2 + 2CH 3COOH ~ Pb(CH3COOh + 2H20
pb(Oft)z +Pb-(CH 3COOh Pb(CH 3COO)2;Pb(OHh -1 diSSQjyes. lead . .
Basic lead acetate Pb(CH3COOh
3[Pb(CH3COO)z'Pb(OH)ZJ + 4C02 + 2H20 ~ 3Pb(CH3COO)z + 4Na2C03 + 2H20 ~
2[2PbC03'Pb(OHhJ + 6CH3COOH 2PbC03'Pb(OH)z + 2NaHC03 + 6CH3COONa
White lead
White lead is washed with water and dried.
White lead is removed from unchanged lead and washed
Properties: It is white, heavy amorphous powder. It is .
with water to remove soluble lead acetate. It is then dried.
insoluble in water. It is poisonous in nature. It is miscible with
2. Carter's process: It is comparatively quicker process.
linseed oil. On heating to 430°C, it decomposes into red
This process is carried in wooden cylinders which are rotated.
lead.
2PbC0 3'Pb(OHh ~ Pb 30 4 + H20 + CO + CO2
Red lead
cO2 + Air It is darkened in air due to formation of PbS.

,'
, I. ,, '' Uses : White lead mixed with linseed oil. is used as a
,, '' ,, ''
! : ! : white paint. It has a large covering power. It is generally mixed
Rotating wooden drum with BaS04 which increases its property of brushing out without
containing finely divided
Pb+CH 3COOH affecting its covering power.
I ' I'
I
I
I
I
I I
1 I
The main drawbacks to the use of white lead are that it
I I I I
,'I I I
becomes black if H2S is present in atmosphere and it is
poisonous in nature. Various substitutes such as lithopone,
titanium dioxide, sublimed white lead, etc., have been suggested.
Fig. 9.13 Carter's process
It is also used for the preparation of red lead and pottery glazes.
'£umple 1. A colourless solution contains a metal nitrate. The metal chloride may be PbCl2 or AgCl or Hg2Cl2.The
A little solution of sodium chloride is added to it when a following tests can be used to ascertain the metal chloride.
cloudy white precipitate appears. How you. will ascertain about (i) If the precipitate dissolves in hot water, it is PbCI 2•
the metal ion? (ii) If the precipitate dissolves in NH40H, it is AgCl.
Solution .: (iii) Ifthe precipitate tumsblack with NH 40H, it is Hg2C12*
The chloride ions have combined with the metal ions to give lEumple 2. (a) If you have to dissolve lead (ll) oxide.
the precipitate of a chloride as sodium nitrate is soluble.
PbO, which acid you will choose?
Metal nitrate + NaCI ~ Metal chloride + NaN0 3 (b) Explain why the reactions with hydrochloric acid and
(Insoluble) (Soluble)
sulphur dioxide show the oxidising nature of Pb02.
(c) Predict the result of reacting Pb304 with concentrated account of small radii of carbon atoms, the various atoms are
hydrochloric acid. [M.L.N.R. 1992] closely packed in the crystal lattice. Graphite possesses layer
Solution: structure in which each carbon atom is sp2 hybridized. There
(a) Nitric acid. This is because lead nitrate formed is soluble' is wide separation between various layers. One layer can slide
in water. If H 2S04 is used, an insoluble layer of PbS04 is easily on the other. This makes graphite soft in nature.
deposited on the surface of powder and prevents the further (iv) In carbon dioxide discrete molecules are present. In
reaction. Likewise, PbCh prevents the reaction with HCI. each molecule carbon is linked with two oxygen atoms by
N II double bonds (O=C=O), while silica possesses a giant three
(b) Pb0 2 + 4HCI --'---7 PbCl 2 + Cl2 + 2H 20 dimensional structure in which each silicon is linked with four
N II oxygen atoms tetrahedrally and each oxygen is linked with two
Pb0 2 + S02 ----? PbS0 4 silicon atoms.
I
In above reactions, lead changes from lead (IV) to lead (II), o
i.e., gain of electrons. I I I
4 2 -Si-O-Si-O-Si-
Pb + + 2e ----? Pb +
I I I
Thus, Pb02 acts as oxidising agent as it oxidises HCI and o
SO2. I
(c) Pb30 4 is considered to possess PbO and Pb02' Pb02 ; This structurejs extremely stable and considerableene.fg;.'-
acts as an oxidising agent. Thus, PbCl 2 and Cl2 are formed. is required to break Si-O bond. Thus, CO 2 is a gas and silica
is a solid.
Pb304 ----? 3PbO + 0 (v) When solid CO 2 evaporates, it changes to the gaseous
2HCI + 0 ----? H20 + Ch . state without coming to the liquid state. It produces cooling
[PbO + 2HCI ----? PbCl2 + H 20] x 3 during evaporation. It is, therefore, known as dry ice.
·t~~ple 4. Write the formulae of the following
compounds:
(a) Butter of tin (b) White lead
(c) Red lead (d) Sugar of lead
(e) Litharge (f) Carborundum
(g) Phosgene (h) Chrome yellOW
(i) Water glass (j) Drykold
Solution:
(a) SnC14·5H20 (Stannic chloride)
(b) 2PbC03'Pb(OHh (BasiC lead carbonate)
(c) Pb 30 4 (Trilead tetra-oxide)
(d) Pb(CH3COOh (Lead acetate)
(e) PbO (Lead monoxide)
(0 SiC (Silicon carbide)
(g) COCl2 (Carbonyl chloride)
(h) PbCr04 (Lead chromate)
(i) Na2Si03 (Sodium silicate)
(j) CO2 (Carbon dioxide in solid state)
)~XBmple S. An aqueous solution of a salt (A) gives a
white precipitate (B) with sodium chloride solution. The
filtrate gives a black precipitate (C) when H2S is passed into
it. Compound (B) dissolves in hot water and the solution gives
a yellow precipitate (D) on treatment with sodium iodide. The
compound (A) does not give any gas with dilute HCI but
liberates a reddish brown gas on heating. Identify the
compounds (A) to (D).
Solution:
Since the crystalline compound (B) dissolves in hot water
/
and gives a yellow precipitate with NaI, it should be lead i.~J3!J8mple 9. [SiF6f- is known whereas [SiCI6f- not. Give
chloride, PbCl2 and the solution (A) consists a lead salt. possible reasons.
PbCl2 + 2NaI ~ PbI2 +2NaCI Solution:
(8) (D) f-
The possible reasons for the non-existence of [SiCI6 are:
The compound (A) does not give any gas with dilute HCI (i) due to large size of CI atoms. Six fluorine atoms can be
but liberates a reddish brown gas on heating, it should be lead easily accommodated around silicon atom due to smaller size
nitrate, Pb(N0\ 3h while six larger chlorine atoms cannot be accommodated around
silicon atom.
2Pb(N0 3h ~ 2PbO + 2N0 2 + O 2
(ii) due to the presence of lone pair of electrons in fluorine
(A) Reddish brown gas
atom on a smaller 2p-orbital, the interaction with d-orbital of
Lead chloride is sparingly soluble in water. When H2S is silicon atom is stronger rather than the presence of lone pair
passed, it gives a black precipitate of lead sulphide, PbS. of electrons in chlorine atom on a larger 2p-orbital, the
PbCl2 + H 2S ~ PbS + 2HCI interaction with d-orbital of silicon atom is poor.
Black
(C) ~~ple 10. (a) Why Sn(lI) is a reducing agent whereas
Thus, (A) is lead nitrate, Pb(N0 3h, Pb(II) is not?
(B) is lead chloride, PbCI 2 , (b) Why d,oes not silicon form an_analogue. ojgraphite? ....
(C) is lead sulphide, PbS, (c) C and Si are always tetravalent but Ge, Sn and Pb show
and (D) is lead iodide, PbI2 . divalency. Why?
Solution:
~~~Example 6. (i) Indicate the principal ingredients of the
(a) Both Sn and Pb exhibit +2 and +4 oxidation states due
following:
to inert pair effect. Inert pair effect is more effective in lead
(a) Coal gas (b) Producer gas (c) Water gas. [M.L.N.R.19911 than in tin. Thus, +2 state is less stable in tin and thus,Sn(II)
(ii) Identify A and B (compound/reaction condition): acts as a reducing agent and converted into more stable Sn(lV)
3+ .
Heat
PbS --:---:-7
B
A + PbS ----7 Pb + S02 [l.I.T. 1991] state .. For example, Fe is reduced by Sn(II).
In mr
Solution: 2Fe3+ + Sn2+ ~ 2Fe2+ + Sn4+

(i) Coal gas, H2+C~+CO (b) On account of bigger size and smaller electronegativity
Producer gas, CO +N2 of spicon atom in comparison to carbon atom, silicon atom
Water gas, CO +H2 does not undergo sl-hybridization and does not form prc-pn
=
(li) A PbO or PbS04 double bonds. Thus, silicon does not form graphite like structure
=
B· high temperature as it requires double bonds:
Air supply is cut off. (c) Carbon and silicon have no d- or j-electrons in inner
~~~~ple 7. Write the balanced equation for reaction of shells. Therefore, they do not show inert pair effect.
< 3
AZ4 C3 and CaNCN with water. [I.I.T.2002] Consequently, they show only tetravalency due to sp
Solution :. hybridization. In all other elements from Ge to Pb either d- or
Al4C3 + 12H20 ~ 4AI(OH)3 + 3C~. both d- and f-electrons are present. Due· to poor shielding
effect, inert pair effect is observed, i.e., showing either divalency
CaNCN + 3H20 ~ CaC0 3 + 2NH3
or tetravalency. The stability of divalency increases while that
~Y1Jj:~ple 8. Like CO why its analogue SiD is not stable? of tetravalency decreases as the inert pair effect becomes
[C.B.S.E. W.M.T.) 20041 more and more prominent from Ge to Pb.
Solution:
Carbon has a strong tendency to form p1C-p1C multiple bonds m.,*rnple 11. (a) Silica is attacked by hydrofluoric acid
wiih the formation of SiF~- anions. The analogous CF~
due to its small size and high electronegativity. Carbon combines
with oxygen and forms stable CO forming p1C-p1C multiple anion does not exist. Account for this.
bonds. CO is actually a resonance hybrid of the following two (b) Diamond is covalent, yet it has a high melting point. Why?
structures: Solution:
(a) Silicon has 3d-orbitals in the valence shell and thus
:C=O:
••
~ :C=O:
+
expands its octet giving sl2
d -hybridization while d-orbitals
are not present in the valence shell of carbon. It can undergo
Silicon, on the other hand, on account of its bigger size and
lower electronegativity has no tendency to form p1C-p1C mUltiple sl-hybridization only. Thus, carbon is unable to form CFg-
bonds and thus does not combine with oxygen to form stable anion.
SiO.
(b) Diamond has three dimensional network, involving strong Solution:

C-C bonds which are difficult to break. Hence, its a high (a) Tin and lead do not show pit-PIt bonding because the
melting point. d-orbitals of Sn and Pb are of much higher energy than that
Example 12. (a) Discuss briefly why tin and lead of the element with which they form a bond in the compound.
compounds do not show pIt-pIt bonding? . (b) Small size, high electronegativity, high ionisation energy
(b) What are the properties responsible for the anomalous and absence of d-orbitals in the valence shell are the main
behaviour of carbon? properties of carbon which lead to its anomalous behaviour.
(c) Which silicon compound is used as a: (c) (i) Silica gel (ii) Zeolites
(i) dehydrating agent (ii) cation exchanger (iii) Silicones (iv) Asbestos
(iii) lubricant (iv) thermal insulator.
b SUMMARY AND IMPORTANT POINTS TO REMEMBER b

1. Group IVA or 14 of the periodic table consists of six ele- Only carbon atoms do form double or triple bonds involving
ments-carbon, silicon, germanium, tin, lead and ununquadium. pn-pIt bonding. Carbon has also the property to form closed
These are p-block elements as the last differentiating ele- chain compounds with 0, S and N atoms as well as forming
ctron is accommodated in np~shell. These elements have four pIt-pIt multiple bOnds withotlier elemenKpafticularly N;S--
electrons in their valency shell, two of which are in s-orbital and O. Carbon can form chains containing as many as carbon
while remaining two in p-orbitals, i.e., ninp2 configuration. atoms but Si and Ge cannot extend the chain beyond 6 atoms.
The reason for greater tendency of carbon for catenation is
Ii J, I L....:-'--'--'---'
due to high bond energy between carbon and carbon atoms.
ns ~np~
This bond energy is approximately of the same magnitude
2. Carbon is seventeenth and silicon is second most abundant as the energies of the bond between carbon and atoms of
element by mass in earth's crust. Carbon is found both in other elements.
native and combined state. Carbon is an essential constituent C-C (83 kcal mol-I); C-O (86 kcal mol-I) ;
l
of all living matter as proteins, carbohydrates and fats. Silicon C-Cl (81 kcal mor )
occurs very widely as silica and a wide variety of silicate 6. The maximum covalency of carbon is four because it has no
minerals and clays. Tin and lead are comparatively low but d-orbitals which· can be used to accommodate more than 8
are found as concentrated ores. The important ore of tin is electrons.
cassiterite (Sn02) and that oflead is galena (PbS). Germanium Remaining elements have vacant d-orbitals. Thus, they have
is rare element. the tendency to show maximum covalency of six involving
3. (a) Non-metallic nature decreases from carbon to lead. sp3d2-orbitals.
C Si Ge Sn Pb 7. The phenomenon of existence of a chemical element to exist
'-v----' Metalloid in two or more forms differing in physical properties but
Non-metals
having almost same chemical nature is known as allotropy.
(b) Density increases from C to Pb.
This phenomenon is due to the difference either in the number
(c) Melting and boiling points decrease down the group.
of atoms in the molecules or arrangement of atoms in the
(d) Atomic radii increase on moving down the group ..
molecules in the crystal structure. Except lead, all other
(e) Electronegativity decreases from C to Si.
members of group 14 exhibit allotropy.
(f) Ionisation energy decreases regularly from C to Sn. Pb,
Carbon exists as diamond, graphite, coal, charcoal, lampblack
however, shows a higher value than Sn due to poor
and fullerene. Silicon exists in two forms, crystalline and
shielding off-orbitals.
amorphous; germanium exists in two crystalline forms and
4. All the elements show tetravalency due to si
hybridization.
tin exists in three forms; grey, white and rhombic form.
Last three members show inert pair effect and show the
S. Diamond is the purest form of carbon. It is the crystalline
tendency to form M2+ ions. The stability of M2+ state
form. It is the hardest natural substance known. It is bad con-
increases as the atomic number increases. The compounds
ductor of electricity and heat. It is transparent to X-rays and
of Ge2+ and Sn2+ are less stable than M4+ state. 'Thus, Ge2+
glows in ultraviolet rays. It has high refractive index (2.45). It
and· Sn2+ compounds act as reducing agents.
4 is chemically inert. It reacts with fluorine at 700"C to form CF4 .
Pb 2+ compounds are more stable than Pb + compounds.
In diamond every carbon is in sp3 hybridized state and linked
Thus, Pb4+ compounds act as oxidising agents.
to four other carbon atoms tetrahedrally by covalent bonds.
5. The tendency of formation of long open or closed chains by
It is, thus, a giant three dimensional polymeric structure in
the combination of same atoms in themselves is known as
which C-C distance is 1.54 A and bond angle 109.5". It is
catenation. This property is maximum in carbon and decre-
used as gem stone and in knifes for cutting glasses and rock
ases down the group. Lead shows no catenation.
borers.
Elements of Group IVA or 14 (Elements of Carbon Family) 4.41
9. Graphite is another crystalline form of carbon. It is found in stream ofHCI gas, germanium chloroform (GeHCI 3) is formed.
nature and is also manufactured by Acheson process. It is Concentrated H2S04 and HN0 3 attack Ge, Sn and Pb.
soft, greasy, dark greyish coloured crystalline solid. It is 14. Except carbon, all other members of group 14 dissolve in
good conductor of electricity. It leaves a black mark on paper aqueous NaOH solution evolved hydrogen.
and is called bl~£k lead or plumbago. It is chemically more M + 2NaOH + H 20 ~ Na2M03 + 2H2
active than diamond. With alkaline KMn04, it is oxidised to 15. All the members of group 14 form covalent hydrides of type
mellitic acid [C6(COOH)6] and oxalic acid. Conc. HN03 or MH4 . Besides CH4, carbon forms a large number of hydrides,
conc. H2S04 oxidises it into insoluble yellowish green saturated and unsaturated. Silicon forms only limited number
substance, known as graphitic acid C II H 40 5 . of saturated hydrides. Germanium gives a still smaller number
. . 2
It has two dimensional sheet structure. Each carbon IS sp while Sn and Pb form only one hydride each. Hydrides are
hybridized and is linked to three carbon atoms in hex~gonal gaseous and their thermal stability decreases and con-
planar structure. The C-C bond distance is 1.42 A. The sequently reducing nature increases.
adjacent layers are held by van der Waals' forces and 16. All the members of group 14 form tetrahaIides of the type
distance between layers is 3.4A. Graphite is thermodyna- MX4 except PbBr4 and PbI4. The halides are covalent and
mically more stable form. formed by sp3 hybridization. The thermal stability decreases.
It is used for lining and making electrodes, refractory CX4 > SiX4 > GeX4 > SnX4 > PbX4
crucibles, lead pencils. It acts as a moderator in nuclear Except carbon halides, other halides are readily hydrolys7~~~
reactor. It is also used as a lubricant in machinery. by water. The hydrolysis is due to utilization of d-orbitals.
10. An allotropic form called fullerenes or Buckminster- The tetrahalides of Si, Ge, Sn and Pb can form hexahalo
fullerenes or Buckyballs recently discovered is C 60 or C70. complexes. The tetrahalides of Si, Ge, Sn and Pb act as strong
Such molecules are made from interlocking hexagonal and Lewis acids.
pentagonal rings of carbon atoms and exist in chimney soot 17. CO is a colourless, odourless, poisonous and neutral oxide.
or candle smoke. It is' slightly soluble in water. It is obtained by heating
11. Carbon has three amorphous forms. These are coal, charcoal K4Fe(CN)6 with conc. H2S04 , It is absorbed by ammonical
and lampblack. Coal is the crude form of carbon. It is found Cu2CI 2 solution. It is combustible but does not support
in various forms depending upon the carbon content (peat, combustion. Its poisonous nature is due to its reaction with
lignite, bituminous, steam coal and anthracite). Anthracite is haemoglobin to form carboxy-haemoglobin which is not
the superior quality of coal. capable of absorbing oxygen. It is a good reducing agent.
When coal is subjected to destructive distillation, it loses The bonding in CO is represented as : C f- O. It acts as a
volatile constituents and the residue left is known as coke.
x-acid ligand. It forms addition compound with a number of
Coal is used as a fuel, for making fuel gases and synthetic
substances. It combines with metals like Ni, Cr, Fe, etc. The
petrol and coke.
compounds formed are called carbonyls.
Charcoal is formed when wood, cellulose or any other
It is used as a fuel in the form of water gas, producer gas, etc. It is
carboneous matter are burnt in limited supply of air. This is
used in the manufacture of methanol, synthetic petrol, formic
the most active form. It has number of applications.
acid, phosgene gas, etc. It is 'used as a regucing agent in
Lampblack, carbon black or soot is obtained by burning
extraction of iron and in Mond's process for extraction of Ni.
substances rich in carbon such as kerosene, turpentine oil,
18. CO2 is a colourless, odourless and tasteless gas. It is present
etc., in a limited supply of air. These substances yield a large
in atmosphere. It is slightly soluble in water but more soluble
amount of smoke which is passed into chambers having wet
. under pressure. It is heavier than air. It is easily liquefied
blankets. The soot collected on blankets is called lampblack.
under pressure into a colourless mobile liquid. If C02 under
It is almost pure carbon. It is a soft black powder and is used
pressure is allowed to escape through a nozzle, a white solid,
as a pigment in black inks and paints. It is also used as a
i.e., dry ice is obtained. Solid CO2 is soft, white, snow like
filler in making rubber tyres.
substance. It sublimes and leaves no residue. Solid CO 2 is
12. The elements of group 14 react with oxygen on strong heating
used as a refrigerant under the commercial name drikold.
to form oxides of the type M02. The acidic nature decreases
It is neither combustible nor a supporter of combustion.
with increase in atomic number. CO 2 and Si02 are acidic while
However, burning magnesium, sodium or potassium conti-
Ge02, SnOz and Pb02 are amphoteric in nature. They dissolve
nues burning in the gas. CO2 is converted by plants into
in alkalies forming carbonates, silicates, germanates, stanna-
glucose and higher carbohydrates in the presence of sunlight
tes and pfumbates of the type Na2M03 respectively.
and chlorophyll. This process is known as photosynthesis.
They also form oxides of the type MO.SiO is unstable. CO is
Carbogen is a mixture of O2 and CO2 (5 to 10%). It is used
neutral while SnO and PbO are amphoteric.
for artificial respiration.
13. Non-oxidising acids do not attack carbon and silicon. Tin
A mixture of solid CO2 and ether is used to produce low
dissolves slowly in dilute HCl but readily in conc. HCI. Lead
temperature of the order of - 80°C to 100"C.C02 is used as
also dissolves in HCl forming insoluble PbC1 2. Germanium is
a fire extinguisher.
not attacked by dilute HCl but when metal is heated in a
442 \ GR.B. Inorganic Chemistry for Competitions
(a) Dry powder extinguishers contain sand and baking soda Amorphous silicon is chemically more active than crystalline
(NaHC03)· silicon.
(b) Baking soda and sulphuric acid type extinguishers. 22. Sodium silicate is commercially called water glass. It is
(c) Foamite ,extinguishers contain baking soda and chemically sodium metasilicate containing an excess of silica.
aluminium sulphate. Its composition varies from Na2Si03·Si02 to Na2Si03·3Si02·
19. The, carbides 'are binary compounds in which carbon It is soluble in water and its solution is alkaline.
combines with elements of lower or about equ'al electro- Some coloured salts like cobalt nitrate, nickel chloride, ferrous
negativity. Carbides are divided into three categorj.es. sulphate, copper sulphate, etc., are plaCed in the solution of
(i) Salt-like or ionic or electrovalent carbides: These sodium silicate and whole solution is left as such for a night.
are formed by strong electropositive elements of group A beautiful hollow tubes of metallic silicate gels possessing
1,2 and 13 (except boron), coinage metals, Zn, Cd and colours shoot up from these crystals and look like plants.
some lanthanides. These are further classified into three This is called silica garden.
classes: 23. Silicones are organosilicon polymers containing Si-D-Si
(a) Methanides: These give methane on hydrolysis. linkages. These are formed by the hydrolysis of alkyl or aryl
They contain C4- ions, e.g., Be2C, Al4C3. substituted chlorosilanes and their subsequent polymeri-
(b) Acetylides: These give acetylene on hydrolysis. zation. The substituted chlorosilanes are formea by the
They containC5- (C=C)2- ions, e.g., CaC2, BeC2, reaction of Grignard reagents and silicon tetrachlQride.
Li2C2, Na2C2, etc. RMgcr +SiCI4~R~iCr3 'oiRiSiCl2 or R3OO- . .-'
HOH •
(c) AIIylid~: These giv~ pr~~ne or allylene on R2SiCl2 ---7 R2Si(OHh----t HO-Si(Rz)-O-Si(Rz)-OH
hydrolYSIS. These contam C3 lon, e.g., Mg2C3'
Polymerization continues on both ends and thus chain
(ii) Covalent carbides: Boron carbide and carborundum
increases in length (linear thermoplastic polymer)
(SiC) belong to this category. They are covalent,
polymeric, thermally stable, extremely hard, high melting RSiCl3 HOH) RSi(OHh. This gives crossed linear silicone.
and inert solids. SiC has diamond like structure. Lower silicones are oily iiquids while higher members
(iii) Metallic or interstitial carbides: These are formed containing long chains or ring structures are waxy and rubber
by transitional elements. Carbon atoms being small in like solids. These are stable towards. heat and chemical
size occupy interstitial positions of metal atoms. These reagents and are good electrical insulators. These are non-
carbides are hard and possess high melting points, used toxic and are water repellents. These have variety of industrial
. as refractory materials. applications .
20. Water gas, producer gas, coal gas, oil gas, natural gas, LPG, 24. Silicates are metal derivatives of' silicic acid, ~Si04 or
etc., are gaseous fuels. These have high calorific values. Si(OH)4' Silicates are formed by heating metal oxides or
(i) Water gas or synthetic gas is a mixture of CO and H2. carbonates with sand. Silicates have basic unit SiOt. Each
It is made by passing steam over red hot coal at 1000 . silicon atom is tetralledrally bonded to four oxide ions.
14OO'C. (i) Orthosilicates Contain single discrete unit ofSiO;r-
(ii) Producer gas is a mixture of CO and.N2' It is made by tetralledi:a, e.g., zircon (ZrSi04).
passing air on hot coke. It has lower calorific value than (ii) Pyrosilicates Contain two units of SiOt joined along
water gas. a corner containing oxygen. Pyrosilicate ion, si2 of,
(ill) Coal gas is a mixture of hydrogen, methane, carbon e.g., thorteveitite SC2Si207.
monoxide, acetylene, etc. It is obtained by destructive (iii) Cyclic or ring silicates - General formula (SiO~)1l> e.g.,
distillation of coal at 1000°C. It has high calorific value. beryl Be3Al2 Si60 18 •
(iv) Oil gas is obtained by cracking of kerosene. It is a (iv) Chain silicates - By sharing two oxygen atoms of each
mixture of lower hydrocarbons. tetrahedra.
(v) Natural gas mainly contains C~. (v) Two dimensional sheet silicates - By sharing three
(vi) LPG is a mixture of butane and isobutane. oxygen atoms of each tetralledra. General formula
(vii) Semiwater gas is a mixture of water gas and producer (Siz05)~-' .
gas. (vi) Three dimensional sheet silicates - Involve all the four
21. Silicon is the second most abundant element in the earth's oxygen atoms of each tetralledra - examples quartz,
crust (about 28% by mass). Unlike carbon, it is never found tridymite, feldspar, ultramarines, etc.
in' free state but always in combined state. Silicon is widely 25. Glass is a transparent or translucent super cooled solid solu-
present as .silica (Si02) in various forms such as simd, quartz, tion of silicates and borates. The most common silicates are
flint, etc. Silicon exists in two forms (a) amorphous and (b) those of sodium, potassium, calcium and lead. An approxi-
crystalline. The amorphous variety is obtained by heating dry mate formula is R20·MO·6Si02, where R == Na or K and M ==
powdered silica with magnesium. The crystalline form is Ca, Ba, Zn or Pb. Si02 may be replaced by Al 20 3, B20 3; P20s,
obtained by heating finely powdered sand or quartz with 26. Glass is attacked by HE This property is used in the etching
carbon in an electric furnace. of glass.
27. The most important ore of tin is cassiterite, Sn02' The ore is fire proofing cotton and for increasing weight of silk.
crushed and powdered. It is washed with running water to 30. SnC12·2H20 isa crystalline solid. It is soluble in water. It acts
remove lighter siliceous matter. Iron tungstate is removed by as a reducing agent. It is used for making purple of cassius
electromagnetic separator. The ore is now roasted to remove and as a mordant.
sulphur and arsenic. The roasted mass is mixed with about 31. Lead is mainly extracted from galena (PbS) ore. The ore is
one. fifth of its mass with anthracite (carbon) and subjected concentrated by froth floatation process. It is extracted either
to heat in a reverberatory furnace. The liquid metal is drawn by air reduction process or carbon reduction process.
off from the furnace. It is further purified by liquation and 32. Pbis not affected by pure water. However, it dissolves slowly
poling. in water having dissolved oxygen. The dissolution of lead in
28. (a) Tin produces a peculiar sound whenever it is bent. The water is known as plumbosolvency. Lead salts are poisonous
cracking sound is known as Tincry. in nature and lead pipes are often used in conveying water.
(b) It exists in three allotropic forms. White tin is the In order to minimise dissolution, hard water is first conveyed
common and most stable. which forms a protective layer on the inner walls.
18~C 170"C 33. Lead forms three oxides PbO, Pb02 and Pb304. Pb0 2is a strong
Grey tin ~ White ~ Rhombic oxidising agent. Pb 30 4 is known as red lead (minium or
. The conversion of white tin to grey tin in cold countries sindhur). Pb02 is used in storage batteries and in match
is accompanied by decrease in density, comes into industry. PbO exists in two forms (a) a yellow powder commonly
powdered form. This is termed tin disease or tin pest or known as massicotand· (b) ouff-colbliredf6rrhKriown--a:s-·
tin plague. litharge. PbO is used for making glass, paints and varnishes.
(c) Tin is not attacked by organic acids. This property is 34. The solution of lead acetate is sweet in taste and is known
utilised for tinning cooking vessels made of copper or as sugar of lead but it is poisonous in nature.
brass. 35. Basic lead carbonate (white lead), 2PbC03·Pb(OHh in linseed
(d) Tin is largely used in forming a protective coating over oil is used as white paint..1t has large covering power but is
iron. The process of depositing tin over the sheets of poisonous and affected by H2S in air.
iron or steel is called tin plating. 36. PbCr04, chrome yellow is used as a yellow pigment and basic
(e) Tin foil is used for wrapping cigarettes, confectionary lead chromate PbCr04·PbO known as chrome red, is also used
and for making the tooth-paste tubes. Tin amalgam is as pigment.
used in making mirrors. 37. PbCl2 is more ionic than PbC1 4. It is more stable.
(f) It is used for making useful alloys. 38. Lead blocks are used to protect harmful emissions from radio-
(i) Solder - Sn 67%, Pb 33% (ii) Bronze - Cu 75~90%, . active minerals .
Sn 10 - 25% (iii) Bell metal Cu 80%, Sn 20%. . 39. Tetraethyllead Pb(C2HS)4 is used as an antiknock agent to
29. SnC4 is hygroscopic and forms crystalline hydrates con- improve the quality of gasoline.
taining 3, 5, 6 and 8 molecules of water as water of 40. The hardness order of some abrasives is :
crystallization. The pentahydrate, SnC4·5H20 is known as Boron nitride> Diamond> Boron carbide> Silicon carbide
butter of tin or oxymuriate of tin. It is used as a mordant, for
PRACTICE PROBLEMS ~
• Subjective Type Questions (d) The element which is most abundant in earth's crust.
(e) The element which is used as a semiconductor.
1. Answer the following: (f) The element which is commonly found in +2 oxidation
(a) Name three allotropic forms of carbon. Which one is a state.
good conductor of electricity? 3. Give reason for each of the following:
(b) What is name of recently discovered allotrope of carbon, (i) Why Ge, Sh and Pb show divalency?
i:e.,C60 ? (ii) Out of methane and silane which is more stable and why?
(c) Which isotope of carbon is radioactive? (iii) Aqueous solutions of carbonates of alkali metals are
(d) Which allotrope of carbon is used as a moderator in alkaline in nature?
atomic reactors? (iv) Carbon tetrachloride cannot be hydrolysed with water.
(e) N.ame the purest form of carbon. (v) SnCl2 is a solid while SnCl4 is a liquid at room temperature.
2. Among group 14 elements name : 4. Answer the following:
(a) The element having highest tendency to form p1t-p1t (a) Which is the basic building unit of all silicates?
bonds. (b) Why are carbon compounds relatively inert?
(b) The element which is most electropositive. (c) What is dry ice? Why is it so called?
(c) The element which is radioactive in nature.
444 GR.K''fnorganic Chemistry for Competitions
(d) Why is diamond a bad conductor of electricity but a good (iv) What are carburetted water gas and semiwater gas?
conductor of heat? (v) What is a metal carbonyl?
(e) Which halide of carbon is used as a refrigerant? (vi) What is tin disease or tin plague?
5. Indicate tbe principal ingredients of the following: (vii) .How does SiCl4 differ from CCI 4 ?
(a) Coal gas [M.L.N.R. 1991] (viii) What is plumbosolvency?
(b) Producer gas [M.L.N.R. 1991] 10. Write short notes on the following:
(c) Water gas [M.L.N.R. 1991] (i) Structure of diamond (n) Structure of graphite
(d) Natural gas (iii) Alloys of tin (iv) Fuel gases
(e) Soft glass (v) Silicones (vi) Various forms of coal
(f) Hard glass (vii) Fire extinguisher (viii) Catenation
6. What happens when the following are heated? 11. Explain the following with proper reasoning.
(a) Redlead (b) Lead nitrate (c) Lead acetate (i) Carbon dioxide does not support combustion but a
(d) Hydrated stannous chloride (e) White lead burning magnesium ribbon continues to bum in it.
7. What happens when? [Hint: Mg reduces CO2 to carbon,
(i) Dilute nitric acid is slowly reacted with tin. 2Mg .j. C02 ~ 2MgO + C
(ii) Carbon dioxide is passed through a suspension of and therefore continues to burn in CO2,]
limestone in water. [I.I.T. 1991J (li) Graphite is. a conductor but dimpond is .. not a
(ili)Carbon and steam are heated, conductor;
(iv) Red lead is treated with nitric acid. [M.L.N.R. 1992] [Hint: Graphite has layer structure in which each carbon is
(v) Iodine is added to stannous chloride. s/ hybridized. 1t-electrons are delocalised and
(vi) Carbon dioxide is passed through a concentrated conduct electricity. In diamond each carbon is
aqueous solution of sodium chloride saturated with si hybridized and no mobile or delocalised electrons
ammonia. are available.]
(vii) Tin is treated with concentrated nitric acid.
(iii) Carbon tetrachloride is not affected but silicon
(viii) Lead is obtained from galena by air reduction.
tetrachloride is hydrolysed by water.
(ix) NaOH solution is added to SnCl2 solution.
[Hint: In silicon d-orbitals are available, i.e., it increases its
(x) Silica is heated with CaF2 and conc. H2S04 ..
coordination number to 6.
(xi) Stannous chloride reacts with ferric chloride.
(xii) Stannous chloride reacts with mercuric chloride. Cl)Si <Cl + 2H20 H) 0 Cl)s i <Cl
~ ~ f- 0 <H
(xiii) SnS reacts with yellow ammonium sulphide. Cl CI H Cl CI H
(xiv) Lead is reacted with acetic acid in presence of oxygen. CI
(xv) Nitrobenzene is treated with acidified stannous I
chloride. ~ HO-Si-OH+2HCl
I
(xvi) Methyl chloride is passed over powdered silicon in the Cl
presence of copper catalyst at 275-375°C. In carbon d-orbitals are not present.]
(xvii) Potassium ferrocyanide is heated with conc. H2S04 , (iv) Dilute HCI is preferred to dilute H 2S04 for the
(xviii) Carbon monoxide is passed over nickel at BO°C. , preparation of carbon dioxide from marble.
(xix) Silicon is fused with soda ash. [Bint ~ In case of dilute H ZS04,CaS04 is formed. This is
(xx) Lead chloride is heated with cone. HCI. deposited on the surface of marble and acts as a
8. How will you preparetbe following? protective layer. This layer stops the further reaction
(i) Tin metal from cassiterite. to liberate CO2 ,]
(ii) Litharge from red lead. (v) Sn2+ and Fe3+ cannot coexist in the same solution.
(iii) Red lead from litharge. [Hint .: Redox reaction occurs.
(iv) White lead from lead. 2Fe3+ + Sn 2+ Sn4+ + 2Fe2+.]
(v) Stannous oxide from stannous chloride. (vi) CCl4 is used as fire extinguisher but not CS 2.
(vi) Silanes from silicon. [Hint ; CCl4 is heavy non-combustible liquid but CS 2 is
(vii) Crystalline silicon from silicon tetrachloride. highly combustible liquid.
(viii) Tetraethyllead from sodium lead alloy. 2CS 2 + 502 ~ 2CO + 4S02]
(ix) Chrome yellow from litharge. (vii)" Sn is used in making solder.
(x) Carbon monoxide from water gas. [Hint: It is easily fusible alloying metal.]
9. Answertbetollowing: (viii) The lead of lead pencils is not lead but graphite.
(i) Which elements have the electronic configuration [Hint; Graphite has the property of marking paper.]
2? G'lve th·
ns 2 np. err names. (ix) PbO does not dissolve in H2S04 while SnO is
(n) What is chemical formula of soft glass? soluble in H2S04 ,
(iii) What is gas carbon? [Hint .: PbS04 is insoluble while SnS04 is soluble in water.]
(x) Alkali cannot be stored in a Sn or Pb vessel. [Aos. (A) = SnCI2 ; (B) = Sn(OH)Cl; (C) Sn(OHh
[Hint: Sn and Pb dissolve in alkali.] SnCl 2 + H20 Sn(OH)Cl + HC1
(xi) Alkanes are more stable than sHanes. (A) (8)
[Hint : The C-C bond energy is higher than Si-Si bond SnCl 2 + NaOH ----) Sn(OHh + 2NaCl
energy.] (C)
(xii) CCl4 does not act as a Lewis acid while SiCl4 and SriCl 4 Sn(OHh + 2NaOH ----:, Na2Sn02 + 2H20
act as Lewis acids. 3SnCl2 + 2AuCl 3 ----) 3SnCl4 + 2Au
[Hint : SiCL! and SnCl4 act as Lewis acids as they can extend SnCh + 2HCl + 12 SnCl 4 + 2HI]
their coordination number beyond 4 due ~o the 14. A colourless crystalline solid (BA) dissolves in water. When
presence of d-orbitals.]
the solid is heated with concentrated H2S04, a reddish brown
(xiii) Radioactive materials are shielded by lead blocks.
gas (X) is liberated. A solution of the salt when treated with
[Hint : The penetration of radioactive rays is minimum potassium chromate solution gives a yellow precipitate (Y)
through lead.] insoluble in acetic acid. The same solution gives a white
(xiv) SnCl2 has high melting point (is solid) while SnCl4 has precipitate which dissolves in excess of NaOH to form a
low melting point (is a liquid). compound (Z). Identify (X), (Y), (Z) and the salt (BA).
[Hint : SnCl2 has ionic nature while SnCl4 is a covalent [Ans. (BA) = Pb(N0 3h; (X) = N02 ; (Y) = PbCrO,,; (Z) =Na2Pb02]
compound involving sp3 hybridization.] 15. A white solid (A) is not completely soluble in dilute HCI or
(xv) Lead pollution is caused by car exhaust. dilute H2S04 but dissolves in dilute HN03 with effer-
[Hint:Lead tetraethyl is added to petrol as antiknock. It is vescences. In the evolved gas, a bUllung magnesiumribben-~~ ~~~
evolved oUIing ignition of petrol as lead tetrabromide continues to burn. (A) when heated forms a yellow solid (B)
which causes pollution.] which is an amphoteric oxide. (B) when heated in air forms a
(xvi) Carbon atom is tetravalent inspite of the fact that there red coloured compound (C). (C) when dissolved in
are only two unpaired electrons in it. concentrated RN03 gives a brown residue (D). Identify (A)
[Hint : One of the p-orbitals is empty. The ns electron pair to (D).
is unpaired and the electron is shifted to np orbital, [Aos. (A) PbC0 3; (B) = PbO; (C) = Pb304; (D) = Pb021
i.e., in excited state, the electronic configuration is . 16. A white coloured inorganic salt (A) gives the following
2s1 2p.~ 2pj 2p~. There is sp3 hybridization and four reactions:
hybrid orbitals each having one electron come into (i) It is soluble in water and the solution has sweet taste.
existence, showing tetra valency.] The solution turns black in presence of H2S.
(xvii) PbCl4 exists while PbBr4 and PbI4 do not exist. (ii) The solution gives a white precipitate with dilute HCI
[Hint : Pb4+ is an oxidising agent and readily changes into which is soluble in hot water.
Pb2+. The Br- and r ions are reducing agents. Thus, (iii) The salt when heated gives acetone and a yellow
redox reaction occurs indicating that PbBr4 and Pb4
coloured residue.
are unstable compounds.
Identify the salt (A) and give chemical reactions.
Pb4+ + 4Br- ----:, PbBr2 + Br2]
[Aos. (A) is Pb(CH 3COOh
(xviii) C02 is an acidic anhydride while Pb0 2 is basic
anhydride. Pb(CH 3COOh + H 2S PbS + 2CH3COOH
Black
[Hint : C is a non-metal. Its oxide, CO2, is thus acidic in
Pb(CH 3COOh + 2HCl ----:, PbCl2 + 2CH 3COOH
nature while.1ead is a metal and its oxide is basic in
Soluble in
nature.] hot water
12. A substance (X) is dissolved in concentrated hydrochloric Pb(CH3COO)2 ----:, PbO + CO 2 + CH3COCH3]
acid and on treating the solution with sodium hydroxide
solution a white precipitate formed which dissolved in excess, 17. Starting from SiCl4 prepare the following in steps not e.xceed-
giving a solution with strongly reducing properties. ing the number given in parentheses (give reactions only):
On heating (X) with sulphur, a brown powder (Y) was formed (i) Silicon (I).
which dissolved in yellow ammonium sulphide and on adding (li) Linear silicon containing methyl groups only (4).
HCI, a yellow precipitate was formed. (iii) Na2Si03 (3). [I.I.T. 2001)
When (X) was strongly heated in air, a white powder (Z) was [Hint ~: (i) SiC14 + 2Mg ----:, Si + 2MgCl2
obtained. When (Z) was fused with sodium hydroxide and
extracted with hot water, white crystals were obtained. (li) (a) SiCl4 + 2Mg ----:, Si + 2MgCl2
Identify (X), (Y) and (Z) and write the reactions. Cn Catalyst
13. An inorganic compound (A) is a strong reducing agent. Its 28Qo:-300.C ) (CH 3h SiC12
hydrolysis in water gives a white turbidity(B). Aqueous
solution of (A) gives a white precipitate (C) with NaOH CH 3 CH 3
I I ~
solution which is soluble in excess of NaOH. (A) reduces auric
(e) Cl-Si-Cl + 2H20 HO-Si-OH + 2HCl
chloride to produce purple of cassius. (A) also reduces iodine
and gives chromyl chloride test. What are (A) to (C) and give I I
CH 3 CH3
the chemical reactions.
CH 3 CH3 CH3 eH3 (d) Cassiterite (iv) PbCr04

I I I I (e) Lignite (v) Lead monoxide
(d) OH-Si--OH +HO-Si-OH~ HO-Si-O-Si-OH (f) White lead (vi) PbCr04'PbO
I I I I (g) Chrome yellow (vii) Minium
CH3 CH3 CH3 CH3 (h) Chrome red (viii) An ore of lead
OH CH3 CH 3 CH 3 [B] (a) Diamond (i) A poisonous gas
(CH 3 hSi
<
_ _ _ _O;;:.:H~)
I
HO-Si-O-Si-O-Si-OH
I
I
I
I
I
(b) Graphite
(c) Phosgene
(ii) Metal carbonyls
(iii) A fuel
CH 3 CH 3 CH 3 (d) Producer gas (iv) Fire extinguisher
This chain increases finally a polymer is obtained. (e) Water glass (v) Refrigerant
(f) Carbon monoxide (vi) Lead pencils
(iii) (a) SiCI4 + 4H20 ~ Si(OH)4 + 4HCI
(g) Solid carbon dioxide (vii) Sodium silicate
(b) Si(OH)4 Heat) Si02 + 2H20 (h) Carbon dioxide gas (viii) Abrasive
(c) Si02 + Na2C03 ~ Na2Si~ + CO2] [C] (a) SnC4'5H20 (i) Carborundum
(b) (CH3COO)zPb (ii) An alloy of tin and lead
(c) Pb02 (iii) Soda glass
• Matching Type Questions (d) SiC (iv) Hydrides of silicon
Match the foUowing : (e) SnCl2 (v) Butter of tin
[A] (a)"Red lead (i) Carbon (f) Solder (vi) An oxidising agent
(b) Litharge (ii) An ore of tin (g) Silanes (vii) Sugar of lead
(c) Galena (iii) A white pigment
(h) Na20CaO'6Si02 (viii) A reducing agent
Answers : Subjective Type Questions (e) Soft glass--Na20, CaO, Si02

1. (a) Diamond, graphite and coal. Graphite is a good conductor of (D Hard glass-K20, CaO, Si02
electricity. 6. (a) On heating above 470DC, it decomposes into PbO and O2,
(b) Fullerene or Bucky ball 2Pb304 ~ 6PbO + 02
(c) I~C (used for carbon dating) (b) On heating, it breaks up into PbO, N02 and 02'
(d) Diamond. 2Pb(N03h ~ 2PbO + 4N0 2 + 02
2. (a) Carbon (c) On heating, it'decomposes giving acetone.
(b) Lead (CH3COOhPb ~ PbO + C~ + CH3COCH3
(c) Ununquadium (114) (d) Hydrolysis occurs with water of crystallisation.
(d) Silicon SnCI2'2H20 ~ Sn(OH)CI + HCl + H20
(e) Silicon and germanium (f) Lead (e) On heating, it decomposes into red lead.
3. (i) Due to inert pair effect. _ 2PbC03'Pb(OHh ~ Pb30 4 + CO + CO2 + H20
(ii) Methane. Silicon atom is bigger in size in comparison to 7. (i) [2HN03 + Sn ~_ Sn(N03h + 2H] x 4
hydrogen, thus, silane is unstable. 2HN03 + 8H ~ N~N03 + 3H20
(iii) Carbonates of alkali metals are salts of strong bases and weak Sn + IOHN03(dil.) ~ 4Sn(N03h + NH4N03 + 3H20
acid and hence undergo hydrolysis. (ii) Limestone dissolves in the form calcium bicarbonate.
(iv) The maximum covalency of carbon is 4 due to absence of CaC03 + H20 + CO2 ~ Ca(HC03h
d-orbitals. It cannot expand its octet. (iii) Water 'gas is formed.
(v) SnCl'l is an ionic compound while SnC4 is covalent in nature. C + H20 ~ CO+H2
'----v---'
4. (a) SiOt is the basic building unit of all silicates. -Water gas
(b) Carbon-carbon bond dissociation energy is quite high. (iv) Pb 30 4 ~ 2PbO + Pb~
(c) Solid carbon dioxide, it does not wet the surface when it melts.
(d) Mobile electrons are not present in diamond. Conduction of
electricity requires movement of electrons. The conduction of Pb304 -t: 4HN0 3 ~2Pb(N03h + P~ + 2H20
heat does not require movement of electrons. (v) It decolourises iodine.
(e) Freon, CF2CI2. ' 2SriCl2 + 212 ~ 2SilCl 2I2 SnCl4 + Sn4
S. (a) Coal gas-H 2, CH4, CO, N2 (vi) NRtOH + CO 2 ~ NH4HC03
tb) Producer gas-CO, N2 NaCI + NH4HC03 ~ NaHC03 + NH4Cl
(c) Water gas-CO, H2
NaCl + NH 40H + CO 2 ~ NaHC03 + N~Cl
(d) Natural gas-CH 4, C2H6 , C 3Hs
Elements of Group IVA or 14 (Elements of Carbon Family)
(vii) [2HN03 ~ H20 + 2N0 2 + 01 x 2 (vi) Silicon is fused with magnesium. Magnesium silicide is now
. Sn + 20 + H 2 0~· HZSn03 treated with dilute HCl when a mixture of silicon hydrides is
obtained.
Sn + 4HN03 ~ H2Sn03 + 4N02 + H20
Metastannic acid 2Mg + Si ~ Mg 2Si DiL HC] ) A mixture of silicothydrides
(Silanes)
(viii) 2PbS ;: 02 ~ 2PbO + S02
(vii) By passing a current of silicon tetrachloride over molten
PbS + 202 ~ PbS04
aluminium.
. Roasted in a limited supply of oxygen. Air supply is cut-off
3SiCl4 + 4Al ~ 3Si + 4AlCl3
and fresh galena is added and the temperature is raised. Galena
(viii) 4C2HsCI + 4Pb---Na ~ (C2Hs)~b + 4NaCl + 3Pb
reduces both PbO and PbS04 to metallic lead.
2PbO + PbS ~ 3Pb + S02 (ix) PbO + 2CH3COOH ~ (CH3COO)zPb + H20
PbS04 + PbS ~ 2Pb + 2S0 2 (CH 3COOhPb + K2Cr04 ~ PbCr04 + 2CH3COOK
Chrome yellow
(ix) SnCl2 + 2NaOH ~ Sn(OHh + 2NaCl
Sn(OHh + 2NaOH ~ Na2Sn02 + 2H20 (x) CO + H2 ZOO atm. ) CO is absorbed.
'----v-----' Amm.Cu 2Cl2
Water gas
SnClz + 4NaOH ~ Na2Sn02 + 2NaCl + 2H20
It is released when pressure is removed.
(x) [CaF2 + H2S04 ~ CaS04 + 2HF] x 2
9. (i) Elements oflVA or 14th group:
Carbon, Silicon, Germanium, Tin and Lead.
2CaF2 + SiOz + 2H2S04 ~ 2CaS04 + SiF4 + 2H20 (ii) Na2Si03'CaSi03'4Si02
-(xi)- . SnC12+2FeCI3~SnCI4F2FeCI2 . (iii) The amorphous form: of carbon obtained by scrapping the walls
(xii) HgCl2 + SnCl2 ~ Hg + SnC1 4 of a retort which has "been used in destructive distillation of coal.
(xiii) SnS + S ~ SnS2 (iv) The water gas mixed with volatile hydrocarbons is known as
SnS2 + (NH4)2S ~ (NH 4h SnS 3 carburetted water gas. Semi water gas is a mixture of water gas
k
(xiv) Pb + 2CH3COOH + O2 ~ (CH 3COOhPb + H20
and producer gas. It is obtained by passing a mixture of steam
and air over incandescent coke.
(xv) C()1sN02 + 6HCI + 3SriCl2 ~ C()1sNH2 + 3SnCl4 + 2H20
(v) A coordination compound of metal with carbon monoxide
(xvi) 2CH3C1 + Si ~ (CH3hSiC1 2 molecules as ligands is known as metal carbonyl.
(xvii)KiFe(CN)6 + 3H2S04 ~ 2K2S04 + FeS04 + 6HCN (vi) The crumbling of white tin into grey powder from a very low
[HCN + 2H20 ~ HCOOH + NH3] x 6 temperature is called tin disease or tin plague.
[2NH3 + H2S04 ~ (NH4hS04] x 3 (vii) CC4 does not undergo hydrolysis while SiC4 undergoes
[HCOOH ~ CO + H20] x 6 hydrolysis.
(viii) The dissolution of lead in water in presence of dissolved oxygen
. KiFe(CN)6 + 6H2S04 + 6H20 ~ 2K2S04 + FeS04 +
is known as plurnbosolvency. .
3(N~hS04 + 6CO 12. X = Sn; Y = SnS; Z Sn02
(xviii) Ni + 4CO ~ Ni(CO)4
Sn + 2HCl~ SnCh +H2
Nickel carbonyl
(X)
(xix) Si + Na2C03 ~ Na2Si03 + C
(xx) PbC1 2 + 2HCl ~ H2PbCl4 SnCl2 + 2NaOH ~ Sn(0H)2 + 2NaCI
Chloroplumbous acid Sn(OHh + 2NaOH ~ Na2Sn02 + 2H 20
(Soluble) Reducing agent
8. (i) The ore is fIrst roasted to remove sulphur, arsenic as S02 and Sn+S~ snS
Asi03 respectively. The roasted mass.js mixed with about one (YlBrown
fIfth its mass of powdered anthracite and a little lime. The mixture SnS + (~hSnS2 ~ (NH4hSnS3
is heated in reverberatory furnace when tin metal is formed. (NH4hSnS3 + 2HCl ~ SnS2 + HzS + 2NH4Cl
Sn02 + 2C ~ Sn + 2CO Yellow
(ii) On heating above 470°C, red lead decomposes into litharge. Sn + 02~ Sn02
2Pb30 4 ~ 6PbO + 02 (Z)
(iii) On heating litharge in air about 450°C. . Sn02 + 2NaOH ~ Na2Sn03 + H20
6PbO + 02 ~ 2Pb 30 4 White crystals
(iv) Lead is converted into white. lead by Dutch process or Answers : Matching Type Questions
electrolytic process. See text on page 436. [A] (a-vii); (b---v); (c-viii); (d-ii); (e-i);(f-iii); (g-iv); (h-vi)
(v) .NaOH is added to stannous chloride: The stannous hydroxide [Bl (a-viii); (b---vi); (c-i); (d-iii); (e-vii); (f-ii);(g-v); (h-iv)
precipitilted is heated in atmosphere of CO 2. [C] (a-v); (\)-...:..vii); (c-vi); (d-i); (e-viii); (f-ii); \g-iv); (h-iii)
SnCl2 + 2NaOH -----7 Sn(OHh + 2NaCI
Sn(OHh SnO + H20.
..-~ .. -~ .. -~ .. -~ .. - - - -.. -----~

·ttttlSTRA1'ONS OF OBJECTIVE QUESTIONS'

1. Graphite is not : 8. In (Si04)4-- (tetrahedral structure), three oxygen atoms are
(a) a good conductor of heat shared in which of the following? [I.I.T.2005]
(b) an amorphous allotrope of carbon (a) Sheet silicates (b) Three dimensional silicates
(c) softer than diamond' (c) Linear silicate (d) Pyrosilicate
(d) used for making lubricants ADS. (a)
Ans. (b) [Hint : See page No. 427]
[Hint : Graphite is crystalline allotrope of carbon.] 9. In silicon dioxide: [A.I.E.E.E. 2005]
2. Carbon atoms in diamond are bonded with each other in a (a) each silicon atom is surrounded by four oxygen atoms
configuration : and each oxygen atom is bonded to two silicon atoms
(a) linear (b) planar (b) each silicon atom is surrounded by two oxygen atoms
(c) tetrahedral (d) octahedral and each oxygen atom is bonded to two silicon atoms
Aus. (c) (c) silicon atom is bonded to two oxygen atoms
3. When heated with concentrated H ZS04, ~Fe(CN)6 gives: (d) there are double bonds between silicon and oxygen atoms.
(a) CO (b) CO2 ADS. (a)
(c) (CNh and CO . (d) (CNh and COz [Hint: Each silicon atom is ·surroun.ded ,tetrahedrally by__ follL
Ans. (a) oxygen atoms.
[Hint : K 4Fe(CN)6 + 6H 2S04 + 6H 20 ~ 2K 2S04 + FeS04 I I
o 0
+ 3(NH4hS04 + 6CO 1 I I
4. Carbon monoxide is absorbed by : - 0 - Si-O-Si-O- ]
(a) plants I I
o 0
(b) alcohol I I
(c) Ni(CO)4
10. Silica reacts with magnesium to form a magnesium compound
(d) ammonical solution of cuprous chloride
(X). (X) reacts with dilute HCI and forms (Y). (Y) is :
Ans. (d)
[E.A.M.C.E.T.2004]
[Hint : All the four valencies of carbon are not satisfied. It behaves
(a) MgO (b) MgCl 2
as an unsaturated compound and forms addition products.
Hioh
(c) MgSiO (d) SiC4
CuCl + CO pres~ure) CuCI·CO] Ans. (b)
Ammonical
[Hint: Si02 + 2Mg ~ 2MgO + Si ; MgO + 2HCI ~ MgCl 2
solution
(X) (X) (Y)
5. Which of the following is correct? + HP]
(a) Silicones are organosilico polymers containing
11. Silica is reacted with sodium carbonate. What is the gas
Si-O-Si linkage.
liberated ? [E.A.M.C.E.T.2005]
(b) R3SiClon hydrolysis gives R3Si-O-SiR3
(a) CO (b) Oz
(c) Both
(c) COz (d) ~
(d) None
ADS. (c)
ADS. (c)
[Hint: Si02 + Na2C03~ Na2Si03 + CO2 ]
6. The general formula of cyclic or ring silicates is :
12. Pb and Sn are extracted from their chief ores by :
(a) (Si205)~n- (b) (Si03)~-
[I.I.T. 2004 J
(c) (SiO~-)n (d) both (b) and (c) (a) carbon reduction and self reduction
Ans. (d) (b) self reduction and carbon reduction
7. Which one of the following statements is wrong? (c) electrolysis and self reduction
(a) Ionic carbides are formed by highly electropositive (d) self reduction and electrolysis
metals. ADS. (b)
(b) Carborundum and boron carbide are true covalent [Hint : PbS + 2PbO ~ 3Pb + S02 (self reduction) ; Sn02 + C
carbide. ~ Sn + CO 2 (carbon reduction)].
(c) Carborundum and boron carbide are used as abrasive.
13. The soldiers of Napoleon army while at Alps during freezing
(d) MgzC 3 like CaC z on hydrolysis evolves C zH 2.
winter suffered a serious problem as regards to tin buttons
Ans. (d) of their uniforms. White metallic buttons of tin got converted
[Hint : Mg 2C3 on hydrolysis evolves propyne. Mg 2C3 + 4H 20
to grey powder. This transformation is related to :
~ 2Mg(OHh + CH3~;;;ECH (propyne)] [A.I.E.E.E. 2004]
(a) an interaction with nitrogen of the air with very low (c) ionic radii of Pb 2+ and Pb4+ are larger than those of Ge 2+
temperature and Ge 4+
(b) an interaction with water vapour present in humid air (d) more pronounced inert pair effect in lead than in Ge.
(c) a change in the partial pressure of oxygen present in the Ans. (d)
air 15. Buckminsterfullerene is :
(d) a change in the crystalline structure of tin (a) graphite (b) diamond
Ans. (d) (c) C-60 (d) bone charcoal
[Hint: White tin converts itself into grey tin at 18°C,] Ans.(c)
14. Ge (II) compounds are powerful reducing agents whereas Pb [Hint : Fullerene, a carbon allotrope, consists of spherical C-60
(IV) compounds are strong oxidants. It can be due to : molecules with the extra ordinary shape of a soccer ball. It
(a) Pb is more electronegative than Ge has 12 pentagonal and 20 hexagonal faces with each atom
... -
(b) ionisation potential of lead is less than that of Ge sp2 hybridized and bonded to three other atoms.]
Set I : This set contains questions with single correct answer.
-
1. In the ground state the carbon atom has ......... unpaired 10. Which of the following is the chemically inactive allotropic
electron/electrons: form of carbon?
(a) 2 D (b) 3 D (a) diamond D (b) coal D
(c) 4 D (d) no D (c) charcoal D (d) animal charcoal D
2. What is the general electronic configuration of group 14 or 11. The use of diamond as a gem depends on its:
IVA elements: (a) hardness D (b) high refractive index D
(a) ni n/ D (b) ns2 np 2 D (c) purest form of carbon D (d) chemical inertness D
(c) ni np6 D (d) ns2 D 12. CO forms a volatile compound with:
3. The element whkh forms only one hydride is : (a) nickel D (b) copper D
(a) C D (b) Si D (c) sodium D (d) aluminium D
(c) Pb D (d) none of these D 13. A colourless gas which bums with blue flame and reduces
4. Carbon shows tetra valency due to: CuO to Cu is:
(a) i / hybridization D(b) i p hybridization D
(a) N2 D (b) CO D
(c) dS/ hybridization D (d) sp3 hybridization D
(c) CO2 D (d) N0 2 D
5. In group IVA or 14 of the extended form of the periodic table
14. Fire extinguishers contain a bottle of H2S04 and:
with increase in atomic number, the metallic character:
(a) Caco3 D (b) MgC0 3 D
(a) increases D
(b) decreases
(c) NaHC0 3 D (d) any carbonate D
D
(c) remains the same D 15. H2S04 is not used for the preparation of CO2 from marble
(d) first "increases then decreases D chips because:
6. The species present in solution when CO 2 is dissolved in (a) it does not react D
water: (b) huge amount of heat is evolved D
(a) H2C0 3, CO~- D (c) the reaction is vigorous D
(b) HCO-3, C0 32- [J (d) calcium sulphate is sparingly soluble and get deposited
(c) CO2, H2C0 3 D on marble chips and stops the reaction D
(d) CO2, H2C0 3, HC0 3, CO~- [J 16. Producer gas is the mixture of:
[Hint : CO 2 . + H 20 .----'" H 2C0 3 ~ H+ + HCO) ~ (a) CO and N2 D (b) CO andH2 D
2H+ + CO~-] (c) N2 and NH3 D (d) CO, H2and N2 D
7. Diamond and graphite are: 17. A dry ice piece is composed of:
(a) isomers D (b) allotropes [J (a) solid He D (b) solid CO2 [J
(c) isotopes D (d) polymers D (c) solid S02 D (d) solid C6~ 0
8. Carbon has valency four in CH4. Its valency in acetylene is: 18. In laboratory burners, we use:
(a) 1 0 (b) 2 D (a) producer gas D (b) coal gas 0
(c) 3 0 (d) 4 [J (c) oil gas D (d) gobar gas 0
9. Which of the following is a good conductor of electricity? 19. Maximum ability of catenation is shown by:
(a) diamond D (b) graphite D (a) carbon D (b) nitrogen 0
(c) coal D (d) none of these D (c) oxygen D (<1) sulphur 0
.---__ i_ _
20. Graphite is a good conductor of electricity because it 32. The structure and hybridization of Si(CH3)4 is:
contains: (a) bent, sp 0 (b) trigonal, s/ 0
(a) bonded electrons 0 (b) mobile electrons 0 (c) octahedral, sp3J2 0 (d) tetrahedral, sl 0
(c) strong C-C bonds 0 (d) strong C=C bonds 0 33. Among the following substituted silanes, the one which will
21. Which form of the carbon has a two dimensional sheet like give rise to cross linked silicone polymer on hydrolysis is :
structure? (a) RSiCl 3 0 (b) R4Si 0
(a) Diamond 0 (b) Coal 0 (c) R2SiQ2 0 (d) R3SiCI 0
(c) Graphite 0 (d) Coke 0 34. Structural units of ice and dry ice are respectively:
22. If CO2 is passed in excess into lime water, the milkiness first (a) H20,CO 0 (b) COZ,H20 0
formed disappears due to: (c) H20,C02 0 (d) CO, C02 0
(a) reversal of the original reaction 0 35. Which of the following is a semiconductor?
. (6) formation of volatile calcium derivative [J (a) C 0 (b) Pb 0
(c) formation of water soluble calcium bicarbonate 0 (c) Ge 0 (d) Sn 0
(d) the solution getting heated by exothermic reaction 0 36. Carbon atoms in diamond are bonded with each other in a
23. When steam is passed through red hot coke: configuration:
(a) C02 and H2 are obtained 0 (a) linear 0 (b) planar 0
(b) CO and N2 are formed 0 (c) octahedral 0 (d) tetrahedral 0
(c) CO and H2 are obtained 0 37. Carbon dioxide is used for exting';ishing fire because:
(d) petrol gas is obtained 0 (a) it has a relatively high critical temperature -B-
24. Glass could be considered as: (b) in solid state, it is called dry ice 0
(a) amorphous solid 0 (b) an organic polymer 0 (c) it is neither combustible nor a supporter of combustion
(c) crystalline solid 0 (d) super cooled liquid 0 o
25. An important ore of lead is: (d) it is a colourless gas 0
38. The glass having the smallest coefficient of thermal
(a) magnesite 0 (b) camallite 0
expansion is :
(c) bauxite 0 (d) galena 0
26. Glass is soluble in:
(a) soft glass o (b) hard glass 0
(a) HF 0 (b) H2S04 o (c) sodalime glass o (d) pyrex glass 0
39. When the destructive distillation of coal IS done, the
(c) HQ04 0 (d) aqua-regia o non-volatile residue left in the retort is:
n. An alloy which does not contain copper is: (a) gas carbon 0 (b) coke 0
(a) bell metal 0 (b) bronze o (c) coal-tar 0 (d) lampblack 0
(c) brass 0 (d) solder o 40. A fuel will have a large fuel value if one gram of it on burning
28. Coal gas is a mixture of : gi ves more of:
(a) CO and H2 0 (a) carbon dioxide 0 (bY water vapours 0
(b) H2, saturated and unsaturated hydrocarbons, CO, CO2, (c) ash . 0 (d) calories 0
N2 and O2 0 41. For complete combustion of a fuel we shall need:
(c) saturated and unsaturated hydrocarbons 0 (a) high temperature 0
(d) CO, CO2 and CH4 . 0 (b) an excess of air 0
29. [Si04]4- has tetrahedral structure, the silicate formed by using (c) high air pressure 0
three oxygen has a : (d) an excess of air and high temperature 0
(a) linear polymeric structure 0 42. Annealing of glass is done to:
(b) three dimensional structure 0 (a) prevent it from becoming brittle and fragile 0
(c) pyrosilicate structure 0 (b) make it opaque 0
(d) two dimensional sheet structure 0 (c) make it transparent 0
30. Coal gas: (d) make it brittle 0
(a) burns with a smoky flame 0 43. Colour is imparted to glass by mixing:
(b) burns with non-smoky flame 0 (a) synthetic dyes 0 (b) metal oxides 0
(c) is not used for lighting purposes 0 (c) non-metal oxides' 0 (d) coloured salts 0
(d) is not a good fuel 0 44. Which of the following is not hydrolysed?
31. Mark the correct statement: I,J.KE. (OrissH) 2010]
(a) Water gas is used in the manufacture of methyl alcohol (a) CCl4 0 (b) SiCl4 0
o (c) SnCl4 0 (d) PbCl 4 0
(b) Water gas has the highest calorific value o 45. The poisonous gas present in the exhaust fumes of car is:
(c) Water gas burns with luminous flame o (a) methane 0 (b) acetylene 0
(d) The production of water gas is exothermic process o (c) carbon monoxide 0 (d) ethane 0
46. Phosgene is the common name given to: (d) it has strong catenation property 0
(a) carbonyl chloride 0 (b) phosphine 0 61. The heat of combustion of carbon is 94 kcal. The calOlific
(c) phosphorus oxychloride 0 value of carbon is about:
(d) phosphorus trichloride 0 (a) 7.8kcal 0 (b) l5.6kcal o
47. Red lead is: (c) 47.0kcal 0 (d) 94kcal o
(a) PbO 0 (b) Pb02 0 62. Which compound is called sugar of lead?
(c) Pb30 4 0 (d) Pb203 0 (a) PbCl 2 0 (b) Pb(N03}z 0
4&. Which of the following halides is least stable and has (c) PbS04 0 (d)Pb(CH3COO}z 0
doubtful existence? 63. The number and type of bonds between two carbon atoms
(a) 04 0 (b) Sn4 0 inCaC 2 are:
(c) GeL. 0 (d) PbL. 0 (a) one sigma and one pi bond 0
49. Which one of the oxides is neutral? (b) one sigma and two pi bonds 0
(a) CO 0 (b) Sn02 0 (c) one sigma and one and a half pi bond 0
(c) Zno 0 (d) SiOz 0 (d) one sigma bond 0
50. An example of major air pollutant is: 64. When a mixture of air and steam is passed over red hot coke,
(a) Oz 0 (b) COz 0 the outgoing gas contains:
(c) CO 0 (d) He 0 (a) producer gas 0 (b) water gas o
51. Identify the correct statem.~nt with respect ,t,o CO: (c) coal gas 0 (d) none of these o
(a) it combines with water to give carbonic acid 0 65. Tin reacts with conc. HN03 and gives: ""', .. ,
(b) it combines with haemoglobin of the blood 0 (a) stannic nitrate 0 (b) stannous nitrate o
(c) it is a powerful oxidising agent 0 (c) metastannic acid 0 (d) none of these o
(d) it is used to prepare aerated water 0 66. Which substance is used as lubricant?
52. Which of the following compounds is used as a reducing (a) SnCh 0 (b) Si02 o
agent? (c) graphite 0 (d) quartz o
(a) Sn02 0 (b) SnS2 0 67. The colour imparted by Co(II) compounds to glass is :
(c) SnC4 0 (d) SnClz 0 [A.I.I.M.S.2006]
53. Which of the following statements is not correct? (a) deep blue 0 (b) green o
(a) Lead salts are slow poisons 0 (c) yellow 0 (d) red o
(b) Lead metal is used in accumulators 0 68. The principal constituent of pyrex glass is:
(c) Plumbosolvency increases by the presence of carbo- (a) Zn 0 (b) B o
nates, sulphates, phosphates, etc. 0 (c) Pb 0 (d) Fe o
(d) Lead is a soft metal 0 69. The difference in properties of €H4 and Si~ is due to:
54. Chrome yellow is chemically called: (a) large difference in the e1ectronegativity of carbon and
(a) lead chromate P (b) lead sulphate 0 ~oo 0
(c) lead iodide '0 (d) basic lead acetate 0 (b) large difference in size of carbon and silicon atoms 0
55. The formula of white lead is: (c) the inability of carbon to expand its octet 0
(a) Pb(OHh'PbC03 0 (b) 2PbC03'Pb(OH}z 0 (d) the inability of silicon to form double bonds 0
(c) Pb(OH}z'Pb(CH3COO}z0 (d) PbC03'PbO 0 70. CCl4 is inert towards hydrolysis but SiCI4 is readily hydro-
56. Which of the following is a covalent carbide? lysed because:
(a) Cac2 0 (b) Al4C3 0 (a) carbon cannot expand its octet but silicon can expand
(c) wc 0 (d) SiC 0 its octet 0
57. The anhydride of carbonic acid is: . (b) ionisation potential of carbon is higher than silicon 0
(a) C O ' 0 (b) COz 0 (c) carbon forms double and triple bonds 0
(c) C30z 0 (d) none of these 0 (d) electronegativity of carbon is higher than that of silicon
58. The hydroxide of which metal ion is soluble in excess of o
sodium hydroxide solution: 71. Which of the following oxides has three dimensional
(a) Fe3+ 0 (b) Cr3+ 0 structure?
(c) Sn 2+ 0 (d) eu2+ 0 (a) CO 0 (b) COz 0
59. Which one of the oxides is most acidic? (c) SiOz 0 (d) S02 0
(a) Na20 0 (b) NiO 0 72. When carbon bums in air it forms two oxides CO and CO2,
(c) Cao 0 (d) SnO Q This shows that carbon has:'
60. The number of carbon compounds is very large because: (a) two allotropic forms 0
(a) carbon is tetra-valent 0 (b) two oxidation states 0
(b) it has non-metallic character 0 (c) two isotopes 0
(c) it shows allotropy 0 Cd) four electrons in valency shells 0
73. In silicon dioxide: 86. Solder is an alloy of: [A.F.M.C. 2005]

(a) there are double bonds between silicon and oxygen (a) 70 % Pb, 30 % Sn o(b) 33 % Pb,67 % Sn 0
atoms 0 (c) 80 % Pb, 20 % Sn o(d) 90 % Cu, 10 % Sn 0
(b) each silicon atom is surounded by four oxygen atoms 87. Solid carbon dioxide is used as :
and each oxygen atom is bonded to two silicon atoms. (a) poison 0 (b) five extinguisher o
. 0 (c) refrigerant 0 (d) artificial respirant o
(c) silicon is bonded to two silicon atoms 0 88. When Pb02 reacts with conc. HN03, the gas evolved is:
(d) each silicon atom is surrounded by two oxygen atoms [A.I.E.E.E.2005]
and each oxygen atom is bonded to two silicon atoms (a) N02 0 (b) ~ 0
o (c) N2 0 (d) N20 0
74. In the manufacture of glass the addition of Mn02 gives: 89. When steam reacts with red hot coke to form C02 and
(a) yellow colour 0 (b) red colour 0 hydrogen:
(c) violet colour 0 (d) pink colour 0 (a) water acts as oxidising agent o
75. Which is not used as pigment in paints? (b) water acts as reducing agent o
(a) PbCr04 0 (b) Pb02 o (c) carbon acts as oxidising agent o
(c) White lead 0 (d) Pb 30 4 o (d) there is no oxidation or reduction [J
76. Lead dissolves most readily in: 90. Synthesis gas is a mixture of:
(a) acetic acid 0 (b) sulphuric acid .0 (a) CO + steam 0 (b) CO + N2
(c) nitric acid 0 (d) hydrochloric acid 0 (c) CO + H2 0 (d) CO2 +CH4'·
77. Which of the following metals is an important ingredient of 91. Bond energy is highest for:
transistors? (a)Sn-Sn 0 (b) C-C 0
(a) Osmium o (b) Germanium o (c) Si-:-Si 0 (d) Ge-Ge 0
(c) Gold o (d) Sodium o 92. Graphite is soft and lubricant, extremely difficult to melt. The
78. The gas which is present both in producer gas and in water reason for this anomalous behaviour is that graphite:
gas is: [A.I.E.E.E.2003]
(a) N2 0 (b) H2 0 (a) has carbon atoms arranged in large plates of rings of
(c) CO 0 (d) CO2 0 strongly bound carbon atoms with weak interplate
79. Which glass has the highest percentage of lead? bonds 0
(a) Soda glass 0 (b) Flint glass 0 (b) is a non-crystalline substance 0
(c) Jena glass 0 (d) Pyrex glass 0 (c) is an allotrope form of carbon 0
SO. Which does not exist? (d) has molecules of variable molecular masses like
polymers 0
(a) [CCl612- 0 (b) [SiCld- 0
93. Which of the fOllowmg is correct'composition of water gas?
(c) [GeF6]2- 0 Cd) [SnCI6f- O·
(a) CO+CI2 0 (b) CO +N2 0
81. The material used in solar cells contains:
(C)CO+H2 0 (d) CO+H2+N2 0
(a) Si 0 (b) Sn 0
94. What is the formula of carbon suboxide?
(c) TI 0 (d) Cs 0
82. 'Softening of lead' means:
(a) CO 0 (b) ~ o
(a) conversion of lead to PbO o (c) C20 4 0 Cd) C3~· o
95. Which of the following halide of carbon is used as
(b) conversion of lead to Pb 30 4 o refrigerant?
(c) removal of impurities (metallic) from lead o (a) CCl4 0 (b) CF4 0
Cd) washing lead with HN03 foHowed by a dil. alkali (c) CH2Cl2 0 (d) CH2F2 0
solution 0 96. The carbide which gives propyne on hydrolysis:
83. 'Lead pencil' contains: (a) A4C3 0 (b) CaC2 0
(a) graphite 0 (b) lead o (c) Fe3C 0 (d) Mg2C3 0
(c) charcoal 0 (d) lead sulphide o 97. Which among the following carbides is methanide?
84. .Electrolytic bath in electrolytic refining of lead contains: (a) Al4C3 0 (b) CaC2 0
(a) H2SiF6 only 0 (c) B~C 0 (d) SiC 0
(b) PbSiF6 only 0 98. Percentage of lead in lead pencil is:
(c) H2SiF6 in presence of gelatin 0 (a) zero 0 (b) 20 0
(d) H2SiF6 and PbSiF6 in presence of gelatin 0 (c) 80 0 (d) 70 0
85. Which of the following oxides is amphoteric in character? 99. CCl4 is used as fire extinguisher because:
[A.I.E.E.K 20051 (a) its m.pt. is high 0 (b) it fonns covalent bondO
(a)Cao o (b)~ o (c) its b.pt is low 0
(c) Si~ o Cd) Sn02 o (d) it gives incombustible vapours 0
100. The correct order of increasing C-O bond length of CO, 112. Which is likely to show inert pair effect?
CO~-, CO2 is: [C.B.S.E. 2007] [D.C.E. (Engg.) 2007]
(a) CO~- < CO2 < CO 0 (b) CO2 < CO~- < CO 0 (a) K 0 (b) Mg 0
(c) QO < CO~- < CO2 0 (d) CO < CO2.< CO~- 0 (c) AI 0 (d) Pb 0
101. PbF4, PbC14 exists but PbBr4 and· PbI4~do not exist 113. The stability of dihalides of Si, Ge, Sn and Pb increases
because of: [C.E.E. (Haryana) 2000] steadily in the sequence: [A.I.E.E.E.2OO7]
(a) large size of Br- and r 0 (a) PbXz < snX2 < GeX2 < SiX2 0
(b) strong oxidising character of Pb4+ 0 (b) GeX2 < SiXz < snX2 < PbX2 0
(c) strong reducing character of Pb4+ 0 (c) SiX2 < GeX2 < PbX2 < snX2 0
(d) low electronegativity of Br- and r 0 (d) SiX2 < GeX2 < SnX2 < PbX2 0
102. Marsh gas contains: [A.F.M.C. 2001] 114. Which of the following oxidation states are the most charac-
(a) ~ 0 (b) COz 0 teristic for lead and tin respectively? [C.B's.E, 2007]
(c) C2H6 0 (d) N2 0 (a) +2,+4 0 (b) +4,+4 0
103. Which of the following is most stable? [C.P.M.T. 200]] (c) +2, +2 0 (d) +4, +2 0
(a) Sn 2+ 0 (b) Ge2+ 0 us. Which one of the following is present in the chain structure
2
(c) Si + 0 (d) Pb2+ 0 of silicates? [C.B's.E. 2007]
104. Butter of tin is: [B.V. (Pone) 2002]
(a) (Si20~-)n 0 (b) (Si~ln --=D=--_.~...
(a) SnCI2'SHin 0 (b) SnQ2'2HzO 0
(c) (Si04)4- 0 (d) Si20r- 0
(c) SnC4'4H20 0 (d) SnCI 4'SH20 0
116. Which of the following has the highest calorific value?
lOS. Biogas and producer gas are made up of:
[B.H.U. 2007]
[B.V. (Pune) 2002}
(a) biogas contains CO2 but producer gas does not 0 (a) Coal gas 0 (b) Water gas o
(b) producer gas contains CO but not CO2 0 (c) Producer gas 0 (d) Carbon dioxide gas o
117. The hybrid state of carbon atoms in C60 molecule is:
(c) both biogas_and producer gas have N z 0
(d) all the three above 0
(a) sp 0 (b) sl o
106. Me2SiCI2 on hydrolysis will produce: [I.l.T. (8) 2003]
(c) dsi 0 (d) sp2 o
118. Litharge is chemically: lA.I.I.M's. 2007]
(a) Me§i(OH)2 0
(b) Me2Si 0 0
(a) PbO o (b) Pb02 o
(c) -[~ehSi-O---]1I 0 (c) Pb304 o (d) Pb(CH3COOh o
(d) Me2SiCIOH 0 119. SiCl4 H 20) X Y
107. Carborundum is: (B.H-U. 20031 In the above reaction, X and Y respectively are:
(a) AI 20:, 0 (b) SiC 0 [E.A.M.C.E.T. (Moo.) 2007}
(c) BF3 0 (d) B4C 0 (a) Si02 and Si 0 (b) ~Si04 and Si02 0
108. Which of the following is the composition of solder? (c) H2SiC16 andSi0 2 0 (d) H4Si04 andSi 0
[A.F.M.C. 2003] 120. Ai4C3 on hydrolysis gives ...... gas.
(a) Cu + Zn 0 (b) Pb + Sb 0 [J.E.E. (Orissa) 2007]
(c) Cu + Sn 0 (d) Pb + Sn 0 (a)~ o (b) C2H6 0
109. For making good quality mirrors, plates of float glass are (c) C2~ o (d) C2H2 0
used. These are obtained by floating molten glass over a 121. Diamond is hard because: [V.LT.E.E.E.2008]
liquid metal, which does not solidify before the glass. The
(a) all the four valence electrons are bonded to each carbon
metal used is: [AJ.E.E.E.2003}
atoms by covalent bonds 0
(a) Hg 0 (b) Sn 0
(b) it is a giant molecule 0
(c) Na 0 (d) Mg 0
(c) it is made up of carbon atoms 0
110. 'A' when added to silica will give 'B'. 'A' and 'B' are:
(d) it cannot be burnt 0
[D.P.M.T. 2007]
122. Among the following substituted silanes the one which will
(a)HF,H2SiF4 0 (b) HF,H2SiF6 0
give rise to cross-linked silicone polymer on hydrolysis is:
(c) HCI,H2Si~ 0 (d) HI,H2Si~ 0
[A.I.E.E.E. 2008]
111. In SiF~- arid SiCI~- which one is known and why? (a) R3SiCl 0 (b) 14Si 0
[D.C.E. (Eogg.) 2007]
(c) RSiCI 3 0 (d) R2SiCI2 0
(a) SiF~- because of small size of F 0 123. The incorrect statementls among the following is/are:
(b) SiF~- because of large size of F 0 [P.E.T. (Kerala) 2008]
(c) SiCl~- because of small size of Cl 0 I. NCls does not exist while PCI5 does.
(d) SiCI[ because of large size of CI 0 IT. Lead prefers to form tetravalent compounds.
III. The three C-O bonds are not equal in the carbonate (c) hydrolysis of (CH3hSiC1z followed by condensation
ion. polymerisation 0
Iv. Both 02 and NO are paramagnetic. (d) hydrolysis of (CH3)3SiCI followed by condensation
(a) I, ill and IV 0 (b) land IV 0 polymerisation 0
(c) II and III 0 (d) I and III 0 128. Which of the following statements is not correct?
(e) -IV only 0 [J.E.E. (W.B.) 2009]
[Hint : Lead prefers to form divalent compounds due to inert pair (a) Silicon is used extensively as a semiconductor .0
effect. In carbonate ion, all the three C-O bonds are equal (b) Carborundum is SiC 0
due to resonance.] (c) Silicon occurs in free state in nature 0
124. In silica, SiOz, each silicon atom is bonded to: (d) Mica contains the element silicon 0
(U.P.s.E.E. (Engg.) 2008]
129. On heating K4Fe(CN)6 with Conc. HZS04 gives the gas:
(a) two oxygen atoms 0 [J.E.E. (Orissa) 2009]
(b) four oxygen atoms 0 SOz
(a) 0 (b) COz 0
". (c) one silicon and two oxygen atoms 0 (c) CO 0 (d) NO z 0
(d) one silicon and four oxygen atoms 0 130. Products fonned, when Pb(N03h is heated, are :
125. C-C bond length is maximum in: [U.P.S.E.E. (Engg.) 2008] [J.E.E. (Orissa) 2009]
(a) diamond 0 (b) graphite 0 (a) PbO,N2>Oz 0 (b) Pb(NOzh,Oz 0
(c) naphthalene 0 (d) fullerene 0 (c) PbO,NO z, 0 z D (d)Pb,Nz,Oz c
126. Silica is reacted with sodium carbonate. What is the gas

131. The products of the following reaction are :
liberated? [C.P.M.T. 2008] . Heat
(a) CO 0 (b) ~ 0 S102 + C-----t Products
[J.E.E. (Orissa) 2010]
(c) ~ . 0 (d) 0 3 0
127. The straight chain polymer is fonned :
(a) SiC and CO2 0 (b) SiO and CO 0
[C.B.8.E. (P.M.T.) 2009"1 (c) SiC and CO 0 (d) Si and CO 0
(a) hydrolysis of CH3SiC13 followed by condensation poly-
132. Which of the following has' least tendency to undergo
catenation? lA.M.U. (Engg.) 2010]
merisation 0
(a) C 0 (b) Si 0
(b) hydrolysis of (CH3)4Si followed by addition poly-
(c) Ge 0 (d) Sn 0
merisation 0
Set n : This set contains questions with two or more correct answers.
133. Carbon dioxide is isostructural with: (c) C30 2 is also toxic like CO 0
(a) HgCI2 0 (b) SnClz 0 (d) Zircon, ZrSi04 is a gemstone 0
(c) C2H2 0 (d) N~ 0 139. The non-existence of PbI4 is due to:
134. CO is isostructural with: [I.I.T. (8) 19921 (a) highly oxidising nature of Pb4+ 0
(a) SnC12 0 (b) HgClz 0 (b) highly reducing nature of Pb4+ 0
(c) SOz 0 (d) ZnIz 0 (c) sufficiently large covalent character 0
135. Which of the given is/are amphoteric? (d) highly reducing nature of r ions 0
[l.S.M.(Dhanbad} 1994) 140. Which is not correct?
(a) BeO 0 (b) AgzO 0 (a) Ge(OHh is amphoteric 0
(c) COz 0 (d) SnOz 0 (b) SnC14 is more stable than SnCl2 0
136. Decomposition of oxalic acid in presence of conc. HzS04 (c) Trisilylamine is pyramidal 0
gives: (d) GeC4inHClfonnsHz[GeC~] 0
(a) CO 0 (b) COz 0 141. Carbon differs from the rest of the family members because
(c) formic acid 0 (d) HzO 0 of:
137. Which of the following are true about silicones? (a) number of unpaired electrons in valence shell 0
(a) They are fonned by hydrolysis oi;,Rz SiClz 0 (b) small size 0
(b) They ate polymer, made up of Rz '~i02 units 0 (c) non-availability of vacant orbitals in valence shell 0
(c) They are made up of SiOt units 0 (d) non-availability of d~orbitals in valence shell 0
(d) They are macromolecules 0 142. Which of the following carbides on treatment with water
138. Which among the following statements are correct? give methane? [B.H.U.2007]
(a) Aqua dag and oil dag are made up of graphite 0 (a) Cac2 0 (b) BezC 0
(b) Graphite reacts with conc. RN0 3 to fonn mellitic acid (c) A4C3 0 (d) Mg zC3 0
4(COOH)6 0
143. Which of the metal oxides are reduced by CO? 144. Which of the following are the ores of lead? [B.H.U. 2007]
(a) ZnO 0 (b) Fe203 o (a) Galena 0 (b) Anglesite 0
(c) Cao 0 (d) Na20 o (c) Cerussite 0 (d) Plumbago 0
1. (a) 2. (b) 3. (e) 4. (d) 5. (a) 6. (d) 7. (b) 8. (d) 9. (b) 10. (a)
11. (b) 12. (a) 13. (b) 14. (c) 15. (d) 16. (a) 17. (b) 18. (c) 19. (a) 20. (b)
21. (c) . 22. (c) 23. (c) 24. (d) 25. Cd) 26. (a) 27. (d) 28. (b) 29. (d) 30. (b)
31. (a) 32. (d) 33. (a) 34. (c) 35. (c) 36. (d) 37. (e) 38. (d) 39. (b) 40. (d)
41. (d) 42. (a) 43. (b) 44. (a) 45. (c) 46. (a) 47. (c) 48. (d) 49. Ca) SO. (c)
51. (b) 52. (d) 53. (c) 54. (a) 55. (b) 56. (d) 57. (b) 58. (e) 59. (d) 60. (d)
61. (a) 62. (d) 63. (b) 64. (d) 65. (c) 66. Cc) 67. (a) 68. (b) 69. (a) 70. (a)
71. (c) 72. (b) 73. (b) 74. Cd) 75. (b) 76. (c) 77. (b) 78. (c) 79. (b) 80. Ca)
81. (a) 82. Cc) 83. (a) 84. (d) 85. Cd) 86. (b) 87. (c) 88. (b) 89. (a) 90. (c)
91. (b) 92. (a) 93. (c) 94. (d) 95. (d) 96. (d) 97. (a) 98. Ca) 99. (d) 100. (d)
101. (b) 102. Ca) 103. (d) 104. (d) 105. (d) 106. (c) 107. (b) 108. (d) 109. (a) 110. (b)
111. (a) 112. (d) 113. (d) 114. Ca) 115. (b) 116. (a) 117. (d) 118. (a) 119. (b) 120. (a)
121. (a) 122. (c) 123. (c) 124. (b) 125. (a) 126. (c) 127. (c) 128. (c) 129. (c) 130. (c)
131. (c) 132. (d) 133. (a, c) 134. (b, d) 135. Ca, d) 136. (a,b,d) 137. (a,b,d) 138. (a,b,d) 139. (a, d) 140. (b,c)
141. (b,d) 142. (h,c) 143. (a, b) 144. (a,b,c)
O. Objective Questions for liT ASPIRANTS .~

1. A red coloured mixed oxide (X) on treatment with conc. HN0 3 7. A mixture of two gases is formed when an organic acid is
gives a compound (Y). (Y) with HCI produces a chloride (Z) heated with conc. H 2S04, When the gaseous mixture is
which is insoluble in cold water but soluble in hot water.(Z) passed through KOH solution, one gas is absorbed. The
can also be formed by treating (X) with conc. HCl. Com- unabsorbed gas combines with chlorine and forms a
'pounds (X), (Y) and (Z) are: poisonous gas. The organic acid and the two gases evolved
(a) Pb304, Pb0 2, PbCl 2 (b) Mn304, Mn02, MnCl2 with conc. H 2S04 are respectively:
(c) Fe304, Fe203, FeCl3 (d) Fe304, FeO, FeCl2 (a) CH3COOH, CO 2, CO (b) oxalicacid,C02,CO
[Hint : Pb304 (X) is red coloured mixed oxide consisting PbO and (c) HCOOH,CO,H20 (d) none of these
Pb0 2 • [Hint: C OOH Conc.H,SO.
Pb 30 4 + 4HN0 3 ---7 2Pb (N0 3)2 + Pb0 2 + 2H20; -H 0 ) CO + CO2 KOH ) CO ~
(Y)
1
COOH
2
CO2 is t
Pb02 + 4HCl ---7 PbCl2 + 2H20 + Cl 2 absorbed COCI
2
(Y) (Z) Poisonous gas ]
PbCh is insoluble in cold water but soluble in hot water. Cupowder HO PI 't'
Pb30 4 + 8HCI ---7 3PbCl2 + 4H 20 + Cl2 ] 8. 2RCI+Si ) R2S'CI ~ R S'(OH) oymensalon
570K . 1 2 2 1 2 )
(X)
(A). (A) is:
2. An inorganic compound (A) made of two most occurring (a) cyclic silicone (b) cross linked silicone
elements in the earth's crust and used in building construc- (c) linear silicone (d) none of these
tion when made to react with carbon, forms a poisonous gas [Hint : See page no. 426]
(B) which is most stable diatomic molecule. Compounds (A) +Na?C0 3
and (B) are: 9. SiCl4 ~ (A) ~ (B) H~at . > (C). The
(a) Si02, C02 (b) Si02, <:;0 compound (C) is:
(c) Si02,N2 (d) CaO,C02 (a) Si02 (b) Si (c) SiC
[Hint : Si02 is a compound of oxygen and silicon, the two most [Bint : SiCl4 + H20 ---7 Si(OH)4 Si0 2
abundant elements of earth's crust and is used in building
(A) (B)
construction.
SiOz + 2C ---7 Si + 2CO (poisonous gas and a stable Na2Si03 ]
(C)
diatomic molecule) ]
3. SnCl2 + HCI + Iz~ (A) + (B) 10. When a mixture of air and steam is passed over red hot coke,
The compounds (A) and (B) are: the outgoing gas contains:
(a) Sn12, Cl 2 (b) H2SnCI 4 , HI (a) producer gas (b) water gas
(c) SnC4, HI (d) HSnCI 3 , HI (c) coal gas (d) mixture of (a) and (b)
[Hint: Coke +air ---7 CO + N2 ; Coke + H20 ---7 CO+ H2 ]
[Bint : SnCI 2 decolourises iodine forming colourless HI. Producer gas Steam Water gas
SnCl 2 + 2HCI + 12 ---7 SnCl4 + 2HI ]
11 •. Lead oxide (PbO) can be dissolved in:
4. Bucky ball or buckminsterfullerene:
(a) HN~ (b) HCI
(a) .is an allotrope of carbon
(c) H2S04 . (d) H20
(b) is referred as C-60 [Hint : PbO dissolves in HN0 3 as it forms lead nitrate which is
(c) has sp2 hybridized nature and resembles with soccer soluble.
ball PbO + 2HN0 3 ---7 Pb(N03h + H20
(d) all of the above Hel forms insoluble PbCI 2 and H2S04 forms insoluble
S. When concentrated H 2S04 is added to K~e(CN)6' CO is PbS04. PbO is insoluble in water also.]
evolved. If in place of concentrated H2S04, dilute H 2S04 is 12. Which silicon compound is used as lubricant?
used, what gas will be evolved? (a) Asbestos (b) Silicone
(a) CO (b) .HCN (c) Zeolite (d) Mica
(c) N2 (d) CO2 13. A colourless solution (X) gives black precipitate on passing
[lJipt; K,;Fe(CN)6 + 3H2 S04 (di!.) -t 2K2S04 + FeS04 + 6HCN] H2S. (X) also gives a white precipitate with stannous chloride
6. Which tetrahalide does not act as Lewis acid ? which gradually changes to grey. What may be (X)? .
(a) CC4 (b) SiF4 (a) PbCl 2 (b) CdBr2
(c) Ge~14 (d) SnCl4 (c) HgC12 (d) Cu(N03h
[Hint : CCI 4 does not form hexachloro complex as d-orbitals are [Hint : HgCI2 + H2S ---7 HgS + 2HCI ;
not present in carbon but rest of the tetrahalides can form Black
hexahalo complexes.] SnCll
HgCI2 + SnCI2 ---7 Hg2CIz ---? 2Hg ]
White Grey
[Hint : The solution of lead acetate is sweet in taste, when HCl is
14. CaC03(s)~ (A)(s) + (B)(g) added to its solution, it fonns PbCl2 which is soluble in
+Carbon hot water.
'----_he_at_( C) (s) + (D) (g) Lead acetate on heating gives acetone and lead oxide (yellow
residue).
(C)(s) + H 20 ~ (E)(g). Pb(CH3COOh -----7 CH3COCH 3 + PbO + CO 2 ]
The compound (E)(g) is : 16. Which of the following bonds is the weakest?
(a) CO (a) Si-Si (b) Si-O
(c) C~ (c) Si-O (d) Si-H
[Hint : Caco3 CaO + CO2 17. Which metal does not form nitrate when heated with conc.
(A) (B) RN03?
(a) Zn (b) Mg
CaO+ C CaC 2 + CO
(c) Sn (d) Pb
(C) (D)
[Hint: Sn + 4HN03 -----7 H2Sn03 + 4N02+ H20]
CaC 2 + 2HzO -----7 Ca(OHh + C 2H 2 ]
(E)
18. Germanium (II) compounds are powerful reducing agents
15. A white coloured inorganic salt gives the following reactions: whereas lead (IV) compounds are strong oxidising agents. It
is due to:
(i) It is soluble in water and the solution has sweet taste.
The solution turns black in presence of H2S. (a) Pb is more electronegative than Ge.
(n) The . salt when heated· gives acetone and a yellow (b) the ionisation energy of Pb is less than ·thafof Ge. --_.
coloured residue which is used in paints. (c) the ionic radii of Pb2+ and Pb4+ are less than those of
Ge2+ and Ge4+.
(iii) The solution of the salt gives a white precipitate with.
(d) more pronounced inert pair effect in Pb than in Ge.
dilute HCI which is soluble in hot water.
[Hint : Inert pair effect increases in IVth group as the atomic number
The inorganic salt is: increases, i.e., the stability of divalent state increases from
(a) Ca(CH3COOh (b) Zn(CH3COOh Ge2+ to Pb 2+.]
(c) Pb (CH3COO)2 (d) Ba(CH3COOh
1. (a) 2. (b) 3. (c) 4. (d) 5. (b) 6. (a) 7. (b) 8. (c) 9. (d) U). (d) 11. (a) 12. (b)
13. (c) 14. (d) 15. (c) . 16. (a) 17~ (c) 18. (d)
I Assertion-Reason· Type Questions·

In each of the following questions two statements are given 4. (A) Carbon forms a large number of compounds.
as Assertion (A) and Reason (R). Examine the statements and (R) Carbon is found in abundance in nature.
answer the questions according to the instructions given below: S. (A) Both CO 2 and Si0 2 have same structure.
Mark (a) if both (A) and (R) are correct and (R) is the correct (R) CO2 is a gas while Si02 is a crystalline compound.
explanation of (A). 6. (A) Carborundum is used as an abrasive.
Mark (b) if both (A) and (R) are correct but (R) is not the correct (R) Its structure is similar to diamond.
explanation of (A). 7. (A) Maximum covalency of carbon is four.
Mark (c) if (A) is correct but (R) is wrong. (R) Carbon has no d-orbitals in valence shell.
Mark (d) if (A) is wrong but (R) is correct. S. (A) Lead leaves a black mark on paper.
Mark (e) if both (A) but (R) are wrong: (R) Lead is used for making lead pencils.
1. (A) Graphite is a good conductor of heat and electricity. 9. (A) SiF~- is known but SiCI~- is not.
(R) Free electrons are spread out in the structure of graphite. (R) Size of fluorine is small and its lone pair of electrons
2. (A) Carbon dioxide is a poisonous gas. interacts with d-orbitals of silicon strongly.
(R) Carbon dioxide combines with haemoglobin of blood to 10. (A) Silicones are hydrophobic in nature.
form carboxyhaemoglobin which is not capable of (R) Si-O-Si linkages are moisture sensitive.
absorbing oxygen. 11. (A) CO 2 is linear.
3. (A) + 4 oxidation state of Pb is less stable than +2 state. (R) It is not in sp hybridized state.
(R) Pb~ is not a stable compound. [E.A.M.C.E.T. (Med.)2007}
12.. (A) Pb4+ compounds are stronger oxidising agents than Sn4+ 13. (A) Graphite is soft while diamond is very hard.
compounds. (R) Graphite has three dimensional structure while diamond
. (R) The higher oxidation states for the group 14 are more has planar, [B.H.U.20081
stable for the heavier members of the group due to inert 14. (A) Silica is soluble in HE
pair effect. [1.1.1: 2008] (R) Si02 + 4HF ~ SiP4 + 2H20
SiF4 + 2HF ~ H2SiF6 [B.H.V. 20081
1. (a) 2. (e) 3. (b) 4. (c) 5. (d) 6. (b) 7. (a) 8. (c) 9. (a) 10. (c)
11. (c) 12. (c) 13. (c) 14. (a)

6. A special type of glass which c()ntains ceriuIlloxide'andll(Jl;'<rs- -
not allow the passage of ultraviolet rays. This glass is used
When a mixture of sodium carbonate and calcium carbonate is
for making lenses. The glass is called:
fused with silica at 1500°C, a liquid consisting silicates of sodium
(a) flint glass (b) Crooke's glass
and calcium is formed. When this liquid is cooled, it becomes
(c) hard glass (d) pyrex glass
viscous and eventually ceases to flow. It becomes solid and called
glass. By varying the proportions of the three basic ingredients
and by adding other substances, the properties of glass can be THOUGHT 2
altered. An approximate formula for ordinary glass may be given Gaseous fuels have become very popular these days. The
as, following are the advantages of gaseous fuels.
R20·MO·6Si0 2 (i) They have high calorific value.
where R = Na or K and M = Ca, Ba, Zn and Pb, (ii) They do not produce smoke and leave no ash after
SiOz may be replaced by Alz03' B20 3, PzOs. Coloured glasses combustion.
are obtained by adding certain metallic oxides or salts in the fused (iii) Gaseous fuels can flow through pipes and can be ignited
mass. Glass is attacked by HF and this property is used to make at the moments notice at any place. No special devices
marking on the glass, This is kno,-,;n as etching. are required for their combustion.
The glass if cooled rapidly b~comes brittle and fragile. The Coal gas is a good gaseous fuel as it contains 95% combustible
articles of glass are cooled neither very slowly nor very rapidly. gases such as hydrogen, methane, carbon monoxide, etc. It is
The articles are cooled gradually. This process is termed annealing. obtained by destructive distillation of coal at about lOOO°C, Water
1. Glass is described as a: gas which is essentially a mixture of hydrogen and carbon
(a) solid (b) liquid monoxide is prepared by passing steam over incandescent coke.
(c) super cooled liquid (d) colloidal solution The reaction is however endothermic. Producer gas which
2.' Which acid cannot be stored in glass? possesses lowest calorific value is prepared by passing air over
(a) HF (b) HCl red hot coke. It contains mainly nitrogen and carbon monoxide.
(c) flBr (d) HI Semiwater gas is a mixture of water gas and producer gas. Oil gas
[Hint: HF attacks glass, Na2Si03 + 6HF ~ Na2SiF6 + 3H20] which is used in laboratories is obtained by cracking of kerosene.
3. Ordinary glass is: It is a mixture of hydrocarbons (saturated and unsaturated) mainly
(a) sodium silicate (b) potassium silicate lower hydrocarbons. LPG (liquefied petroleum gas), which contains
(c) calcium silicate C3 and C4 hydrocarbons of the alkane and alkene series supplied
(d) a mixture of sodium and calcium silicates with silica in cylinders for domestic uses is very popular these days.
4. Annealing is the best described as: 1. Which one is the best fuel?
(a) slow and gradual cooling (a) Wood (b) Coal
(b) sudderi and rapid cooling (c) Kerosene (d) LPG
(c) cooling by water 2. Which gaseouf'; fuel has the highest calorific value?
(d) very slow cooling (a) Producer gas (b) Semiwater gas
5. A blue colour can be imparted to glass by use of: (c) Coal gas (d) Water gas
(a) Fe2~ (b) COO 3.. Which of the following contains the highest percentage of
(c) NiO (d) CuzO carbon monoxide?
(a) Coal gas (b) Water gas 2. Which of the following statements is incorrect?
(c) Producer gas (d) Natural gas (a) Boron shows only +3 oxidation state.
4. Which of the following is a cracking process? (b) In Ga + 3 oxidation state is more stable than + 1 oxidation
(a) C3~ + H2 ~ C 3Hg state.
(b) nC214 ~ (C 214)n (c) In Sn + 2 oxidation state is more stable than +4 oxidation
(c) C16H34 ~ 6CH4 + 2C214 + C 2H 2 + 4C state.
(d) 3C2H 2 ~C6~ (d) In Tl + 1 oxidation state is more stable thim +3 oxidation
5. Which gas is essential constituent of the most of fuel state.
gases? 3. The strongest reducing agent among the Jollowing is:
(a) CO (a) GeCl2 (b) SnCl2
(c) N2 (c) PbCI2 (d) TICl
4. The strongest oxidising agent among the following is:
THOUGHT 3 (a) SiOz (b) Ge02
(c) Sn02 (d) PbOz
The heavier elements of group 13, 14 15 besides their
5. Inert pair effect is not exhibited by:
group oxidation state exhibit another oxidation state which is two
(a) Pb (b) Bi
units lower than the group oxidation state. The stability of lower
(c) TI (d) B
oxidation state increases down the group.
6. Which of the following compounds do ..Jlot . undergO--..
The display of-lower oxidation state is 'due to·inert' pair effect.
disproportionation in aqueous solution ?
1. Which of the halide does not exist?
(a) TICl3 (b) GaCl
(a) l1CI (b) PbBr4
(c) InCl (d) TICl
(c) PbCl 2 (d) SnCl 2
Thought 1 1. (c) 2. (a) 3. (d) 4. (a) 5. (b) 6. (b)

Thou~ht2 1. (d) 2. (c) 3. (b) 4. (c) 5. (a)
Thought 3' 1. (b) 2. (c) 3. (a) 4. (d) 5. (d) 6. (a. d)
(;
1. Which among the following halides is coloured and why? 6. Sn2+ (aq.) may also be written as [Sn(HzO)6]2+, this ion is
CC14• SiBr4 and Sn4. acidic by hydrolysis, write a possible equation for this
[ADS. SnI4 yellow/orange solid] hydrolysis.
2. Which crystalline allotropic form of carbon has the lowest 7. Which among the following oxides oflead is strong oxidising
energy? agent? .
[ADS. Graphite-It has 30 and 1t-bond whereas in diamond there PbO, PbOz, Pb304
are 4cr-bonds. Thus, graphite has low energy.] [ADS. Pb02-It oxidises HCI to CI21
3. What are the differences in following two classes of carbides? 8. Which method is used to get semiconductor grade silicon?
Class 1. Be2C, Al4C 3 [ADS. Zone refining]
Class 2. CaC2. Al2C 6 9. What is peCUliarity in electrical property of quartz?
[Ans. Class 1. Carbides are methanides because they evolve [ADS. Quartz crystals exhibit piezoelectric effect. Compression
methane gas on hydrolysis. of the crystal in particular direction causes an electric voltage
Class 2. Carbides are called acetylides because they evolve to develop across. Such crystals are used in phonograph;
acetylene on hydrolysis.] microphones to convert sound vibrations to alternating
4. What do you understand by semiwater gas? electric current. The opposite effect is also possible; the
[Ans. Mixture of producer and water gas is called semiwater gas.] alternating current when applied to piezoelectric crystal
can make it to vibrate.]
5. Explain the structure of C 30 2 in terms of bonding in the
molecule. 10. Which of the following oxides of carbon act as a reducing
[Ans. It is carbon suboxide with following linear structure, agent and why?
O=C=C=C=O CO, CO2, C 30 2
Each carbon lies in sp hybrid state. The 1t-electrons are [Ans. CO; there is lone pair of e- at carbon to be denoted; hence
delocalized from one end to other. The delocalization does carbon monoxide acts as reducing agent.]
not alter the geometry of molecule.]
11. Classify the following silicates: unsaturated hydrocarbons (13-16%); CO 2 (upto 2%) and
(a) Beryl (b) Feldspar (c) Spodumene (d) Zircon (N 2 upto 5%).
[ADs. (a) Cyclic, (b) Three dimensional sheet, (c) Chain silicate, (viii) Crooke's glass is used in UV filter glasses. It contains Ce02'
(d) Orthosilicate] (ix) Sometimes CaF2 is added to obtain opal glass.]
12. Explain why the silicate olivine (FeMghSi04 does'not follow 14. Give the names of ions that produce deep blue, light blue,
the law of constant composition. ruby red, green colour and yellow-brown colour in the glass.
[ADs. Any ratio of iron to magnesium may be found. It may be [ADs. Colour Metal ions
treated as solution of Fe2Si04 in Mg 2Si04 and vice-versa.] Deep blue Co 2+
13. What are the following compounds? Give their uses: Light blue Fe 2+
(i) Vitrosil (ii) Carbogen Ruby red Cu +ICu 2+
(iii) Kieselguhr (iv) Chrome yellow and Green colour Mixture of Fe 2+ and Fe 3+ ions
chrome red Yellow-brown Fe 3+]
(v) Butter of tin (vi) Litharge and Massicot 15. Give the molecular formula of talc and muscovite. Comment
(vii) Carburated water gas (viii) Crooke's glass on their structure and use.
(ix.) Opal glass [ADs. Talc: Mg 3 Si40 IO (OHh. It is one of the very soft material.
[ADs. It is used in talcum powder.
(i) QuartZ glass used in the manufacture of optical instruments Muscovite: KAl2 Si3AIO IO(OHh; it is a mica. It has layer
is called vitrosil. type' structure involving· weak ·vander·Waals'-force.]-.:-..- _....
(ii) Carbogen is a mixture of 95% O2 and 5% CO 2, It is used for 16. Complete the following road map.
artificial respiration for the victims of carbon monoxide
poisoning.
H 2C20 4 Cone. :2 4)(A)
S0
+ (B) + (C)
(iii) Kieselguhr-It is a mass of hydrated silica (Si0 2) formed Gas Gas Liquid
from skeletons of minute plants known as diatoms. It is highly Gas (A) bums with blue flame and gas (B) turns lime water
porous and absorbent material used in the manufacture of milky. Gas (A) on oxidation gives gas (B). Liquid (C) produces
dynamite. blue colour when comes in contact with anhydrous copper
(iv) Chrome yellow (PbCr04) is used as yellow pigment chrome sulphate.
red (PbCr04'PbO) is used as red pigment. (A) + Cl 2 ----7 (D) (E)
(v) SnCI 4'5H 20 is called butter of tin and is used as a mordant
in dyeing.
(vi) Red form of PbO is called litharge and yellow form of PbO
(B) NH3
L1
t
is called massicot. What are the compounds (A) to (E)?
(vii) Carburated water gas is a mixture of carbon monoxide [Ans. (A) CO; (B) CO 2; (C) H20; (D) COCI 2; (E) NH2CONH2]
(23-28%); H2 (34-38%), saturated hydrocarbons (17-21 %),
:1':'::'~,
, I - -,...~. ",,,,, " 'f \ ..: ' ) ' - . . ' - ~
\
:.,':; ~ ;" 1·' /'.>,i( \ .:: 'fIJf):) r.)II~.. .l·'i·1fJ[t·'" <
.J
;.:J
• .. • ' • • • • -" •••• l ,'" ." J , )""'~,:F'
The answer to each of Ihe following questions is a single 5. How many methanides are presenfin the following carbides?
digit integer, ranging from 0 to 9. SiC, CaCZ, Be2C, Al2C6, A4C3, B4C
1. The bond order of carbon monoxide is : 6. Carbogen is a mixture of O2 and CO 2, It is used for artificial
2. What is the value of x in the following silicate mineral? respiration. What is the percentage of CO 2 in this mixture?
Be3Al2SixOl8 7. In the giant ,structure of silica, each silicon atom is
3. The ratio of copper and tin in bell metal alloy is : surrounded by how many oxygen atoms?
4. Pb30 4 is regarded as a compound oxide of PbO and Pb02.
How many parts of PbO are present in it?
1. (3) KK( cr2s)2 (cr 2s)2 (1t2 Px)2 (1t2 p y )2 (cr2 pz )2 4. (2) 2 parts PbO and 1 part Pb0 2.
10-4 5. (2) Be2C and Al4C3 are methanides.
Bond order = -- =3
2 6. (5) 95% O2 and 5% CO 2,
2. (6)
7. (4) Each silicon atom, is surrounded by four oxygen atoms
3. (4) Cu 80% Sn 20% ratio = 80/20 = 4 tetrahedrally.
10
Elements of Group VA or 15
(Elements of Nitrogen and
Phosphorus Family, ns2np3)
--c-,----,--...........
to.1 POSITION IN PERIODIC TABLE

~
IVA VA VIA VA group or 15th group of the extended form of the
Period 14 15 16 periodic table consists of six elements-nitrogen (N),
phosphorus (P), arsenic (As), antimony (Sb), bismuth
Contents: 2 C N 0
(Bi) and ununpentium (Uup)*. This group of six elements
10.1 Position in Periodic Table (6) (7) (8)
constitutes a family. These elements are collectively
10.2 Abnonnal Behaviour of Nitrogen 3 Si P S
known as pnictogens. These are p-block elements as
10.3 Nitrogen (N2) (14) (IS) (16)
the last differentiating electron is accommodated on np
10.4 Important Compounds of Nitrogen 4 Ge As Se shell. These elements have five electrons in the valency
10.5 Nitrates (32) (33) (34) shell. The elements of. the group possess the same
10.6 Phosphorus
5 Sn electronic configuration and show l'imilarities as well as
Sb Te
10.7 Compounds of Phosphorus (50) (51) (52) gradation in their properties with rise of atomic number
10.8 Arsenious Oxide or Arsenic Trioxide from nitrogen to ununpentium. Thus, their: inclusion in
6 Pb Bi Po
10.9 Fertilizers the same group is justified on the basis of electronic
(82) (83) (84)
configuration and physical and chemical properties which
7 Uuq Uup Uuh
are given below:
(114) (lIS) (116)
1. Electronic configuration: The distribution of electrons in various energy shells of the atoms of these elements is
given below:
Element At. No. Electronic configuration Inert gas core
N 7 2,5 ll, 2i [He) 2i 2p3

2
P 15 2,8,5 Ii, 2i 2/, 3s 3i [Ne) 3s2 3p3
As i 33 2, 8, 18, 5 Ii, 2i 2p6, 3s2 3p6 3d lO , 4i 4p 3 [Ar] 3d lO , 4i 4p3
2 lO lO
Sb 51 2, 8, 18, 18, 5 Ii, 2s 2l, 3i 3/ 3d , 4i 4/ 4d1O, 5i 5i [Kr] 4d , 5i 5i
lO 2
Bi 83 2, 8, 18, 32, 18, 5 li, 2s2 2i, 3i 3p6 3d , 4i 4p6 4d1O 4/,4, 5i 5l 5d lO
, 6s 6i [Xe) 4f14, 5d lO , 6s2 6i
Uup i 115 2, 8, 18, 32, 32, 18, 5 Ii, 2i 2l, 3i 3p6 3d lO , 4i· 4p6 4d lO 4f'4, 5i 5l 5d lO 5/ 4, [Rn) 5/ 4, 6d lO , 7i 7p3
I ~. . :~6~26p6 6d lO, 7s2 7p3

"''',.:';
*Ununpentium (115) has recently beendiseovered. It is a synthetic element. It is radioactive and is unstable in nature. Very little is known about
its properties.
The configurations show that these elements have same The considerable increase in covalent radius from N to P can
number of electrons in the valency shell, i.e., 5 electrons in the be attributed to strong shielding effect of s- and p- electrons
valency shell, two of which are in s-orbital and remaining three present in the inner shells. Small increase in covalent radiifrom
in three p-orbitals. Thus, they have ni nl configuration, i.e., As to Bi is, however, due to poor shielding effect of d- and/
s-orbital is paired and three p-orbitals are unpaired. or f-electrons present in the inner shells on valency electrons.
ns np This brings increase in effective nuclear charge which reduces
lliJlililil or the effect of the addition of a new energy shell to some extent.
(d) Ionisation energy or Ionisation enthalpy: The
The penultimate shell, in nitrogen contains 2 electrons
values of first ionisation ener~y are higher than the corresponding
(saturated), in phosphorus contains 8 electrons (saturated), in .
group 14 elements. However, the values gradually decrease on
arsenic contains 18 electrons (saturated) while in antimony
going down the group from nitrogen to bismuth.
and bismuth contain 18 electrons (unsaturated) each. This
On account of increased nuclear charge, reduced atomic
shows why riitrogen differs from phosphorus in some respects
radii and stable half filled configurations, it is more diffiCUlt
and these two differ from the remaining elements of this group.
to remove an electron as it is more tightly held by the nucleus.
In accordance with the Hund's rule, electronic configurations
Subsequently, the values of ionisation energy of these elements
involving fully filled or exactly half filled orbitals are the most
are higher than the elements of group 14. The decrease in the
stable, the elements of group VA, having exactly half filled values of ionisation energy from nitrogen to bismuth is due to
orbitals, are also fairly stable and not so reactive. Nitrogen gradual increase in atomic size.
behaves as a noble element under ordinary conditions.
The ionisation energy of nitrogen is very high; this is due to
2. Similarities and gradation in physical properties :
its small size. The difference·between Nand P is comparatively
(a) Metallic and non-metallic character: Metallic high but the difference afterwards between two consecutive
nature increases as the atomic number increases. N and P are
members is small. This is due to less shielding effect of
purely non-metals while Sb and Bi are metals. Arsenic behaves
d-electrons in As and Sb, d and J-electrons in Bi.
as a metalloid. Successive ionisation energies of these elements increase as
N P As. Sb Bi expected, i.e., E1 < E2 < E3.
'---v--" Metalloid '------v--'
Non-metals Metals Element N P As Sb Bi
Ionisation energy EI 1402 1012 947 834 703
Metallic nature increases
(kJ mol-I) E2 2856 1903 1798 1595 1610
N and P combine with electropositive elements and form E3 4577 2910 2736 2443 2466
nitrides and phosphides, respectively. Nitrides are more stable
(e) Electronegativity: Electronegativity decreases gra-'
than phosphides. Bi and Sb form alloys with other metals.
dually on descending the group from N to Bi.
Thus, Nand P are non-metals while Sb and Bi are metals.
Element N P As Sb Bi
. (b) Physical state: There is a gradual change in physical
Electronegativity 3.0 2.1 2.0 1.9 1.9
state of these elements under ordinary conditions. Nitrogen,
Nitrogen is most elect:rcinegative element, i.e., typical non-
the first element, is a gas while phosphorus, the second member,
metal.
though a solid, can pass readily into vapour state. It is soft
(f) Density: It increases gradually on descending the group.
waxy solid. The remaining elements are solids; These are hard
Element N P As Sb Bi
and possess metallic lustre.
Density (glmL) 0;809 1.823 5.73 6.62 9.78
(c) Atomic radii: The atomic radii of the element& of
group 15 are smaller as compared to the elements of group 14 (g) Allotropy: All the elements except bismuth show
in the corresponding periods. allotropy. Nitrogen exists .in two solid. allotropic forms,
a-nitrogen with cubic crystalline structure and ~-nitrogen with
N < C p < Si As < Ge hexagonal crystalline structure. The transition temperature is
·(70 pm) (77 pm) (1l0 pm) (118 pm) (121 pm) (122 pm) -238.5°C. Phosphorus exists in number of allotropic forms
This is due to increased effective nuclear charge which such as white, red, scarlet, a-black, ~-black and violet. Arsenic
brings contraction in size. is known in three allotropic forms, i.e., grey, yellow and black.
Atomic radii increase on going down the group. Antimony also exists In three forms, i.e., yellow, black and
explosive. .
Element N P As Sb . Bi
(h) Catenation: N, P and As exhibit the property of
Atomic radii (pm) 70 110 121 141 148
catenation but this property is much less 'than IVA elements.
The increase is due to addition of a new energy shell in each No nitrogen compound containing nitrogen chain with more
succeeding element. than two atoms is stable although compounds having a chain
There is considerable increase in covalent radius from N to of eight nitrogen atoms have been prepared. The bond energies
P but from As to Bi only a small increase is observed. of C-C, N-N, P-P and As-As linkages are 85.0, 48.0,
Elements of Group VA or 15 (Elements of Nitrogen and Phosphorus Family) 463
39.0 and 35.0 kcaUmol. Thus, the tendency of catenation of these elements are observed with halogens and sulphur. The
decreases from N to P and from P to As. P and As can form stability of +3 oxidation state increases and that of +5 oxidation
a chain of only two atoms. state decreases on moving down from N to Bi.
(i) Atomicity: Nitrogen is diatomic gaseous molecule at Nitrogen and phosphorus generally exhibit -3 oxidation state
ordinary temperature. The existence of nitrogen as diatomic due to high electronegativity and small size: Nitrogen forms
molecule is due to its ability to form multiple bonds. The nitride ion (N3-) with highly electropositive elements. Phosphorus
molecule has one sigma and two 1t-bonds. also forms phosphide ion (P3-) to some extent. The tendency
: N :: N : or : N= N : (N 2) to show -3 oxidation state decreases from nitrogen to bismuth.
The triple bond in nitmgen molecule is very stable as the Note: Nitrogen besides -3, +3 and +5 oxidation states, exhibits a large
dissociation energy is very high (225 kcallmol). It is, number of oxidation states from -3 to +5; -3 in NH3 and nitrides
(Li3N, Ca3NZ, AIN), -2 in NH2NHz, -I in NH 20H, 0 in N2, +1
therefore, inert under ordinary conditions.
in N20, +2 in NO, +3 in NZ0 3 and HNO z, +4 in N02 and +5 in
X HN0 3 and NzO s.
Disproportionation: All the oxidation states of nitrogen from
+ 1 to +4 show disproportionation in acidic medium.
For example,
+3 +5 +z
3HN02 ~ HN03 + 2NO + H20
Phosphorus exhibits disproportionation in all the intermecli-are-
oxidation states from -3 to +5 in acidic and basic medium'l.
X~------+-----~X For example,
+1 +5-3
Heat
2H3P02 -----? H3P04 + PH3
X +3 +5-3
Fig. 10.1 X = P, As or Sb 4H3P03 ~ 3H3P04 + PH3
This tendency decreases from As to Bi due to inert pair
Phosphorus, arsenic and antimony all exist as discrete effect as stability of +3 state increases from As to Bi.
tetratomic tetrahedral molecules, viz., P4, As4 and Sb4 (Fig. (k) Valency and nature of bonding: There are five
10.1) as these> are not capable of forming multiple bonds due electrons present in the valence shell of these elements. To
to repulsion between non-bonded electrons of the inner core. achieve stable configuration, they require three more electrons
3
The angle between X-X-X is 60°. The pTCr-p1t bonding in which is not easy to accept as to formtrinegative ion (M -)
phosphorus, arsenic, etc., is therefore not possible. Elements due to energy considerations. Such an ion is formed by nitrogen
of this group form giant lattice in which bonding changes from which is smallest and most electronegative element of the
covalent to metallic, e.g., violet and red phosphorus has layer family when it combines with highly electropositive metals.
. structure involving covalent bonding. Bismuth. on the other This tendency is much less in phosphorus. These elements
hand involves purely metallic bonding. Metallic layer structure easily attain stable configuration by sharing three p-electrons,
of bismuth is given below: i.e., by forming three covalent bonds. Except nitrogen, all
other elements have d-orbitals in the valence shell. As a result,
one of the two ns-electrons may be promoted to nd-orbitals to
have five unpaired orbitals in the valence shell. These can be
used to form five covalent bonds. This is not possible in
nitrogen as it has no d-orbitals (nitrogen never shows penta-
valency). However, nitrogen can show a maximum covalency
of> 4 when it donates thens-electron pair to Lewis acids.
Sb and Bi can lose three electrons forming M3+ ions but
ionisation energy is too high for the other elements. Both SbF3
and BiF3' exist as ionic solids. The M3+ ions are not very
stable in solution. They can exist in fairly strong acid solution
but are rapidly hydrolysed in water to give the antimony oxide
(j) Oxidation states: The elements of this group have
ion or bismuth oxide ion, SbO+ and BiO+. The change is
five electrons in their outer shell. They exhibit a maximum
reversed by adding 5M HCl.
oxidation state of +5 towards oxygen by using all the five H20
electrons of outer shell. The tendency of the pair of ns electrons Bi3+ ~ [Biot + 2H+
to remain inert (the inert pair effect) increases with increase of He1 Bismuthyl ion
atomic number. Thus, only the p-electrons are used in bonding, BiC1 3 + H20 ---? BiOCI + 2HCl
Sb + + H 20 ~
3
i.e., +3 oxidation state is observed. +3 and +5 oxidation states [SbOt + 2W
Antimonyl ion
Multiple bonding: Nitrogen forms pTt - pTt multiple bonds Greater is the electro negativity more is the acidic character
easily with itself and also with carbon and oxygen. Nitrogen of its oxide. Moreover, among the oxides of same element
exists as triply bonded diatomic gaseous molecule (N=N) at higher oxidation state is responsible for greater acidic character.
ordinary temperature. The bond strength is very high (941.4 Besides these three types of oxides, nitrogen fonns two
kJ mol-I) and this is responsible for its inertness at ordinary more oxides N20and NO (these are neutral) and bismuth
conditions. Other members show reluctance to form multiple forms bismuth monoxide (BiO).
bonds. However, phosphorus can form pTt-dTt type multiple (i) Acidic nature of each type decreases from nitrogen
bonds, e.g., ° PX3, RN = PX3. to bismuth.
Maximum covalency: The maximum covalency of N20 3 and P203 are acidic,As 20 3 and Sb203 are amphoteric
nitrogen is four as it does not possess d-orbitals in the valence while Bi20 3 is more basic and less acidic.
shell, i.e., it cannot extend its valency beyond four [NHt,
N20 3 + H20 .~ 2HN02 (Nitrous acid) -t acidic
R4N+]. On the other hand, other members have empty
d-orbitals and can utilise these orbitals to show covalency of P20 3 + 3H20 ~ 2H3P03 (Phosphorus acid) -t acidic
five or six, e.g., PCIs, [SbF6r. . . As 20 3 + 6HCI ~ 2AsCl3 + 3H20 -t basic }
(I) Thermal and electrical conductivity: Both these amphoteric
.. AS203 + 6NaOH ~ 2Na3As03 + 3H20-t acidic
properties increase on moving down the group because delo-
calization of electrons increases from nitrogen to bismuth. Sb20 3 + 6HCI ~ 2SbCl3 + 3H20 -t baSic}
.. N: 'p c " X s ''''''''Sb;'''131 .
c
Sbi0:3 + 6NaOH 2Na3Sb03 + 31120-t acidic ampimteric
Poor conductor Semiconductor Good conductor
Bi 20 3 + 6HCI 2BiCl3 + 3H20 -t basic
3. Occurrence: Nitrogen is found in free as well as in
combined state. Nitrogen forms 75% by mass and 78% by Bi20 3 shows feeble acidic character also as it slightly
volume of the atmosphere. In the combined state, it occurs as dissolves in concentrated NaOH solution.
nitrates, proteins, amino acids, etc. Phosphorus does not occur Bi20 3 + 6NaOH ~ 2Na3Bi03 + 3H20
free in nature. Phosphorus is the eleventh most abundant element Sodium bisrnuthite
in the earth's crust. Phosphorus is essential for life of both plants The acidic nature of. pentoxides decreases from N20 S to
and animals. About 60% of bones and teeth are Ca3(P04h or Bi20s·N20 S, P20 S and As20 S are soluble in water and form
[3{Ca3(P04h}.CaF21 and an average person has 3.5 kg of acids.
calcium phosphate in his body. Phosphorus is present, in DNA, N20 S + H20 ~ 2HN03 (Nitric acid)
RNA, ATP, ADP, etc. It is also found as phosphates in nature. As, P20S + 3H20 ~ 2H3P04 (Orthophesphoric acid)
Sb and Bi are not abundant. They occur as sulphides or oxides.
4. Chemical properties: Elements of this group differ As20 S + 3H20 ~ 2H3As04 (Arsenic acid)
from one another appreciably in their chemical activity. Nitrogen Sb20 S and Bi20 S. are insolubl~ in water but dissolve in
is chemically inert under ordinary conditions. Due to this reason, alkalies.
it is found free in atmosphere. The chemical inertness is due Sb20 S + 6NaOH ~ 2Na3Sb04 + 3H 20
to high stability of the triple bond between the two nitrogen Sodium antimonate
atoms. The dissociation energy of the bond is high, i.e., 225 Bi20 S + 6NaOH ~ 2Na3Bi04 + 3H20
kcal per mole. It is, therefore, at high temperature only when Sodium bismuthate
nitrogen can react with other elements. Acidic nature of M 20 4 oxides also decreases from N20 4 to
Phosphorus especially white form is extremely reactive. It Bi20 4. The acidic nature of these oxides is less than X20 S type
readily burns in oxygen to form oxides. The strained structure and more than X 20 3 type. The decrease in acidic nature of the
of P4 is responsible for high chemical activity. The heavier oxides from nitrogen to bismuth is due to decrease in non-
elements are less reactive as they burn only when heated in air metallic character and increase in metallic character from N to
or oxygen to form oxides. Bi.
(a) Oxides: All these elements form oxides of the type (ii) In the oxides of a particular element, the acidic nature
X 20 3 , X 20 4 and X20S. increases as the percentage of oxygen increases or as the
Element Nitrogen Phosphorus Arsenic Antimony Bismuth oxidation state increases. For example, N20 S is most acidic
Type of '"
0
while N20 3 is less acidic, similarly P20 s is more acidic than
'"
oxides P20 3 and P20 4.
X203
X Z04
X 2 0s
N203
N20 4
N20 5
P203
P204
P 20 S
AS203
AS204
AS20S
Acidic nature decreases

Sb 20 3
Sb20 4
Sb 20 S
Bi 20 3
Bi204
Bi20S
) II '13
<C
N2 0 3 + H 2 0 2HN02 .
N20 4 + H20 ~ HN02 + HN03
N20 S + H20 ~ 2HN0 3
HN03 is stronger than HN0 2.
Elements of Group VA or 15 (Elements oj Nitrogen and Phosphorus Family) 465
P20 3 + 3H:20 ~ 2H3P03 (ii) All the hydrides are colourless gases. Their smell becomes
P20 4 + 3H20 ~ H3P04 + H3P03 more and more disagreeable as atomic number increases from
N to Bi.
P20S + 3H20 ~ 2H3P04
(iii) The poisonous nature increases from NH3 to BiH3;
H3P04 is stronger than H3P03' (iv) NH3 is highly soluble in water but other hydrides are
(iii) Stability'1:>f oxides of higher oxidation states decreases less soluble.
with increasing atomic number. (v) The basic character decreases from NH3 to BiH3. The
Thermal stability decreases in each series from N to Bi·N20 3 basic nature is due to the presence of lone pair of electrons 'on
is most stable oxide. It is more stable than other oxides. N20 S the central atom. NH3 is the strongest electron pair donor due
is less stable. However, P20S is thermally stable, but As20 S to its small size' as the electron density of the electron pair is
aniSb20 S are less stable. Bi20 s is least stable. Except P20 S, concentrated over a small region. As the size increases the
all the pentoxides show oxidising properties. N20 S is the electron density gets diffused over a large region and hence the
strongest oxidising agent. ability to donate the electron pair (hasic nature) decreases.
Nitrogen forms two more oxides, nitrous oxide (N 20) and NH3 and PH3 form NHt and PH! ion~ with protons. NHt is
nitric oxide (NO). Both are' neutral in nature. Structurally, the more stable than PH! ion. PHj is less basic than NH3 while
oxides of nitrogen are different from the oxides of the rest of AsH3, SbH3 and BiH3 are neutral. NH3 is highly soluble in
the elements of this' group. This is due to the fact that only . water whilePH3 is less soluble.
nitrogen is able to form pTC-pTC multiple bonds which are present NH3 +'H20'~ NH40H~~7PH3'+ .HiO ···.··7)· P~OH~
in its oxides. The rest of the elements' do not form multiple Weak base Very weak base
bonds and prefer to form cage structures for their oxides.
(vi) Thermal stability decreases gradually'from NH3 to BiH3.
(b) Oxyacids: All the elements of this group form
The decomposition temperatures decrease from NH3 to ~iH3.
oxyacids. Nitrogen forms a number of oxyacids but two
common oxyacids are-nitrous acid (HN02) and nitric acid NH3 PH3 AsH3' SbH3 . BiH3
l3000e 440 0 e 280 0 e 1S0oe Room temp.
(HN03). Nitric acid is a stable acid while HN02 is unstable.
Phosphorus forms a large number of oxyacids. The important The size of the central atom increases from N to Bi,therefore,
oxyacids are: the tendency to form a stable covalent bond with small hydrogen
. H3P02 H3 P03 H 4P20 4 atom decreases. As the bond length inj::reases, the .strength
Hypophosphorus Phosphorus Hypophosphoric decreases and therefore, thermal stability decreases. .
acid acid acid (vii) The reducing nature increases. This shows that bond
H3P0 4 HP0 3 H4P 20 7 strength M-H decreases as e1ectronegativhy of M decreases.
Orthophosphoric Metaphosphoric Pyrophosphoric. NH3 is a weak reducing agent while AsH 3, SbH3 and BiH3
acid acid acid are powerful reducing agents.
Arsenic forms two oxyacids, H3As03 (arsenious acid) and (viii) The shape of these hydrides is pyramidal. The
H3As04 (arsenic acid). Antimony forms one oxyacid H 3Sb0 3 formation is' due to sl hybridization of centra1..atom, i.e.,
which exists in solution. Bismuth also forms one stable oxyacid forming a tetrahedral configuration. However, on one of
HBi03 , meta-bismuthic acid. tetrahedral positions, a lone pair of electrons is present. The
The strength and stability of oxyacids having the element in bond angle (HMH) in various hydrides is never equal to ideal.
the same oxidation state decreases gradually with decrease in tetrahedral angle of 109°28'. The actual bond angles are:
electronegativity of central atom.
NH3 PH3 AsH3 SbH3
HN03 H3P04 H3As04 . H3Sb04
Strong Weak Very weak Weakest
107.5" 93.so 91S 91.3°
(c) Hydrides: All the elements of this group form hydrides The bond angle in ammonia is less than 109°28' due .to
of the type MH3 . repulsion between lone pair present on nitrogen atom and
NH3 PH3 AsH3 SbH3 BiH3 bonded pairs of electrons. The decreased bond angle in other
Ammonia Phosphine Arsine Stibine Bismuthine hydrides can be explained by the fact that the s/!
hybridization
becomes less and less distinct with increasing size of the
. (i) All the hydrides are formed by the action of water or
central atom, i.e., pure p-orbitals are utilised in M-H bonding.
dilute acids on binary metallic compounds such as Mg3N2,
Bond lengths and bond dissociation energies of the hydrides
Ca3P2, Zn3As2, Mg3Sb2 and Mg3Bi2' of group 15 .elements are listed below: .
The hydrides are also obtained by reduction of trichlorides
of these elements (except that of bismuth) with Znlacid or Hydride NH3 PH3 AsH3 SbH3
M-H bond length (pm) 101.7 141.9 151.9 170.7
LiAlH4· M-H dissociation energy 391 322 297 255
4MCl 3 + 3LiAI~ ----7 4MH3 + 3LiCI + 3AlCl3 (kJ mol-I)
(M == N, P, As, Sb)
(ix) Hydrogen bonding: Hydrogen bonding is present in Note : The NCl 3 is hydrolysed to a base (NH 3) while PCl 3 is
NH3 as the electronegativity difference between nitrogen and hydrolysed to an acid (H 3P0 3). It is due to the fact that NCl3
is an electron pair donor while PCl 3 is an acceptor as P has vacant
hydrogen is high and the N-H bond' shows polarity. The
3d-orbitals.
electronegativity of rest of the elements is nearly equal to
hydrogen, hence M-H bond is purely covalent and no
:6 ---
t-
hydrogen bonding is present in their hydrides. CI-N: ----+ H
(x) The boiling points of these hydrides vary as follows: I
CI
Hydride NH3 PH 3 AsH3 SbH3 BiH3
Boiling point ("C)' . -33 -89 "':63 -9 17
In NH3, molecules are associated by hydrogen bonding and
thusits boi';.lg is comparatively high in comparison to PH3 and
AsH} where no hydrogen bonding is present. In moving from
(ii) Pentahalides: Phosphorus pentachloride is' the most
PH3to BiR3, boiling points increase due to increase in the magni-
well known of the pentahalides. Bismuth does not form
tude of van der Waals' forces due to increase in molecular size.
pentahalides because of inert pair effect. The pentahalides have
(d) Halides.: The main halides formed by the elements
a trigonal bipyramid shape (sl d-hybridization) in gaseous and
of this group are listed below:
liquid states which is not very stable structure, hence these
Element TribaIides Pentabalides pentahalides decompose into stable lower halides.
Nitrogen" NF3,NCI3, "NBfj,' NI3 "
PCIs ~ PCl 3 + Cl2
Phosphorus PF3, PCI 3, PBr3, PI 3 pcls, PFs, PBrs
These are also hydrolysed by water.
Arsenic AsF3, AsCI3, AsBr3, AsI3 AsFs
PCls'+ H 20 ~ POCl3 + 2HCI
Antimony SbF3, SbCI), SbBr), SbI3 SbFs , SbCIs
Bismuth BiF3, BiCI 3, BiBr3, BiI3 BiF5 POCI3 + 3H20 ~ H 3P0 4 + 3HCI
[PCIs acts as an effective chlorinating agent.]
All form trihalides. One or more peritahalides are formed by
X-ray studies have shown .that the solid J.>CIs is an ionic
the elements except nitrogen. Nitrogen does not form penta-
compound composed of [PC4t [PCI6f. Solid PBrs exists as
halides due to absence of d-orbitals.
[PBr4tBr-.
(i) Trihalides: The elements directly combine with halo-
All the pentahalides act as Lewis acid!"; due to the presence
gens and form trihalides, MX3. All the trihalides are stable
of d-o.rbitals.
e~cept NCI3, NBr3 and N13. The unstable nature of NCI3,
MXs + X- ~ [MX6f
NBr3 and NI3 is due to low polarity of N-X bond and a large
difference in the size of nitrogen and halogen atoms. The hybridization of the central atom (M) changes from .
The trihalides have .a tetrahedral structure involving sp 3d to sp 3d 2 .
sp3 -hybridization of the centr~l atom. They have pyramidal (e) Snlphides: With the exception of nitrogen, all other
shape. A lone pair of electrons is present on the central atom. elements of this group form sulphides. The sulphides of arsenic
Due to the presence of a lone pair of electrons on the central .and antimony are soluble in yellow ammonium sulphide or
atom, they act as Lewis bases. In the case of nitrogen halides, ammonium sulphide and form thio-compounds.
the tendency to act as Lewis base decreases from NI3 to NF3. AS 2S 3 + 3(NH4hS ~ 2(NH 4 )3AsS3
Ammonium thio-arsenite
NI3 > NBr3 > NCl 3 > NF3
As 2S S + 3(N~)zS ~ 2(NH4 hAsS 4
This is due to increased electronegativity from I to F. Ammonium thio-arsenate
Also the tendency to act as Lewis base decreases from N Antimony sulphides form similar compounds. The sulphides
to Bi for a given halide .. are also soluble in caustic alkali.
The .trihalides of phosphorus and antimony especially
AS2S3 + 6NaOH Na3AsS3 + Na3As03 + 3H20
fluorides and chlorides act as Lewis acids also by using the Sodium thio- Sodium
vacant d~orbitals. arsenite arsenite
Except NF3 and PF3, all the trihalides are hydrolysed by The stability of sulphides increases with increase in atomic
water. number of the element.
N03 + 3H20 ~ NH3 + 3HCIO
PCl3 + 3H 20 ~ H 3P03 + 3HCI ABNORMAL EiEHAVIOUR OF
AsCl3 + 3H20 ~ H3As03 + 3HCI NITROGEN
SbCl 3 + H 20 SbOO + 2HCI Nitrogen differs considerably from the rest of the family
BiCl3 + H20 ~ BiOCI + 2HCI members. The differences or abnormal properties are mainly
due to the following four factors:
(a) Small size of nitrogen atom.
1 NITROGEN (N2)
(b) High value of electronegativity.
Scheele, in 1772, showed that air is a'mixture of two gases :
(c) Absence of d-orbitals in the valency shell.
fire air (oxygen) which supports combustion and respiration
(d) Tendency to form multiple bonds.
andfoul air (nitrogen) which does not take part in combustion.
The important points in which nitrogen differs from other D. Rutherford named foul air as mephitic air (killer of life).
members of VA group are listed below: Later on the element was found to be present in nitre and thus,
(i) Nitrogen is a gas while other members are solids. the name nitrogen was proposed.
(ii) Nitrogen molecule is diatomic (N N) while other Occurrence: Nitrogen exists in its elemental form as
elements form tetratomic molecules such as P 4, AS4 and Sb4. diatomic molecules (N2), it is therefore, called as dinitrogen.
(iii) The catenation property is more pronounced in nitrogen. Nitrogen is widely distributed in nature both in free as well as
Chains containing upto eight nitrogen atoms are known but in in the combined state. Air is the most abundant source of free
the case of other elements, catenation is limited to two atoms nitrogen. It forms 75% by mass and 78% by volume of the air.·
only. In combined state, it is found as nitrates such as Chile saltpetre
(iv) Nitrogen forms five oxides. N 20 (nitrous oxide), NO (NaN0 3), Indian saltpetre (KN0 3) and ammonium compounds.
(nitric oxide), N 20 3 (nitrogen trioxide), N02 (nitrogen dioxide) It is an essential constituent of all living things (animals and
and N20s (nitrogen pentoxide). Others can form at the most vegetables both) where it is found in the form of proteins,
amino acids· and nucleic acids:· ItS existence in ·atmospnere is···
three types of oxides, X203, X204 and X20S.
very important because it acts as inert diluent for the highly
N 20 3 and N 20 S are monomeric in nature but oxides of
reactive gas, Le., oxygen.'·Without nitrogen, every spark in our
other elements are dimeric.
atmosphere would cause a massive fire.
(v) Hydride of nitrogen (NH3) is stable while the hydrides Preparation: Nitrogen can be obtained from the following
of other elements are not stable. Hydrogen bonding is present two sources:
in ammonia (NH 3) but not present in other hydrides. (i) Nitrogen compounds and (ii) Air.
(vi) Except NF3, the halides of nitrogen (NCI 3, NBr3 and (i) From nitrogen compounds: (a) Nitrogen in the
NI3) are unstable and explosive. The halides of other elements laboratory can be obtained by heating ammonium nitrite or
are stable. Unlike P, As and Sb, nitrogen does not form ammonium dichromate. Ammonium nitrite is not a stable
pentahalides. compound and thus it is first formed as an intermediate product
(vii) Due to small size and high electronegativity, nitrogen by heating an ammonium salt with sodium nitrite.
can form trinegative ion N 3-. This tendency is less; in P but NH 4Cl + NaN02 ----? ~N02 + NaCI
absent in other elements. Ammonium nitrite
(viii) As nitrogen does not have d-orbitals in its valency NH~02 ----? N2 + 2H20
shell, its maximum covalency is 3 while in the case of other
(NH4)zCr207 N2 + Cr203 + 4H20
----?
elements, the maximum covalency is 5.
Nitrogen is collected by downward displacement of water.
(ix) Nitrogen is chemically inert under ordinary atmospheric
(b) Pure nitrogen can be obtained by passing the ammonia
conditions. This is due to high dissociation energy of nitrogen
vapours over heated CuO.
molecule. The other elements are quite reactive as they have
single bonds in their molecules; i.e., dissociation energies are 2NH3 + 3CuO N2 + 3Cu + 3H20
----?
low. NH3 can also be oxidised to nitrogen by C1 2, Br2, a
(x) Nitrogen shows a large number of oxidation states from hypochlorite, a hypobromite or bleaching powder. [See for
-3 to +5 such as + 1 in N 20, +2 in NO, +3 in N 20 3, +4 in N02, reactions section 10.4.]
+5 in N 20 S, -1 in NH20H and -3 in NH3 . Other elements (c) It can also be obtained by the action of nitrous acid (or
show.a limited number of oxidation states from -3 to +5. NaN0 2 and dil. H2S04) on urea.
(xi) Nitrogen does not fonn sulphide while all other elements NH2CONH2 + 2HN02 ----? 2N2 + CO2 + 3H20
form sulphides. Urea
(xii) On account of high value of electronegativity, nitrogen (d) Pure nitrogen is obtained in small amount by heating
behaves as a typical non-metal while As, Sb are metalloids and sodium or barium azides in vacuum.
Bi is a metal.
Ba(N 3}z ----? 3N2 + Ba
Nitrogen (N=N), carboft monoxide C f-O and cyanide ion Barium azide
(C Nf are isoelectronicin nature. Nitrogen is inert while
other species are active. The bond between nitrogen atoms is
(ii) From air: (a) Air is the major source of nitrogen.
non-polar. Commercially nitrogen is obtained by liquefaction of air. The
resultant liquid is fractionally distilled in Claude's apparatus.
Air is freed from dust particles and compressed to 60 2B + N2 ~2BN (Boron nitride)
atmospheres. It is cooled. The compressed air is freed from 3Si + 2N2 ~ Si3N4 (Silicon nitride)
C02 by passing through a tower packed with sodalime and (d) Nitrogen combines with calcium carbide to form calcium
then dried by passing through alumina driers. It is then passed cyanamide at 1000°C.
through pipes which are surrounded by cold nitrogen or cold CaC2 + N2 ~ CaCN2 + C
oxygen. The cold co~pressed air is allowed to do work in The mixture of calcium cyanamide and carbon is techni-
Claude's expansion engine when it is partially liquefied. The cally known as nitrolim.
partially liquefied air is passed through a double rectification (e) When nitrogen is passed over heated mixture of alumina
column when more of air is liquefied. Liquefied air is further and carbon, aluminium nitride is formed.
fractionally distilled in Claude's apparatus. Finally, about 90%
1273 K
pure nitrogen escapes through the exit at the top of the apparatus. Al 20 3 + 3C + N2 --~) 2AIN + 3CO
(b) By removing oxygen of the air with the use of chemical This reaction is used for the purification of alumina ore
substances. (Serpeck's process). AIN is hydrolysed with steam.
Purified air ~Hot Cu ~. Nitrogen AIN + 3H20 ~ AI(OHh + NH3
2Cu + O2 ~ 2CuO
J, Heated
Purified air ~ Hot coke ~ CO2, CO, N2
CO2 and CO are removed by usual methods. Al 20 3
Pure alumina
Purified air~ Phosphorus~ -Pl0s--FNr'
Uses: (i) Nitrogen, N2, is a relatively unreactive element
I H 20 because of the stability of the nitrogen-nitrogen triple bond
~H3P04 (The N=N bond energy is 942 kJ/mol compared with 167 kJI
Properties: (i) It is a colourless, tasteless and odourless mol for the N-N bond energy). Therefore, it is used to
gas. It is slightly lighter than air as its vapour density is 14.0. provide an inert atmosphere in certain metallurgical operations
It is sparingly soluble in water. and during welding.
(ii) It is not poisonous in nature but animals do not survive (ii) Large quantity of nitrogen is used as a blanketing gas,
in its atmosphere due to absence of oxygen. the purpose of which is, to protect a material from oxygen
(iii) It can be liquefied to a colourless liquid (b.pt. during processing or storage. Thus, electronic components
-1'9S.8°C). When liquid nitrogen is poured on a table, the liquid are often made uQ,der a nitrogen atmosphere.
sizzles and boils away violently. (iii) It is used for filling electric bulbs.
(iv) It does not help in combustion. Nitrogen itself is non- (iv) It is used in the manufacture of NH 3, RN0 3, CaCN2
combustible. and other nitrogen compounds.
(v) It is chemically inert under ordinary conditions. However, (v) Liquid nitrogen is used as a refrigerant to freeze foods,
it shows chemical activity under high temperatures. to freeze soft or rubbery materials prior to grinding them, and
(a) Nitrogen combines with oxygen under the influence of to freeze biological materials. Liquid nitrogen has found
very high temperature like electric spark. wide use in frozen food preparation and preservation duripg
N2 + 02 \ 3000°C , 2NO (Nitric oxide) transit.
(vi) Liquid nitrogen is also a cryogen. It has uses in medicine
(b) Nitrogen combines with hydrogen in the presence
(cryosurgery), for example in cooling a localized area of skin
of a catalyst (finely divided iron) at 200 atmospheres and
prior to removal of a wart or other unwanted or pathogenic
400-S00°C temperature.
tissue.
N2 + 3H2 ~ 2NH3 (Ammonia)
(c) Nitrogen combines with metals at red heat to form
Active Nitrogen
nitrides.
When an electric discharge is allowed to pass through
4S0°C .. .. d) nitrogen under very low pressure (about 2 mm), a brilliant
6Li + N2 ~ 2Li3N (LIthIUm mtn e
. 4S0°C . . .d) luminiscence is observed which persists for sometime after
3Mg + N2 ~ Mg3N2 (MagnesIUm mtn e the stoppage of the discharge. It is observed that nitrogen after
the discharge is more active. This nitrogen is termed active
2AI + N2 ~ 2AIN (Aluminium nitride)
nitrogen.
Non-metals like boron, silicon at bright red heat also combine This form is not quite stable and gradually changes to normal
with nitrogen. form. Active nitrogen reacts readily with many metals to form
,- .
Elements of Group VA or 15 (Elemints of Nitrogen and Phosphorus Family) 469
nitrides. It reacts with a number of non-metals, e.g., sulphur,
phosphorus, iodine, etc. It is able to decompose many organic
Ammonium Metaphosphoric
compounds. dihydrogen phosphate acid
C2H 2 + N2 ~ C 2N 2 + H2
Active (vii) Urea on treatment with caustic soda forms ammonia.
The exact nature of active nitrogen is not .yet known. NH2CONH 2 + 2NaOH ~ Na2C03 + 2NH3
Urea'
IMPORTANT COMPOUNDS Laboratory preparation: Ammonia is prepared in the
OF NITROGEN laboratory by heating ammonium chloride with slaked lime,
1. Ammonia Ca(OHh in the ratio of 3 : 2 in apparatus shown in Fig. 10.2.
Nitrogen forms three well ~own hydrides with hydrogen:

(i) Ammonia, NH 3, (ii) Hydrazine, NH2.NH2 (N2~)' NH3
(iii) Hydrazoic acid, N3H. Ammonia is the most important of
these hydrides.
CaO
Occurrence: t NH3 is found in traces in atmosphere. This
is formed by bacterial decomposition of nitrogenous matter of
plants and animals. Ammonium salts such as ammonium chloride
and ammonium sulphate are found in small amounts in the soil.
On certain planets (Jupiter and Saturn), it is found in abundance.
Discovery: It was first isolated in 1774 by Priestley by
the action of ammonium chloride and lime. It was named
alkaline air. Berthelot, iii 1788, pointed out that ammonia is a
compound of nitrogen and hydrogen. In 1800, Davy established
its formula NH3.
Preparation: 0) Ammonia is obtained on a small scale ~~~~~W-~ Round bottom
from ammonium salts which evolve it when heated with caustic flask
soda or lime.
+
NH4Cl NaOH ~ NH3 + NaCI + H20
2NH4CI + Ca(OHh ~ 2NH3 + CaCl 2 + 2H 20
(Slaked lime) ,
(ii) Ammonia is formed when ammonium chloride is heated
with litharge.
Fig. 10.2 Apparatus for laboratory preparation of ammonia
2~CI + PbO ~ 2NH3 + PbCl2 + H 20
(iii) By reacting nitrides with water, ammonia is obtained. The mixture is taken in a flask and heated gently. The gas
AIN + 3H20 ~ AI(OHh + NH3 evolved is passed through lime tube and finally collected in a
Mg3N2 + 6H20 ~ 3Mg(OHh + 2NH3 dry jar by downward displacement of air method.
Precautions: (i) The apparatus should be air tight.
(iv) Ammonia can also be formed by doing reduction of
(ii) For the collection of gas, dry cylinders should be used
nitrates and nitrites with zinc and caustic soda. Zinc and caustic
as it is very soluble in water.
soda produce nascent hydrogen which reacts with nitrates and
(iii) The contents in a flask be covered with a layer of calcium
nitrites to form ammonia.
hydroxide as to absorb water otherwise the flask will crack.
NaN03 + 8H ZnlNaOH) NaOH + NH3 + 2H20 (iv) For drying of ammonia gas, the common dehydrating
agents like sulphuric acid or CaCl 2 or P 20 S cannot be used as
NaN02 + 6H Zn/NaOH) NaOH + NH3 + H20 ' these react with ammonia.
(v) Calcium cyanamide on hydrolysis evolves ammonia. 2NH3 + H 2S04 ~ (NH4)2S04
CaCN 2 + 3H20 ~ CaC03 + 2NH3 Ammonium sulphate
(vi) Ammonia is also obtained by heating ammonium CaCl 2 + 8NH3 ~ CaCI2'8NH3

compounds. Addition product
( NH 4hS04 -=~ NH3 + NH4HS04 P 20 S + 6NH3 + 3HzO ~ 2(NH4hP04

Ammonium Ammonium hydrogen Ammonium phQsphate
sulphate sulphate
For drying, quick lime, CaO is used as it does not react with Raw materials: Nitrogen and hydrogen are the chief
ammonia but reacts readily with moisture. raw materials. Nitrogen is obtained from air by liquefaction
CaO + H 20 ~ Ca(OHh followed by fractional evaporation of liquid air. Hydrogen is
Quick lime obtained by electrolysis of water.
The gaseous mixture containing nitrogen and hydrogen is
Manufacture of Ammonia thoroughly dried before it is used for the formation of ammonia.
(i) Haber process : Producer gas
(CO + N2)
Principle: Haber process is the most important industrial
method of preparing ammonia from N2 and H2. This method
Water gas
was discovered by a German chemist Fritz Haber in 1913. He (CO + H2 )
was awarded Nobel Prize in 1918 for this work. The method
involves the direct combination of nitrogen and hydrogen
according to the following reaction:
N2 + 3H2 ~ 2NH3 + 24.0 kcal Ammonical
cuprou's -N2+H2
The reaction is reversible, exothermic and formation of formate
NH3 is followed by a decrease in volume. Accordihg to
COisal)sorneCi
Le Chatelier's p~inciple, the ~ptim~m cl:mditions for the greater
yield of ammonia are: Method: The mixture of nitrogen and hydrogen in the
(a) High pressure: Usually a pressure of 200 atmos- ratio of 1 : 3 is compressed to 200 atmospheric pressure and
pheres is applied. allowed to enter the ammonia converter [Fig. 10.4 (a)] at the
. (b) Low temperature: The working temperature of 450- base. .
550°C is maintained, since reaction is very slow below this
temperature.
(c) Catalyst: At low temperature, although the yield of
ammonia is more yet the reaction is very slow. In order to
speed up the reaction, a catalyst is used. The following catalysts
have been proposed for this purpose:
(i) Finely divided iron with some molybdenum as a promoter.
(ii) Finely divided nickel and sodalime deposited over pumice
stone.
(iii) Finely divided osmium or uranium.
Catalyst
chamber
H2• N2 and ammonia
Recirculating
pump
Cooling
coil
Fig. 10.4 (a) Ammonia converter
The gases are heated to 450-500°C. The gases now enter

the catalyst chamber and interact forming ammonia. The issuing
v V Catalytic Liquid ammonia gases containing about 10% ammonia are cooled in water
chamber
cooler when some ammonia liquefies. The remaining ammonia
Fig. 10.3
is removed from gaseous mixture by dissolving in water. The
unreacted N2 and H2 are mixed with fresh gases and recirculated
Impure gases poison the catalyst; hydrogen and nitrogen through the converter. A diagrammatic sketch of the plant is
used, therefore, be free from CO. etc., which can spoil the shown in Fig. lOA (b).
working of the catalyst.
H
10- 0+ 0-
H-N---H-O
Cooling coil
tI~:"
I" 1
H
1
H
«l~
. - <I)
Ct::
0(1) (iv) It can be easily liquefied at room temper&ture by the
E>
CompreSl>or E g
c application of pressure. The liquid ammonia is colourless and
100-1000 <{
boils at -33°C. Itfreezes at -78°C. Liquid ammonia has a large
atm
heat of vaporisation (327 callg); It is,therefore, used in ice-
plants. " "" "
Liquid Recirculating
ammonia pump (v) Ammonia molecules link together to form associated
Fig. 10.4 (b)
molecules through hydrogen bonding.
H H H
CO2 absorbed in the water during the manufacture of N2 1 I I
and H2 by Haber-Bosch process can be utilised for the H-N- - -H-N-: - -H~N, etc.
manufacture of urea or ammonium sulphate from gypsum. I I 1
2NH3 + CO2 100-300 atm) NH2COONH4 ~ NH 2CONH2 + H 20
Higher melting point and boiling point in comparison to
Ammonium Urea
carbamate other hydrides of V group are due to hydrogen bonding.
CaS04 + 2~OH + CO2 -~) (N~hS04 + CaC03 + H 20 Chemical properties :
Gypsum Ammoniu!1l " (i) Stability: It is highly stable. It decomposes into
sulphate
nitrogen and hydrogen at red heat or when electric sparks are
passed through it.
(II) Cyanamide process :
, 2NH3 ~ N2 + 3H2
The calcium cyanamide is formed by the action of nitrogen
(ii) Combustion: Ordinary," ammonia "is neither com-
on calcium carbide at 800-1100DC. It is then treated with
bustible nor a supporter of combustion. However, it bums in
superheated steam at 180DC under a pressure of 3 to 4
the presence of oxygen to form nitrogen and water.
atmospheres when ammonia is produced.
4NH3 + 302 ---7 2N2 + 6H20
CaC2 + N2 800-1100°C
- - - - 0 0 7 ) CaCN 2+
"C
(iii) Basic nature: Ammonia is a Lewis base, accepting
Calcium Nitrogen Calcium Carbon
carbide cynamide proton to form ammonium ion as it has tendency to donate an
electron pair.
CaCN2 + 4H20 ---7 Ca(OHh +C02 + 2NH3
The flow sheet for this industry is given below:
H
I
H-N:+H+---7 H
H-N~H
r"I
]+ "
Cacog Heat. CaO

Limestone Quick
1 l~
CaC2 800. CaCN 2 18()'C Ca(OH)2
1100'C
"
H
I"
It forms salts with acids. "

H
I"
lime
+C02 + NH3 NH3 + HCI---7 ~Cl'
Ammonium chloride
"Now-a-days low temperature (500-600°C) is used under Thick white
fumes
6-8 atmospheric pressure.
2NH3 + H2S04 ---7 (~hS04
Physical properties: Ammonium sulphate
(i) AInmonia, NH 3, is the most important commercial Ammonia dissolves in water, its solution in water is a weak
compound of nitrogen. It is a colourless gas with a characteristic
)
base. The solution is described as aqueous ammonia. The
irritating or pungent odour. It brings tears into the eyes. reaction between ammonia and water produces relatively few
(ii) It is lighter than air. ions; ammonia remains mostly in the molecular form. It's
(iii) It is highly soluble in water. One volume of water ionisation in water is represented a s , '
dissolves 1300 volumes of ammonia at O°C and 1 atmosphere. NH3 + H 20 ~ NH! + OH-
The high solubility is due to the hydrogen bonding. The solubility Ammonia Wa:ter Ammonium Hydroxide
of ammonia increases with increase of pressure and decreases ion ion
Aqueous 'anunonia
with increase of temperature.
472 GR.B. Inorg~nic Chemistry for Competitions
The relatively few ions present do not conduct electricity CdS04 + 4NH 40H ~ [Cd(NH')4]S04 + 4H20
well and ammonia may thus be caned a weak base or weak Cadmium tetramine
sulphate
electrolyte. (Colourless soln.)
The solution turns red litmus to blue and phenolphthalein
AgN0 3 + NH40H ~. AgOH + ~N03
pink. White ppt.
(iv) Oxidation: [t is oxidised to nitrogen when passed
over heated CuO or PbO. AgOH + 2~OH ~ [Ag(NH3h]OH + 2H20
3CuO + 2NH3 ~ 3Cu + N2 + 3H20 Soluble
. 3PbO + 2NH3 ~ 3Pb + N2 + 3H20 AgCI also dissolves in N~OH solution.
Both chlorine arid bromine oxidise ammonia. AgCI +2NH40H ~ [Ag(NH3h]CI + 2H20
2NH3 + 3Cl 2 ~ N2 + 6HCI Diamine silver chloride
+6HCI~ ZnS04 + 2NH40H ~ Zn(OHh + (~hS04
ppt.
8NH3 + 3Cl 2 ~ N2 + 6NH4CI
(Excess) Zn(OHh + (NH4hS04 + 2NH40H ~
When chlorine is in excess an explosive substance nitrogen [Zn(NH3)41S04 + 4H20
trichloride is formed. Tetramine zinc sulphate
NH3 + 3Cl2 ~ NCl3 + 3HCI (Soluble) Colourless
Iodine flakes when rubbed with iiquor aniinonia form a dark Nickel salt first gives a green precipitate whiCh dissQlves~'
brown precipitate of ammoniated nitrogen iodide which explodes excess of N~OH:
readily on drying. NiCl2 + 2NH40H ~ Ni(OHh + 2~CI
2NH3 + 312 ~ NH3·N13 + 3HI
H ypochlorites and hypobromites oxidise ammonia to nitrogen. Ni(OHh + 2NH4CI + 4NH40H ~ [Ni(NH3)6]CI2 + 6H20
2NH3 + 3NaCIO ~ N2 + 3NaCl + 3H20 It forms a white precipitate with mercuric chloride.
The oxidation of ammonia with bleaching powder occurs HgCl2 + 2NH40H ~. HgNH2CI + NH4CI + 2H20
on warming. Amido mercuric
chloride
3CaOCl 2 + 2NH3 ~ 3CaCl2 + N2 + 3H20
Thus, ammonia acts as a reducing agent. It forms a grey precipitate with mercurous chloride.
The restricted oxidation of NH3 can be done with air, when Hg zCl2 + 2NH40H --7 Hg + HgNH leI + NH4CI + 2H20
'-r-----'
the mixture is passed over heated platinum gauze at 700-800°C. Grey
4NH3 + 502 4NO + 6H 20 (vii) Reaction with Nessler's reagent: A reddish brown
This .is the Ostwald's process and used for the ppt: is formed.
manufacture of HN03* 2KI + HgCl 2 ~ HgI2 + 2KCl
(v) Formation of amides: When dry ammonia is passed
2KI + Hgl2 ~ K2Hgl4
over heated sodium or potassium, amides are formed with
evolution of hydrogen. Alkaline solution of K2Hg4 is called Nessler's reagent. This
gives brown ppt with NH3 called iodide of Millon's base.
2Na + 2NH3 ~ 2NaNH2 + H2
Sodamide 2K2Hgl4 + NH3 + 3KOH ~ H2NHgOHgI + 7KI +. 2H 20
(vi) Reactions of aqueous ammonia: Many metal Brown ppt.
hydroxides are formed which may be precipitated or remain (viii) Reaction with CO2 : When gaseous CO2 is
dissolved in the form of complex compound in excess of reacted with liquid NH3 at 453-473 K under pressure of 220
~OH. atmospheres, it first forms ammonium carbamate which
FeCl 3 + 3NH40H ~ Fe(OHh + 3NH4CI decomposes to give urea.
ppL
2NH3 + C02 ~ NH2COO~ ~ NH2CONH2 + H20
AICl 3 + 3NH40H ~ AI(OHh + 3~CI
ppt. Ammonium carbamate Urea
CrCl3 + 3NH40H ~ Cr(OHh + 3NH4C1 (ix) Reaction with sodium hypochlorite: When a strong
. ppt. aqueous solution of ammonia is boiled with sOdium hypochlorite
CUS04 + 2NH40H ~ Cu(OHh .;:. (N~hS04 in presence of glue, hydrazine is formed.
. Blue ppt. NH3 + NaOCI ----'-7 NH2C1 + NaOH
Cu(OHh + (~hS04 + 2NH40H ~ [CU(NH3)4]SQ4 + 4H 20 NH2Cl + NH3 ~ NHzoNH2 + Hel
Tetramine copper Chloramine Hydrazine
sulphate
(Deep blue soln.)
Hydrazine produced may be decomposed by chloramine H H
into N2. oX
I
or N-H
2NH2Cl + NH2·NH2 ~ N2 + 2NH4CI 'X
H
I
(x) Liquid ammonia as a solvent: Ammonia like water H
undergoes self ionisation in liquid state. The formation of ammonia molecule involves sp3
hybridization of nitrogen atom giving rise to four hybrid orbitals
2NH3 NH~ + NH2:
directed towards the four comers of a tetrahedron.
+OH-
Liquid ammonia is, thus, used for carrying out many reactions
of polar compounds in non-aqueous medium.
2s 2p
[ll] I tJJl1J,
Uses:
Nitrogen \
(i) Liquid ammonia is used in refrigeration on account of its
large heat of evaporation. sp3 hybridization
(ii) Ammonia is used for making artificial silk. ox
(iii) Ammonia is also the starting compound for the preparation H

of most of the other nitrogen compounds. Ammonia is used Three hybrid orbitals having single electron each form
for -the manufacture of nitric acid (Ostwald's process), sOdium sigma bonds with three hydrogen atoms and the fourth hybricr--
bicarbonate (Solvay process) and ammonium compounds. orbital contains one pair of electrons.. On account of the
Ammonium sulphate, ammonium calcium phosphate, ammo- presence of this lone pair of electrons, the molecule gets
nium calcium nitrate, etc., are used as fertilizers. Ammonium
nitrate is used in certain explosives. Ammonia is also used in
...
distorted and acquires a pyramidal structure. The bond angle
/N", is not 109°28' but it is about 107.5°.

the manufacture of urea, NH2CONH2 which is an excellent
fertilizer of nitrogen and is used in the manufacture of
H H
urea-formaldehyde plastics. Ammonium compounds
(iv) Ammonia is used in the form of ammonium hydroxide
(aq. solution) in the laboratory in qualitative and quantitative The compounds having NHt ions are called ammonium
analysis. compounds. Some of the general characteristics of these
(v) Liquid hydrogen is not safe to transport in cylinders. compounds are described below:
Ammonia can be easily liquefied and transported safely in (a) These are generally white crystalline solids, dissolve in
cylinders. Ammonia can be decomposed into hydrogen and water and are strong electrolytes. Salts of strong acids give
nitrogen by passing over heated metallic catalysts. Thus, acidic solutions.
ammonia is the source for the production of hydrogen at .any NH 4CI + H 20 ~NH40H + HCI
destination. (b) They resemble the salts of potassium and rubidium in
(vi) It is used as a cleansing agent fOr removing grease. solubility and structure since the three ions are of comparable
Tests of ammonia: (i) It is identified by its charac- =
radii: NH4 148 pm, K+ = 133 pm, Rb+ = 148 pm.
teristic odour.
(c) When heated with alkali,they evolve ammonia.
(ii) It turns moist red litmus paper blue and moist turmeric
paper brown. NH4Cl + NaOH ~ NH3 + NaCl + H 20
(iii) With a drop of HC1, it forms thick white fumes of or NHt + OIr ~ NH3 + H 20
ammonium chloride. (d) Ammonium compounds with Nessler's reagent give a
(iv) With Nessler's reagent, it forms a reddish brown reddish brown precipitate or colouratiori.
precipitate or colouration. (e) Many ammonium compounds volatilise with dissociation
(v) Ammpnia gas when passed through copper sulphate around 300°C. For example,
solution gives a deep blue colour. ~CI(s) ~ NH3(g) + HC1(g)
(vi). It gives a yellow precipitate with chloroplatinic acid.
NH4N03(S) ~ NH 3(g) + HN0 3(g)
2NH3 + H2PtCl6 ~ (NH4hPtCI6 (f) Salts that contain oxidising anion first decompose
Ammonium chloroplatinate
(Yellow) giving NH3 and then NH3 is oxidised to N2 or N20 or both on
heating.
Structure: Ammonia is a covalent molecule. Three
hydrogen atoms are linked to nitrogen by single covalent bonds. (NH4hCr207 ~ N2 + Cr203 + 4H20
Its simple elestronic structure may be represented as: NH4N02 ~ N2 + 2H20
NH4N03 ~ N 20 + 2H20
[Note : The reaction of ammonium dichromate is often referred to as NH3 + NaOCI ~ NHzCI + NaOH
the "Volcano" reaction. A source of heat, such as lighted match,
will cause the orange crystals to decompose, producing sparks NHzCI + NH3 ~ NHz·NH z + HCI
Chloramine Hydrazine
and a large volume of dark green chromic oxide, Cr203' This
reaction should not be carried in open.] 2NH3 + NaOCI ~ NHz-NHz + NaCI + H 20
Some of the important ammonium compounds are: [Hydrazine produced may be decomposed by chloramine to
0) Ammonium hydroxide, NH40H: It is the aqueous N 2•
solution of ammonia and behaves as a weak base. 2NH2CI + Nz~ ~ 2NH 4Cl + N2
NH3 + HzO -.:-:-"" NH40H ~ NHt + OH- The function of glue is to prevent this reaction. The yield
(ii) Ammonium chloride, NH4 CI: This ammonium is about 60-70%.]
compound is also known as salammoniac. It is obtained by Recovery of hydrazine from the above solution is made in
reacting NH3 with HCl. the following manner:
NH3 + HCI NH4CI
Solution H2S04 N H HSO NaOH ) N. Z'J:f
........ H 0·
.. 'Distilled)
) Z S' 4 '4' 2
It is a white crystalline solid, highly soluble in water. It is . Sparingly soluble Hydrazi'le BaO
a volatile salt and decomposes at high temperatures into ammonia hydrate
and hydrochloric acid gas. These two gases again combine on
cooling .
." . NH4CI· ...;....:i·NHi -tIki (ii) Hydrazine may also be obtained by treating a :s.~HUll\ll1
The ~aih uses of ammonium chloride are in soldering and of KzS0 3 saturated with NO with sodium amalgam (reduction
tinning, in making of dry cells, in dyeing and calicoprinting and of NO).
in medicine. It is also used as a laboratory reagent. K ZS03·NzO z + 6H ~ K ZS04 + Nz~ + H 20
(iii) Ammonium sulphate. (NH4~S04: It is known Recovery is made from the solution as described above. It
in India as sindri fertilizer. It can be obtained by absorbing is a colourless fuming liquid. It is miscible with water in all .
NH3 in 60% H ZS04. proportions. It is soluble in alcohol.
2NH3 + H ZS04 ~ (NH4hS04 It acts as diacid base. Thus, it forms two series of salts.
It is a colourless crystalline solid and highly soluble in water.
It is used as a nitrogen fertilizer and a reagent in the laboratory. Hydrazine Hydrazine
(iv) Ammonium nitrate, NH4N03: It is prepared by monochloride dichloride
passing ammonia gas in 60% nitric acid. It burns in air liberating huge amount of energy. The alkyl
derivatives of hydrazine are used these days as potential rocket
NH3 + HN0 3 ~ NH4N0 3
fuels. It reacts with nitrous acid to give hydrazoic acid, N3H.
It is a colourless, deliquescent solid. It i,s very soluble in water.
N2~ + HN02 ~ N3H + 2H20
On gentle heating it decomposes and evolves nitrous oxide.
Hydrazine and its salts act as powerful reducing agents.
NH4N03 NzO + 2H20
PtC1 4 + N2~ ~ Pt + N2 + 4HCI
This is an explosive solid. On rapid heating it explodes.
4AgN03 -+- N zH 4 ~ 4Ag + N2 + 4HN03
2NH4N0 3 ~ 2Nz + Oz + 4HzO 4AuCl3 + 3N2H4 ~ 4Au + 3Nz + l2HCl
It is mainly used for making explosives such as amatol and It reduces Fehling's solution to red cuprous oxide, iodates
ammonal. to iodides and decolourises acidified KMn04 solution. It is
Amatol: 80%NH4N03 + 20% T.N.T. used as a fuel for rockets, reducing agent and a reagent in
Ammonal: NH4N03 + AI powder (small quantity) organic chemistry.
It is also used as a fertilizer. For this purpose, it is mixed H'Za;" H
with other substances, e.g., Structure ~N-~ 110"
Leuna saltpetre NH4N03 + (N~hS04 H/" H
Nitro chalk NlLtN0 3 + CaC03
III 3. Hydrazo.ic Acid, N3H
lB 2. Hydrazine or Diamide, NH2·NH2 orN2H4 It is the third hydride of nitrogen. It is an acid while other
This is another hydride of nitrogen ..It is prepared by following hydrides, NH3 and Nz~ are bases. It is prepared by the action
of nitrous acid on hydrazine.
methods:
(i) Raschig's method: A strong aqueous solution of NH 2·NHz + HN02 ~ N3H + 2H20
ammonia is boiled with sodium hypochlorite in presence of a It is also formed in the form of sodium salt by passing
little glue. nitrous oxide on sodamide.
Elements of Group VA or 15 (Elements of Nitrogen and Phosphorus Family) ·475
FeS04 + NO ---'; FeS04·NO

Na Addition product
Sodium Sodamide Sodium azide H2S04 + 2NH3 ---'; (NH4h S04
Ammonium sulphate
I H 2S04 )
N3H The following reactions can also be used to prepare nitrous
Pure hydrazoic acid is a colourless liquid. It is volatile and oxide.
has very bad odour. It is poisonous in nature. It explodes (a) By the action of cold and dilute nitric acid on zinc metal.
violently when struck or heated. It is soluble in water and 4Zn + lOHN03 ---'; 4Zn(N03h + N20 + 5H20
. alcohol. It is slightly stronger acid. It dissolves many metals
(b) By reducing nitric acid with stannous chloride and
forming azides.
hydrochloric acid.
2N3H + Mg ~ Mg(N3h + H2
Silver, lead and mercurous azides are formed by reacting 4SnCl2 + 8HCI + 2HN03 ---'; 4SnCl 4 + N20 + 5H20
their soluble salts with N3H. (c) By reducing nitric oxide with sulphur dioxide.
AgN0 3 + N3H ---'; AgN3 + HN03 2NO + SOz + H 20 ---'; H2S04 + N 20
These azides explode violently when struck (used as (d) By heating the mixture of hydroxy larnine hydrochloride
detonators). and sodium nitrite (1: 1).
Jt r,e}luce~ cafi<iwe"d_J(MnQ4"AitrQUs acid" .et~.
2N3H + °---'; 3N2 + H20
N3H + HN02 ---'; N z + N20 + H20
NHiOH;HCI + NaN02 ---'; NiO + NaCI + 2H20
Properties: (a) It is a colourless, tasteless gas with a
pleasant and sweet odour.
It oxidises HCI into C12.
(b) When inhaled in moderate quantity, it produces hysterical
N3H + 2HCI ---'; N2 + NH3 + Cl2 laughter, hence named as laughing gas. However, when inhaled
Hydrazoic acid is a resonance hybrid. for long, it produces insensibility and may prove fatal too.
+ + (c) It is heavier than air. .
H-N=N=N:~H N-N=N:
(d) It is fairly soluble in cold water but not in hot water. It
dissolves readily in fats and is tasteless and nontoxic in small
~ 4. Oxides of Nitrogen
,amounts.
Nitrogen forms a number of oxides. The well known oxides . The solution in water is neutral in nature. This is probably
of nitrogen are: due to the following equilibrium which lies in the left hand side.
(i) Nitrous oxide, N20, (ii) Nitric oxide, NO, (iii) Nitrogen
N 20+H 20 --->.. H 2N 20 2 ·
trioxide, N203, (iv) Nitrogen dioxide or Dinitrogen tetroxide,
Hyponitrous acid
N02 or N204 and (v) Nitrogen pentoxide, NzOs. Nitrous
oxide is nontoxic in small amounts but all the other nitrogen The oxide may be taken as an anhydride of hyponitrous
oxides are highly toxic. acid. However, the acid is not obtained by dissolving NzO in
water.
(I) Dinitrogen Oxide' or Nitrous Oxide, N20 or (e) It is neutral to litmus.
(f) It does not burn but supports combustion. The burning
Laughing Gas (Oxidation number +1)
material decomposes nitrous oxide into nitrogen and oxygen.
Preparation: It can be prepared by heating ammonium The oxygen then helps in the burning.
nitrate or a mixture of sodium nitrate and ammonium sulphate.
2N 20 S20-900·C) 2N2 + O 2
NH4N0 3 ---'; N 20 + 2H20
It supports combustion of SUlphur, phosphorus, magnesium,
2NaN0 3 + (NH4hS04 ---'; 2NH4N03 + Na2S04
sodium, candle and a splinter.
1
2N20 + 4H 20
S + 2N 20 ---'; S02 + 2N2
4P + lON20 ---'; 2P20 S + lON 2
The mixture consists of three parts ammonium sulphate and Mg + NzO ---'; MgO + N2
four parts sodium nitrate. It is heated carefully below 240°C.
2Na + N 20 ---'; Na20 + Nz
The evolved gas is collected over hot water as it is fairly
(g) It is decomposed by red hot copper.
soluble in cold water. It is u~ually contaminated with nitric
oxide (NO), ammonia (NH3) and water vapour. The gas is Cu + N 20 ---'; CuO + N2
passed through ferrous sulphate solution to remove nitric oxide (h) A mixture of hydrogep and nitrous oxide (equal volumes)
and through concentrated sulphuric acid to remove ammonia explodes with violence.
and water vapour. N20 + H2 ---'; N2 + H20
(i) It forms sodium azide on reaction with NaNHz (sodamide). (ii) Ostwald's process: By restricted oxidation of
NaNH 2 + NzO ~ NaN3 + HzO ammonia with air in presence of platinum gauze catalyst at
NaNHz + HzO~ NaOH + NH3 750°C, nitric oxide is formed.
4NH + 50 Pt. gauze) 4NO + 6H 0
2NaNHz + N20 -----7 NaN 3 + NaOH + NH3 3 2 7500C, 6 atm. 2
Uses: (i) A mixture of nitrous oxide and oxygen is used Properties: (a) It is a colourless gas, slightly heavier
as an dental anaesthetic and other minor surgical operations. than air.
(ii) It is sometime used as a foaming agent and as a propellant (b) It is sparingly soluble in water.
gas for whipped-cream dispensers. The gas dissolves in cream (c) It is liquefied with difficulty under high pressure and
under pressure. When the cream is dispersed, the gas bubbles low temperature (-151°C).
out, forming a foam. (d) It is paramagnetic indicating the. presence of unpaired
Structure: NzO is linear and unsymmetrical molecule. It electron in the molecule.
is considered as a resonance hybrid of the following two (e) It is neutral to litmus.
structures: (f) It at once reacts with oxygen to give brown fumes of
- nitrogen dioxide.
•- • + •• + ••
:N cr N cr 0: ~:N cr N~O: 2NO + Oz -----7 2N02
1t 21t ••
(g) It is stable oxide. It decomposes into-nitrogen and oxygen-
The bond length between N-N is 113 pm and between when heated at 800°C.
N-Ois 119 pm. .
It has a very small value of dipole moment (0.116 D). 2NO~·N2+ 02
Tests: (i) It is a gas with pleasant odour. (h) It is combustible and supports combustion of boiling
(li) It supports the combustion of glowing splinter. sulphur and burning phosphorus. .
(iii) It does not form brown fumes with nitric oxide. S + 2N0 -----7 S02 + N2
(II) .Nitric Oxide, NO (i) It dissolves in cold ferrous sulphate solution by form-
(Oxidation number +2) ing a hydrated nitrosyl complex.
Preparation: (a) By the action of dilute nitric acid on [Fe(H20)6]S04 + NO -----7 [Fe(H20)sNO]S04 + H20
copper (Lab. method). Ferrous sulphate Hydrated nitrosyl complex
Copper chips are taken in a Woulfe-bottle and some water (brown colour)
is added. Concentrated nitric acid is poured through the thistle
funnel and the nitric oxide liberated is collected over water.
1
Heat
3Cu + 8HN03 -----7 3Cu(N03h + 2NO + 4H20 FeS04 + NO + 5H20

The liberated gas may contain N02 and N20. These are In the complex [Fe(H20)5NO]S04, iron is assumed to
separated by passing the mixture through ferrous sulphate exhibit Fez+ state, but from magnetic moment measurements
solution: NO forms a dark brown nitroso-ferrous sulphate. it is observed that iron exhibits + 1 oxidation state instead of +2.
When this solution is heated, pure nitric oxide is liberated. In this complex, 'NO' exhibits +1 oxidation state.
(j) It is oxidised to nitric acid by oxidising agents like
FeS04 + NO -----7 FeS04·NO ~ FeS04 + NO - acidified KMn04 or hypochlorous acid. Thus, it acts as a
(Impure gas) (Dark brown) (Pure gas)
reducing agent
(b) A pure sample of nitric oxide is obtained when a mixture
of KN0 3, FeS04 and dilute H2S04 is heated. This is also a [2KMn04 + 3H2S04-----7 K2S04 + 2MnS04 + 3H20 + 50] x 3
laboratory method. [NO + 0 -----7 N0 2] x 15
2KN03 + H2S04 -----7 K2S04 + 2HN03 [3N02 + H20 -----7 2HN03 + NO] x 5
2HN03 -----7 H20 + 2NO + 30 6KMn04 + 9H2S04 + 10NO 3K2S04 + 6MnS04 +
-----7
[2FeS04 + H2S04 + 0 -----7 Fe2(S04h + H20] x 3 IOHN0 3 + 4H zO
2KN03+6FeS04+4H2S04--7K2S04+3Fe2(S04h+2NO+4H20 [BClO -----7 HCl + 0] x 3
(c) Nitric oxide is the first product obtained from the [NO +0 -----7 NOz] x 3
following two processes during the manufacture of nitric acid. 3N02 + H20 -----7 2HN03 + NO
(i) Electric arc process: By passing air through an electric 3HCIO + 2NO + H20 -----7 2HN0 3 + 3HCl
arc, nitrogen and oxygen of the air combine together to form
HN03 oxidises nitric oxide into N0 2.
nitric oxide.
2HN03 + NO -----7 H20 + 3N02
Elements of Group VA or 15 (Elements of Nitrogen and Phosphorus Family) '477
(k) It acts as an oxidising agent. It oxidises S02 to H2S04 Preparation: It is obtained by the reduction of nitric acid
and H2S to S. with arsenious oxide.
S02 + 2NO + H20 ~ H2S04 + N20 2HN03 H20. + N20 3 + 20
H2S + 2NO·~ H20 + S + N20 As20 3 + 20 ~ As 20 S
When exploded with hydrogen, it liberates nitrogen. As 20 S + 3H20 ~ 2H3As04
2H2 + 2NO ~ 2H20 + N2 AS20 3 + 2HN03 + 2H20 ~ 2H3As04 + N20 3
It is known in pure state in solid form at very low
However, when a mixture of hydrogen and nitric oxide is
passed over platinum black, ammonia is formed. temperature. In the vapour state, it is present as an equimolecular
mixture of NO and N0 2. The mixture of NO and N0 2 may be
2NO + 5H2 ~ 2NH3 + 2H20 obtained by the action of 6N nitric acid on copper.
Stannous chloride reduces nitric oxide to hydroxylamine.
2Cu + 6HN03 ~ 2Cu(N0 3)2 + NO +N0 2 + 3H20
[Snel2 + 2HCI ~ SnCLi + 2H] x 3 '----v---'
N 20 3
2NO + 6H ~ 2NH20H
Properties: (a) It condenses to a blue coloured liquid at
3SnCl2 + 6HCI + 2NO ~ 3SnCl4 + 2NH20H -30°C. The liquid when warmed at room temperature,
(1) Nitric oxide directly combines with halogens (fluorine, decomposes to a mixture of NO and N0 2 (brown coloured).
chl<'Jrine, bromine) to form corresponding nitrosyl halides. Room temp.
2NO + X2 ~ 2NOX N 20 3 ) NO+N0 2
Blue coloured '----v---'
(F2, Cl 2 or Br2) Nitrosyl halide liquid Brown coloured gas
Uses: (i) In the manufacture of nitric acid.
(b) It is an acidic oxide. It forms nitrous acid with water
(ii) As a catalyst in lead chamber process for the
and hence the name nitrous anhydride.
manufacture of sulphuric acid.
(iii) In the detection of oxygen to distinguish it from nitrous N20 3 + H20 ~ 2HN02
oxide. The oxide combines with caustic alkali forming corres-
Structure: The molecule NO has eleven valency electrons ponding nitrite.
and it is impossible for all of them to be paired. Hence, the
2NaOH + N20 3 ~ 2NaN02 + H2 0
molecule contains an odd electron which makes the gaseous
nitric oxide as paramagnetic. Structure: Since the oxide is unstable in liquid and gaseous
states and decomposes into NO and N02, it may be assumed
that it has" the following electronic structure:
115 pm •• xx •• xx ••
The structure is represented as a resonance hybrid. ..
:O:~Nx·O·xN~:O: or O-N-Q-N-O
The structure is supported by its diamagnetic behaviour.
+ •• - +. , Structure of N203 is of two forms:
:N=O: . ~:N=O: ~:N=O:
. O~ .,/0
In, the liquid and solid states, NO is known to form a loose ~N-N,O
dimer, N20 2. In this form, it is diamagnetic.
Asymmetrical Symmetrical
2.4 A . form form
N --- 0
I I l.l A (IV) Nitrogen Dioxide, N02 or
0--- N
Note : The electron configuration of NO is : Dinitrogen Tetroxide, N204
KK( cr2sh cr2s)2(cr2P z )2(n2Px )2(1t2py )2(1t2 Px)1 ' (Oxidation number +4)
The ft electron is lost easily to give nitrosonium ion, NO+ which This oxide exists as N0 2 in gaseous state while at low
forms many salts. NO+ can be obtained by reacting N203 with temperature, it exists as a dimer N20 4 (solid state).
H 2S04 ,
N20 3 + 3H2S04 ---1 2NO+ + 3HS04 + H30+
From solution, NOHS04 is isolated. Brown gas Colourless solid
Preparation: It is prepared in the laboratory either by
(III) Dinitrogen Trioxide, N203 heating nitrates of heavy metals or by the action of concentrated
(Oxidation number +3) nitric acid on metals like copper, silver, lead, etc.
2Pb(N0 3h 2PbO + 4N02 + 02
This oxide is also called nitrogen sesquioxide or nitrous
The mixture of nitrogen dioxide and oxygen is passed
anhydride.
through a U-tube cooled by freezing mixture. Nitrogen
... ., .
dioxide condenses to a pale yellow liquid while oxygen Uses: (i) It is used for the manufacture of nitric acid.
escapes. (ii) It is employed as a catalyst in the lead chamber process
Cu + 4HN03 ~ CU(N03h + 2N02 + 2H20 for the manufacture of sulphuric acid.
It is also obtained by air oxidation of nitric oxide. Structure: N0 2 molecule has V-shaped structure with
2NO + O2 ~ 2N02 O-N-O bond angle 132° and N-O bond length of about
Properties: (a) It is a brown coloured gas with pungent 119 pm which is intermediate between a single and a double
odour. Above 140°C, it is 100% N02. The liquid as well as bond. Hence, N02 is regarded as a resonance hybrid of the
solid is entirely N204 (dimer) at low temperature. The liquid following two structures:
boils at 22°C and solid melts at -11°C. • •
(b) It decomposes completely into nitric oxide and oxygen N~ ... .~
at 620°C.
o
~0 /
o
132' ~
0
2N02 \ 620'C \ 2NO + O 2
'----v----'
Brown Gaseous mixture The molecule is an odd electron molecule. The paramagnetic
(Colourless) behaviour of N02 confirms this view. Due to possession of
(C) When reacted with .cold water, it forms a mixture of odd electron, it is coloured and has a tendency to polymerise
nitrous acid and nitric acid. to form a colourless dimer, N204' The dimer is planar in
2N02 + H20 ~ HN02 + HN03 structure with N-N bond length 175 pm.
On accounfof this, it is known as mixed anhydride of
these two acids. However, with an excess of warm water it
forms nitric acid and nitric oxide.
O>175pm(~
! ,,,,, \l 0
3N02 + H20 ~ 2HN03 + NO /N-N~
(d) When absorbed by alkalies, nitrites and nitrates are
o Planar 0
formed.
2N02 + 2NaOH ~ NaN02 + NaN0 3 + H20 (V) Dinitrogen or Nitr.ogen Pentoxide, N20 S
(e) It acts as an oxidising agent. It oxidises metals like (oxidation number +5)
sodium, potassium, mercury, tin, copper, etc, This oxide is also known as nitric anhydride.
N0 2 + 2Na ~ Na20 + NO Preparation: It is prepared by distilling concentrated
N02 1': 2Cu ~ CU20 + NO nitric acid with phosphorus pentoxide in a glass apparatus.
Non-metals like carbon, sulphur, phosphorus when burnt in 2HN0 3 ~ H 20 + N 20 S
its atmosphere, are converted into corresponding oxides. P20S + HzO ~ 2HP03 .
5N02 + 2P ~ PzOs + 5NO
PzOs + 2HN03 ~ 2HP0 3 + N20 S
2NOz + S~ SOz + 2NO
It is also prepared by the action of dry chlorine on solid,
2NOz + C ~ COz + 2NO
silver nitrate at 95°C. .
It liberates iodine from KI and tufUS starch-iodide paper
4AgN03 + 2Clz ~ 4AgCl + 2N20 S + O2
blue.
Properties : (a) It is a white crystalline solid. The crystals
2KI + 2N02 ~ 2KN02 + 12
melt at 30°C giving a yellow liquid which decomposes at 40°C
In aqueous solution, it oxidises S02 to sulphuric acid.
to give brown NOz. The decomposition occurs with explosion.
S02 + HzO + N02 ~ H2S04 + NO
2NzOs ~ 4NOz + O2
This reaction is used for the manufacture of H ZS04 by lead
(b) It is an acidic oxide. It reacts with water with hissing
chamber process.
sound forming nitric acid.
H2S is oxidised to S and CO to CO 2.
NzOs + H20 ~ 2HN03
H2S + N02 ~ HzO + S + NO On account of this, it is known as nitric anhydride. With
CO + N02 ~ CO2 + NO alkalies it forms nitrates.
(f) It behaves also as a reducing agent. It reduces ozone to
2NaOH + NZ0 5 ~ 2NaN03 + H20
oxygen.
(c) It acts as a strong oxidising agent. It affects organic
2N02 + 0 3 ~ NzOs +·Oz substances such as cor~ rubber, etc. It oxidises iodine readily
It decolourises acidified KMn04 solution. into iodine pentoxid~.
2KMn04 + 3H 2S04 ~ K2S04 + 2MnS04 +3H 20 + 50 12 + 5N20 5 120 5 + 'lON02
lONOz + 5H 20 + 50 ~ lOHN03 (d) With aqueous NaCl, the ionic reaction takes place.
2KMn04 + 3H2S04 + lON0 2 + 2H20 ~ NzOs + NaCI ~ NaN0 3 + NO~Cl
K~S04 + 2MnS0 4 + lOHNOj
The reaction proves that N20 S exists as ionic nitronium 2HN02 ~ 2NO + H20 + 0
nitrate (NOr N03"). HN0 2 + 0 ~ HN0 3
(e) N20 S is decomposed by alkali metals.
3HN02 ~ 2NO + HN03 + H 20
N20 S ' + Na ~ NaN03 + N0 2 i
On heating, it decomposes into nitric oxide and nitrogen
Structure: In the gaseous state, it exists as a symmetricai dioxide.
molecule having the structure 02N--O-N02' N-O-N bond 2HN02 ~ H20 + N20 3
is almost linear. It may be represented as: .
1l
R)151 pm' ~o/~~R!. NO + N02
~ t.. " (Brown)
. N-R-N~ (d) Oxidising nature: It acts as an oxidising agent due

to ease with which it decomposes to give nascent oxygen. The
o Planar R potential equation when it acts as an oxidising agent is:
X-ray studies suggest that solid N20 S is ionic in nature, i.e., 2HN02 H20 + 2NO + 0
nitronium nitrate, NO; N03 .
(i) Iodine is liberated from potassium iodide.
mI 5. Oxyacids of Nitrogen 2KI + H 2S04 + 2HN02 ~ K2S04 + 2NO + 12 + 2H20
(H) Stannous chlQride is oxidised to stannic chloride.
Nitrogen forms a number of oxyacids. The most common SnCl2 + 2HCI + 2HN02 ~ SnCI4 + 2NO + 2H 20
and important oxyacids are: (iii) Sulphur dioxide is oxidised to sulphuric acid.
(i) Nitrous acid, HN02 and (ii) Nitric acid, HN03.
S02 + 2HN02 ~ H2S04 + 2NO
(I) Nitrous Acid, HN02 (iv) Sulphur is formed by oxidati~n of hydrogen sulphide.
H2S + 2HN02 ~ S + 2H20 + 2NO
The free acid is unknown. It is known· only in solution. . (v) Acidified ferrous sulphate is oxidised to ferric sulphate.
Preparation: Nitrous acid is .unstable and is usually
2FeS04 + H2S04 + 2HN02 ~ Fe2(S04h + 2NO + 2H20
prepared when needed as an aqueous solution. A solution of
(vi) Sodium arsenite is oxidised to sodium arsenate.
nitrous acid can be prepared by acidifying solutions of nitrites
with mineral acids. Na3As03 +. 2HN02 ~ Na3As04' + 2NO + H20
(e) Reducing nature: Nitrous acid acts as a reducing
2NaNOz + H 2S04 ~ Na2S04 + 2HN02
agent as it can be oxidised into nitric acid.
KN02 + HCI ~ KCl + HN0 2
HN0 2 + 0 ~ HN03
Nitrates on heating with lead decompose to give nitrite.
(i) It reduces bromine to hydrobromic acid.
/::,.
NaN03 + Pb ~ NaN0 2 + PbO Br2 + H 20 + HN02 ~ 2HBr + HN0 3
An aqueous solution of the acid, free from 'any salt, can be (ii) Acidified potassium permanganate is decolourised.
prepared by treating barium nitrite with calculated amount of 2KMn04. + 3H 2S04 + 5HN02 ~
dilute sulphuric acid. Since the acid is very unstable, the reaction . K2S04 + 2MnS04 + 5HN0 3 + 3H20
is carried out at low temperature (freezing mixture temperature). (Hi) Acidified potassium dichromate is reduced to chromic
The insoluble barium sulphate is filtered off. sulphate (green).
Ba(N02h + H2S04 ~ BaS04 + 2HN02 K2Cr207 + 4H2S04 +. 3HN02 ~
Insoluble K2S04 + Cr2(S04h + 3HN03 + 4H 20
A solution of nitrous acid may also be prepared by dissolving (iv) Hydrogen peroxide is reduced to water.
N20 3 in water. H20 2 + HN0 2 ~ HN03 + H 20
(f) Reaction with ammonia: It reacts with ammonia to
. N20 3 + H 20 ~ 2HN02
form nitrogen and water.
Properties: (a) Aqueous solution 'of nitrous acid is pale
blue. This is due to the presence of nitrogen trioxide, N20 3. NH3 + HN0 2 ~ [NH4N02] ~ N2 + 2H20
Intermediate
The colour fades on standing' for sometime.
(b) It is a weak acid and reacts with alkalies to form salts (g) Reaction with urea: It decomposes urea and other
known as nitrites. aliphatic primary amines to nitrogen.
. HN02 + NaOH ~ NaN0 2 + H 20 NH 2CONH2 + 2HN02 ~ 2N2 + CO2 + 3H 20
Urea
(c) Auto-oxidation: The acid is unstable and even in
cold solution, it undergoes auto-oxidation. C2HsNH2 + HO'NO ~ C2HsOH + N2 +< H~O
Etlwlamil1l.' Ethyl alcohol
(h) Reaction with aniline and other aromatic amines: The vapours of nitric acid evolved are condensed in a glass
It forms diazo compounds with aromatic amines at low receiver. The nitric acid thus obtained may contain oxides of
temperatures. nitrogen as impurity. The dissolved oxides of nitrogen are
C6HsNH2'HCl + HN02 ~ C6HSN NCI + 2H20 removed by redistillation or blowing a current ofcarbon dioxide
Aniline hydro- Benzene diazonium through warm acid.
chloride chloride
Manufacture; Nitric acid is of great commercial impor-
Uses: (i) It is used in organic chemistry in the preparation tance as it is needed in large amounts for the manufacture of
of diazo compounds which are employed for making aniline explosives, fertilizers, dyes, drugs, etc. Before world war I,
dyes. the only available method for the manufacture of nitric acid
(ii) It is also used for the replacement of -NH2 group by was the distilling of nitre with concentrated sulphuric acid.
-OH group in aliphatic primary amines. Now-a-days the following two processes are employed for the
(iii) In analytical chemistry, it is used both as an oxidising .manufacture of nitric acid :
and reducing agent. (i) Birkeland and Eyde process or Arc process.
Structure: Since nitrous acid forms two types of organic (ii) Ostwald's process. TI:Us process is most recent.
derivatives, the nitrites (R-ONO) and nitro compounds
(R-N0 2 ), it is considered to be a tautomeric mixture of two (a) Birkeland and Eyde Process
forms.
Principle; The reaction between nitrogen and oxygen is
reversible and eIiaotnerrnic iIi natUre.
HON=O
N2 + 02 ..,-- 2NO -43,200 calories
According to LeChatelier's principle, the formation of nitric
:0: oxide is favoured by high temperature. The temperature is thus
or
.. :0:
H:O:N: and . ..··0:
H·N ••
maintained about 3000°C by the use of an electric arc. The
.. nitric oxide· formed is immediately cooled to IOOO°C as to
prevent its decomposition. Nitric oxide further combines with
Note : Possible oxidation state of nitrogen lies between +5 and -3. In
HN02; oxidation state of nitrogen is +3; the oxidation state may oxygen to form nitrogen dioxide.
increase up to +5 and decrease up to -3. Thus, HN02 acts both 2NO + O2 ~ 2N02
as oxidising and reducing agent. On the other hand in HN03,
oxidation state of nitrogen is +5, thus, it acts only as oxidising The vapours are then passed through water when nitric acid
agent (itself undergoing reduction till -3 oxidation state is is produced.
achieved).
2N02 + H20 ~ HN03 + HN02
(II) Nitric Acid, HN03 3HN02 ~ HN0 3 + 2NO + H20
It was named aqua fortis (meaning strong water) by Process: Air is blown into an electric arc established
alchemists. Glauber obtained it by the action of sulphuric acid between two water cooled copper electrodes and spread into
on nitre. a disc with the help of a str~ng magnetic field applied at right
Laboratory preparation: It is prepared in the laboratory angles (Fig. 10.6). The electric arc produces a temperature of
by heating a mixture of alkali nitrate and concentrated sulphuric about 3000°C. Nitrogen and oxygen combine to form nitric
acid in a glass retort as shown in Fig. 10.5. oxide. The gases coming out of this furnace consists of 1.25
to 2% nitric oxide. These gases are cooled down quickly to
KN03 + H 2S04 ~ KHS04 + HN0 3
lOOO°C. The gases are further cooled to 150°C by passing
through boiler pipes. The gases now enter the oxidation chamber
where nitric oxide combines with oxygen and is oxidised to
N02
HNOs
Oxidising ~-A1b~so~rp~t~ion~i'\illJ=))"L
chamber tow.er
To sink Fig: 10.6 Manufacture of nitric acid

Fig. 10.5 Laboratory preparation of nitric acid
nitrogen dioxide. Nitrogen dioxide thus produced is absorbed Concentration of nitric acid: Dilrite nitric acid (50-60%)
in water in the absorption tower (70 ft high and 20 ft in obtained in the above process is concentrated by distillation till
diameter) packed with quartz. The nitric acid in the first tower a constant boiling mixture (b.pt. 121 DC) is formed. This il\>
reaches a strength of 30 to 40% while in the succeeding ordinary concentrated nitric acid (sp. gr. 1.414) and its strength
towers, the strength is about 20, 10 and 5% respectively. is 68%. More concentrated HN03 is produced by distilling the
The utility of this method has declined gradually and today ordinary concentrated nitric acid with concentrated sulphuric
it is practically outdated because the yield in this process is acid. The distillate is 98% HN03 (sp. gr. 1.51). The cent per
very poor and the consumption of electrical power is high. cent HN03 is obtained by cooling 98% HN0 3 in a freezing
mixture. Th~ colourless crystals (m.pt. -42DC) are melted to
g~ (b) Ostwald's Process (Modern Process) get 100% HN03.
Principle: The mixture of ammonia and air when passed Fuming nitric acid: It contains dissolved N02 in·
. over platinum gauze catalyst at 750-900°C, the ammonia: is concentrated nitric acid. It is brown in colour. Fuming acid is
oxidised to nitric oxide (NO), obtained by distilling concentrated HN0 3 with a little starch.
4NH3 + 502 . Pt ) 4NO + 6H20 + 21,600 calories

z
Nitric acid is reduced by starch into NO which dissolves in
.. 7S0-900·C the remaining acid to form fuming nitric acid. Fuming nitric
The reaction is exothermic and the heat of reaction maintains acid is a strong oxidising agent.
the temperature of the catalyst. Physical properties: Anhydrous nitric acid is a colour-
Therutricoxide is then oxidisedto nitrogen dioxide, (N0 2), less fuming liquid having a pUligent smell. Concentrated nitric·
by O2 from the air which is cooled to 50°C and absorbed in acid is often pale yellow as a result of partial decomposition of
water. The resulting NO can be volatilized and recycled. the acid to N02. It boils at 84.1 DC and freezes at -42°C. It is
2NO + O 2 ----7 2N02 . soluble in water in all proportions. The aqueous solution
containing about 68% of HN03 by weight forms a constant
3N02 + H20 ----7 2HN03 + NO
boiling mixture. This is the ordinary concentrated HN03 (sp.
PrOcess: A mixture of dry ammonia and purified air (free gr. 1.414). Nitric acid usually acquires yellow colour due to its
from carbon dioxide and dust particles) in the ratio of decomposition by sunlight into N02.
1 : 10 (by volume) is passed through the catalyst chamber
Sunlight
containing platinum gauze (Fig. 10.7). The gauze is initially 4HN03 ) 4N02 + 2H20 + O2
_NO The yellow colour of the acid can be removed by warming
it to 60-80°C and bubbling dry air through it.
It has extremely corrosive action on the skin and causes
. painful sores. .
. Chemical properties:
(A) It is a very strong acid. It e:x;hibits usual properties of
acids. It reacts with basic oxides, carbona,tes, bicarbonates
and hydroxides forming corresponding salts.
CaO + 2HN03 ----7 Ca(N03h + H20
Na2C03 + 2HN03 ----7 2NaN03 1: H20 + CO2
NaOH + HN03 --';7 NaN03 + H20
Absorption tower (8) Oxidising nature
Fig.10.7 Ostwald's process Nitric acid acts as a strong oxidising agent as it decomposes
to give nascent oxygen easily.
heated to about 800 DC electrically. Subsequently, the temperature
2HN03 ----7 H20 + 2N02 + 0
is maintained by heat of reaction. Ammonia is rapidly oxidised
to nitric oxide. The yield varies from 90-95%. or
The gases issuing from the converter are cooled and then (i) Oxidation of non-metals: The nascent oxygen
mixed with air in large empty chamber known as oxidation oxidises various non-metals to their corresponding highest
chamber. Nitric oxide gets oxidised to nitrogen dioxide. Nitrogen oxyacids.
dioxide is now absorbed in water in the absorption tower (I) Sulphur is oxidised to sulPi1.uric acid.
packed with broken quartz. The nitric Qxide formed is again [2HN03 ----7 H20 + 2N02 + 0] x 3
oxidised by oxygen and nitrogen dioxide is further absorbed by S + 30 + H 20 ----7 H2S04
water. The total reaction thus is:
4N0 2 + 2H20 + O2 ----7 4HN03 S + 6HN03 ----7 H2S04 + 6N0 2 + 2H20
Cone. and hot
The concentration of acid produced is about 50-60%.
(2) Carbon is oxidised to carbonic acid. [Nitrate + ferrous sulphate + conc. sulphuric acid ~
[2HN0 3 ~ H20 + 2N02 + 0] x 2 a brown ring (FeS04NO)]
C + 20 + (4) Iodine is liberated from KI.
C + 4HN03 ~ H2C03 + 4N02 + H20 2HN03 ~ 2NO + H20 + 30
(3) Phosphorus is oxidised to orthophosphoric acid. [2KI + 2HN0 3 + 0 ~ 2KN03 + 12 + H20] x 3
[2HN0 3 ~ H20 + 2N02 + 0] x 5 6KI + 8HN0 3 ~ 6KN03 J 2NO + 31 2 + 4H20
2P + 50 + 3H20 ~ 2H 3P0 4 (5) HEr, HI are oxidised to Br2 and 12, respectively.
2P + IOHN03 2H3P04 + ION0 2 + 2H20 . 2HN0 3 ~ H20 + 2N02 + 0
Cone. and not 2HBr + 0 ~ H20 + Br2
(4) Iodine is oxidised to iodic acid. . 2HBr + 2HN0 3 ~ Br2 + 2N02 + 2H 20
[2HN03 ~ H20 + 2N02 + 0] x 5 Similarly, 2HI + 2HN0 3~ 12 + 2N02 + 2H2(')
12 + 50 + H20 ~ 2HI0 3 (6) Ferrous sulphide is oxidised to ferrous sulphate.
12 + lOHN03 ~ 2HI03 + lON02 + 4H20 [2HN03 ~ H20 + 2N02 + 0] x 4
Cone. and not FeS +40~
(ii) Oxidation of metalloids: Metalloids like non-metals FeS + 8HN03 ~ FeS04 + 8N02 + 4H20
also form hIghest oxyacids. . J7) Stannous chloride' is oxidised to stannic'chloride-m.--
(1) Arsenic is oxidised to arsenic acid. presence of HCI.
[SnCI2 + 2HCI ~ SnCI 4 + 2H] x 7
[2HN03 ---" H20 + 2N02 + 0] x 5
2HN03 + 14H ~ NH20H + NH3 + 5H20
2As + 50 + 3H20 ~ 2H3As04 Hydroxylamine
2As + lOHN03 ~ 2H3As04 + ION0 2 + 2H20

or As + 5HN03 ~ H3As04 + 5N02 + H20 7SnCl2 + 14HCI + 3HN0 3 ~ 7SnCl4 + NH20H +
Cone. and not ~N03 + 5H20
(2) Antimony is oxidised to antimonic acid. (8) Cane sugar is oxidised to oxalic acid.
Sb + 5HN03 ~ H3Sb04 + 5N02 + H20 [2HN0 3 ~ H20 + 2N02 + 0]x'18
Cone. and not CI2H220 11 + 180 ~ 6(COOHh + 5H 20
(3) Tin is oxidised to metastannic acid. Cane sugar Oxalic acid
[2HN03 ~ H20 + 2N0 2 + 0] x 2 CI2H22011 + 36HN0 3 ~ 6(COOHh + 36N02 + 23H20

Sn + 20 + H20 ~ H2Sn03 (C) Action on metals
Sn + 4HN03 ~ H2Sn03 + 4N02 + H20 Most of the metals with the exception of noble metals like
(iii) Oxidation of compounds: (1) Sulphur dioxide is gold and platinum are attacked by nitric acid. Nitric acid plays
oxidised to sulphuric acid. a double role in the action of metals, i.e., it acts as an acid as
2HN03 ~ H20 + 2N02 + 0 well as an oxidising agent. Armstrong postulated that primary
S02 + 0 + H20 ~ H2S04 action of nitric acid is to produce hydrogen in the nascent
form. Before this hydrogen is allowed to escape, it reduces the
S02 + 2HN03 ~ H2S04 + 2N02 nitric acid into number of products like N02, NO, N20, N2 or
(2) Hydrogen sulphide is oxidised to sulphur. NH3 according to the following reactions:
2HN03 ~ H20 + 2N02 + 0 Metal + HN03 ~ Nitrate + H
H 2S + 0 ~ H 20 + S 2HN03 + 2H ~ 2N02 + 2H20
H2S + 2HN03 ~ 2N02 + 2H20 + S 2HN03 + 6H ~ 2NO + 4H20
(3) Ferrous sulphate is oxidised to ferric sulphate in presence 2HN0 3 + lOH'~ N2 + 6H20
of H 2S04 , 2HN0 3 + 16H ~ 2NH3 + 6H20
2HN03 ~ H20 + 2NO + 30 The progress of the reaction is controlled by a number of
[2FeS04 + H2S04 + 0 ~ Fe2(S04)3 + H20] x 3 factors:
(a) the nature of the metal,
6FeS04 + 3H2S04 + 2HN03 ~ 3Fe2(S04h + 2NO + 4H20
(b) the concentration of the acid,
NO is absorbed by ferrous sulphate and a dark brown ring
(c) the temperature of the reaction,
of nitroso ferrous sulphate is formed. This is the ring test for
(d) the presence of other impurities.
nitrates.
According to another view, reduction of nitric acid with Iron with conc. HN03 forms nitrogen dioxide (N02).
nascent hydrogen occurs only in the case of those metals Fe + 3HN0 3 ---7 Fe(N03h +. 3H
which are above hydrogen in the electrochemical series. In the [HN03+H ---7 N0 2 + H20] x 3
c;ase of metals which are. below the hydrogen in the
electrochemical series, the formation of hydrogen is not possible Fe + 6HN0 3 ---7 Fe(N03h + 3N02 + 3H20
Cone. Ferric nitrate
and thus metals are oxidised by nitric acid. The oxide formed
being basic in nature reacts with nitric acid to form nitrate. Iron is rendered passive by highly concentrated nitric acid
80%.
HN03 ---7 0
(c) Tin: Tin forms ammonium nitrate with dilute nitric
Metal + 0 ---7 Oxide acid.
Oxide + HN03 ---7 Nitrate + Water 4Sn + 1OHN03 ---7 4Sn(N0 3h + NH4N0 3 + 3H20
Dilute Stannous nitrate
(1) Metals which are above hydrogen in electro-
chemical series : Tin forms metastannic acid with conc. HN03 and evolves
(i) When hydrogen is given ott: Magnesium and nitrogen dioxide.
manganese are the metals that liberate hydrogen with dilute Sn + 4HN03 ---7 H2Sn03 + 4N02 + H20
nitric acid. Hot cone. Metastannic acid
Mg + 2HN0 3 ---7 Mg(N03h + H2 (d) Lead: It forms nitric oxide with diluteHNO y ---··
Dilute [P~ + 2HN0 3 ---7 Pb(N0 3h + 2H] x 3
Mn + 2HN03 ---7 Mn(N03h + H2 [HN0 3 + 3H ---7 NO + 2H20] x 2 .

Dilute
3Pb + 8HN0 3 ---7 3Pb(N03h + 2NO + 4H20
(ii) When metal nitrates are formed and nitric acid is Dilute
reduced: It forms nitrogen dioxide with cone. HN0 3.
(a) Zinc: It reacts with very dilute nitric acid (6%) to
Pb + 2HN03 ---7 Pb(N0 3h + 2H
form ammonium nitrate.
[HN03 + H ---7 N0 2 + H20] x 2
[Zn + 2HN03 ---7 Zn(N03h + 2H] x 4
Pb -+ mN0 3 ---7 Pb(N03h + 2N02 + 2H20
HN0 3 + 8H ---7 NH3 + 3H20 Cone.
NH3 + HN0 3 ---7 NH4N0 3 (2) Metals which are below hydrogen in the elec-
4Zn + IOHN03 ---7 4Zn(N0 3 h + NH4N03 + 3H20 trochemical series:
V. dilute (a) Copper: Copper with cold dil. HN03 forms nitric
It reacts with dil. HN0 3 (20%) to form nitrous oxide (N20). oxide (NO).
[Zn + 2HN03 ---7 Zn(N03h + 2H] x 4 2HN03 ---7 H20 + 2NO + 30
[Cu + 0 ---7 CuO] x 3
2HN03 + 8H ---7 N20 + 5H20
[CuO + 2HN03 ---7 Cu(N0 3h + H20] x 3
Dilute· 3Cu + 8HN03 ---7 3CU(N03h + 2NO + 4H20

It reacts with conc. HN03 (70%) to form nitrogen dioxide Copper with hot conc. HN03 forms nitrogen dioxide (N02).
(N0 2 )· 2HN03 ---7 H20 + 2N02 + 0
Zn + 2HN03 ---7 Zn(N0 3h + 2H . Cu + 0 ---7 CuO
[HN03 + H ---7 N~+H20] X 2 CuO + 2HN03 ---7 Cu(N03h + H20
Zn + 4HN03 ---7 Zn(N03h + 2N02 + 2H20 Cu + 4HN03 ---7 Cu(N03h + 2N02 + 2H20
Cone.
Hot cone.
(b) Iron: Iron with very dilute nitric acid forms
(b) Silver: Silver behaves similarly as copper.
ammonium nitrate.
3Ag + 4HN03 ---7 3AgN03 + NO + 2H20
4Fe + 1OHN03 ---7 4Fe(N03h + NH~03 + 3H20 Dilute
Ferrous nitrate
Ag + 2HN03 ---7 AgN03 + N02 + H20
Iron with dilute nitric acid forms nitrous oxide. Cone.
4Fe + 1OHN03 ---7 4Fe(N03h + N20 + 5H20 (c) Mercury: Mercury with dilute nitric acid forms
Dilute
mercurous nitrate and nitric oxide.
2RN0 3 -----7 H 20 + 2NO + 30 Platinum :

[2Hg + 0 -----7 Hg 20] x 3 [RN0 3 + 3HCI -----7 NOCI + 2H20 + 2CI] X 2
[Hg 20 + 2HN0 3 -----7 Hg 2(N0 3h + H20] X 3 Pt + 4CI -----7 PtCl4
6Hg + 8RN03 -----7 3Hg 2(N0 3h + 2NO + 4H 20 PtCl4 + 2HCI -----7 H2PtCl6
Dilute Mercurous nitrate
Pt + 2HN03 + 8HCI ~ H2PtCl6 + 2NOCI + 4H20
Mercury with conc. HN0 3 forms mercuric nitrate and Chloroplatinic acid
nitrogen dioxide.
(D) Action on organic compounds
2RN0 3 -----7 H 20 + 2N02 + 0
(i) Nitration: The replacement of one or more hydrogen
Hg + 0 -----7 HgO
atoms of an organic compound by a nitro group (-N0 2) is
HgO + 2RN0 3 -----7 Hg(N03h + H20 known as nitration. The nitration occurs in presence of conc.
Hg + 4RN03 -----7 Hg(N0 3h + 2N02 + 2H20 sulphuric acid with the formation of nitronium ion, NOr
Cone. Mercuric nitrate
RN0 3 + 2H2S04 ~ NO! + 2HS04 + H30+
Summary : Nitronium ion Hydronium io
Main products
Benzene and phenol when treated with a mixture of conc.
Concentration of Metal
nitric acid . RN0 3 and conc. H2S04 form nitrobenzene and trinitro phenol
(picric acid) respedively. 0 ••••
Mg, Mn H2 + metal nitrate

Very Dilute HN0 3 2
Fe, Zn, Sn
Pb, Cu, Ag, Hg

NH4N0 3 + metal nitrate
NO + metal nitrate
0
Benzene
+ HON0 2
H2SO4
) ON0
: :-. . I +
Nitrobenzene
H2O
Dilute HN03 Fe, Zn N 20 + metal nitrate OH OH
Zn, Fe, Pb, Cu, Ag N0 2 + metal nitrate

0
Phenol
+ 3HON02
H2SO4 02NON02
) :::-...
N0 2
+ 3H2O
Picric acid
Cone. HN03 Sn N02 + H 2Sn0 3
.Metastannie acid Glycerol with conc. RN0 3 in presence of conc. H2S04
below 25°C forms glycerol trinitrate (Nitroglycerine).
(3) Metals which become passive: The concen-
trated nitric acid renders metals like iron, cobalt, nickel, CH20N0 2
chromium, etc., passive. Aluminium is also rendered passive I
H2S04 . ) CHON02 + 3H 20
by nitric acid. Below 25°C I
The inertness exhibited by metals under conditions in
CH20N0 2
which chemical activity is expected is known as passivity.
Nitroglycerine
For example, iron displaces copper from copper sulphate
solution. This property of iron is lost if it is dipped in conc. Action on pr9teins: Nitric acid attacks proteins forming
RN0 3. The phenomenon of passivity (inertness)is best explain- a yellow nitro compound called xanthoprotein. It, therefore,
ed by assuming the formation of a thin film of oxide on the stains skin and renders wool yellow. This property is utilised
surface of the metal which prevents the action of the reagent. for the test of proteins ..
(4) Metals which do not react: Noble metals like (ii) Oxidation: A number of organic compounds are
gold, platinum, iridium, rhodium, etc., are not acted upon by oxidised.
nitric acid. However, these metals dissolve in aqua-regia Sawdust catches fire when nitric acid is poured on it.
(3 parts conc. HCI and one part conc. HN03). Aqua-regia Turpentine oil bursts into flames when treated with fuming
fOlIDS nascent chlorine which attacks these metals. nitric acid. Cane sugar is oxidised to oxalic acid. Toluene is
Gold: oxidised to benzoic acid with dil. HN03.
[RN0 3 + 3HCI -----7 NOCI + 2H20 + 2CI] x 3
Nitrosyl chloride
[Au + 3CI -----7 AuCI3] X 2
[AuCI 3 + HCI -----7 HAuCI 4] X 2
Benzoic acid
2Au + 3HN03 + IlHCI -----7 2HAuCI 4 + 3NOCI + 6H20
Chloroauric acid
Uses: Nitric acid is used : NaHC0 3 + HN0 3 ~ NaN03 + H 20 + CO 2
(i) in the manufacture of explosives like T.N.T. (trinitro- NaZS03 + 2HN0 3 ~ 2NaN0 3 + S02 + H 20
toluene), picric acid, nitroglycerine, dynamite, etc.
Properties: (i) Nitrates are generally soluble in water.
Oi) in the manufacture of fertilizers like ammonium nitrate,
A few nitrates hydrolyse.
basic calcium nitrate, etc.
(iii) in the manufacture of artificial silk, dyes, drugs, Bi(N03h + 3H20 ;;;;:='!: Bi(OHh + 3HN0 3
White ppt.
perfumes, etc.
(iv) in the purification of silver and gold. (U) Action of beat: Nitrates are decomposed on
(v) as a laboratory reagent. neating.
(vi) as a solvent for metals, for etching designs on wares (a) Alkali nitrates form nitrites and oxygen on heating.
of brass, bronze, etc. 2NaN0 3 2NaN02 + O 2
(vii) in the preparation of aqua-regia. 2KN0 3 ~ 2KN02 + O 2
(viii) in the manufacture of sulphuric acid.
(b) Nitrates of alkaline earth metals and heavy metals
(ix) for nitration of organic compounds.
decompose to give mixture of nitrogen dioxide and oxygen
(x) for the manufacture of nitrates such as silver nitrate,
along with a solid residue of metal oxide.
sodium nitrate, potassium nitrate, etc.
Structure.: Nitric acid is a monobasic acid, i.e., the 2Ca(N03h~2CaO -+ 4N02 +02
molecule consists of one hydroxyl group as it is formed by the 2Pb(N03h ~ 2PbO + 4N0 2 + 02
f •
hydrolysis of nitryl chloride, N02Cl. It may be structurally
2CU(N'03h ~ 2CuO + 4N0 2 + O 2
represented as below :
(c) Nitrates of metals of low chemical activity decompose
HO-N<: 0' H:~: ~::~

:0:
into corresponding metals and mixture of nitrogen dioxide and
oxygen.
2AgN03 ~ 2Ag + 2N02 + O2
Gaseous nitric acid is a planar molecule. The bond lengths Hg(N0 3h ~ Hg + 2N02 + 02
and bond angles as present in the molecule are represented in (d) Ammonium nitrate decomposes to form nitrous oxide.
the figure:
~03 ~ N 20 + 2H20
H o (ill) Action of cone. H 2S04 : When heated withconc.
H 2S04. nitrates undergo double decomposition reaction forming
free nitric acid. Some of the nitric acid get decomposed to give
brown fumes of nitrogen dioxide.
KN0 3 + H2S04 ~ KHS04 + HN0 3
4HN03 ~ 4N0 2 + 2H20 + O 2
(iv) Nitrates are good oxidising agents. These are used in
gun powder and explosives.
o
Tests for Nitrates
It is supposed to exist in two resonating forms. . Heat
(a) NItrate + cone. H2S04 ~ Brown fumes of N02
are given off.
HO-N<O ~ HO-N<O (b) Nitrate + cone. H 2S04 + copper turnings ~
o 0
quick evolution of brown fumes of N02.
1 NITRATES (c) Aq. soln. of nitrate + freshly prepared soln. of ferrous
The salts of nitric acid ai'6~alled nitrates. Sodium and potassium sulphate + cone. H2S04 which is added carefully by the side
nitrates occur in nature Whi thers are prepared by the action of the test tube ~ A brown ring is formed at the junction of
of nitric acid on metals, metallic .des, hydroxides, carbonates, two liquids.
bicarbonates, sulphites, etc. (d) Soln. of nitrate + brucine soln. ~ Red colouration.
Ag + 2HN03 ~ AgN03 + N02 + H20 (e) Nitrate + Zn metal + dil. H2S04 BoB for) Solution
5 mmutes
KOH + HN0 3 ~ KN0 3 + H 20
The solution is treated with few drops each of KI and starch
CaC03 + 2HN03 ~ Ca(N03h + H 20 + C02
solutions. Violet colouration is obtained.
Zn + H2S04 ~ ZnS04 + 2H (i) Retort process or old process:

Nascent hydrogen reduces nitrate into nitrite. The phosphorite mineral or bone ash is digested with
NaN0 3 + 2H NaN0 2 + H 20
~ concentrated sulphuric acid (about 60%). Insoluble calcium
2NaN02 + H2S04 ~ Na2S04 + 2HN02 sulphate andorthophosphoric acid are formed.
HN02 acid evolves iodine from KI which gives violet Ca3(P04h + 3H2S04 ~ 3CaS04 + 2H3P0 4
colouration with starch. The syrupy liquid is separated from insoluble residue by
filtration. The liquid is evaporated when it changes into
DISTINCTION BETWEEN NITRITES AND NITRATES metaphosphoric acid with evolution of water.
Test Nitrites Nitrates H3P0 4 ~ HP0 3 + H20

Metaphosphoric
I. Treat the salt with Brown fumes which No action. acid
dilute HCI. tum FeS04 solution
The metaphosphoric acid is mixed with powdered coke and
black.
distilled in fireclay retorts at a bright red heat (Fig. 10.8). The
2. Ring test. To the salt Dark brown colour A dark brown ring
solution add FeS04 even with dilute gets formed with
acid is reduced to phosphorus by carbon .which comes in
and H2S04 • H2S04' cone. H2S04 only. vapourised form. The vapours are condensed below water.
3. To the jicidified 199ine evolvedLgive No action 4HP0 3 + 10C P4 lOCO + ~I:I20
solution of the salt blue colour with
Retort
add KI solution. . starch.
4. To the acidified salt Decolourization No action. Charge
solution add KMn04 occurs.
solution.
S. To the solution add No action. Red colouration. Phosphorus
vapours
brucine solution.
1 PHOSPHORUS
Phosphorus was discovered by Brand in 1669. Scheele isolated Phosphorus
it from bone ash and Lavoisier in 1777 proved that phosphorus
is an element. It glows in the dark and was, therefore, called
phosphorus (Greek word, phos = light, and phero = I carry). Fig. 10.8 Retort process
Occurrence: Since phosphorus is an active element, it is
not found free in nature. It is widely distributed in nature in the
(ii) Electrothermal process or
combined state. It occurs as phosphates in the rocks and in the modern process:
soil and as phosphoproteins in all living beings. Deoxyribonucleic Phosphorus is prepared nowadays by the direct reduction
acid (DNA) is a chainlike biological molecule in which of mineral phosphorite, Ca3(P04h by carbon in presence of
informations aboutinheritable traits resides, contains phosphate silica. The mixture of phosphorite, (phosphate rock) with coke
groups along the length of its chain. Similarly, ATP (adenosine (C) and quartz sand (Si02) is dried and then introduced into
triphosphate), the energy containing molecule of living the electric furnace (Fig. 10.9). The furnace is an iron tank
organisms, contains phosphate groups. It is an essential
constituent of bones, teeth, blood and nervous tissues. It is
necessary for the growth of plants .. Bone ash contains about
80% calcium phosphate. It is present in milk, eggs and guano
(excreta of seabirds). The principal minerals of phosphorus Worm
are:
Phosphorus
(i) Phosphorite or phosphate rock Ca3(P04h =-- vapour
(ii) Fluorapatite, 3Ca3(P04h'CaF2 orCas(P04hF

(iii) Chlorapa:tite, 3Ca3(P04hCaCh or Cas(P04hO
Extraction: Phosphorus is extracted either from phos-
phorite or bone ash by the application of following two
processes:
(i) Retort process or old process.
(ii) Electrothermal process or modem process. Fig. 10.9
Elements of Group VA or IS (Elements of Nitrogen and Phosphorus Family) 487
lined inside with refractory bricks. Carbon electrodes are fitted Ox) It dissolves in caustic alkalies on boiling in an inert
on either side of the furnace. The furnace has two exits, one atmosphere and forms phosphine.
for removal of vapours in the upper part of the furnace and
other for removal of slag in the lower part of the furnace. The
P4 + 3NaOH + 3H 20 - t 3NaH2P02 + PH3 !
Caustic Sodium hypo· Phosphine
charge is introduced through the closed hopper arrangement. soda phosphite
The mixture is heated at 1400-1S00°C by the discharge of an
(x) It is very poisonous and very reactive. If white
alternating current between carbon electrodes. Silica combines
phosphorus is left exposed to air, it bursts spontaneously into
with calcium phosphate and forms phosphorus pentoxide which
flame. Because of its reactivity with oxygen, white phosphorus
is reduced by sarbon into phosphorus. The overall reaction is,
is stored under water, in which it is insoluble.
[Ca3(P04h + 3Si02 - t 3CaSi03 + P20 S] x 2 (xi) It directly combines with halogens forming first,
2P20S + lOC - t P4 + lOCO trihalides and then pentahalides.
2Ca3(P04h + 6Si02 + 10C - t 6CaSi03 + lOCO + P4 P4 + 6Cl2 - t 4PC13 ; P4 + lOCl 2 - t 4PCls
Vapours of phosphorus and carbon monoxide leave the (xii) It combines with a number of metals forming phos-
furnace through the upper exit and are condensed under water. phides.
The other product, calcium silicate glass (called slag) is tapped 6Mg + P4 - t 2Mg3P2 (Magnesium phosphide)
out periodically by an exitfrom the bottom of the furnace. :', ""!'"' . - "....:0-" -. ~
Purification: Phosphorus obtained is further purified 6Ca + P4 - t 2Ca3P2 (Calcium phosphide)

by melting under acidified potassium dichromate solution when (xiii) It combines with sulphur with explosive violence
the impurities are oxidised. It is redistilled. forming a number of sulphides such as P2S 3, P2SS, P4S3 and
P4 S 7 •
rI Allotropic modifications of phosphorus (xiv) It acts as a strong reducing agent. It reduces nitric
Phosphorus exists in a number of allotropic forms. These acid and sulphuric acid.
forms are: [2HN03 - t H20 + 2N02 + 0] x 10
(i) Yellow or white phosphorus (ii) Red phosphorus
P4 + 10 0 + 6H20 - t 4H 3P04
(iii). Scarlet phosphorus (iv) a-black phosphorus
(v) ~-black phosphorus (vi) Violet phosphorus P4 + 20HN0 3 - t 4H3P04 + 20N02 + 4H 20
The main allotropic forms, however, are white phosphorus
and red phosphorus. [H2S04 - t H20 + S02 + 0] x 10
P4 + 10 0 + 6H 20 - t 4H3P04
White or yellow phosphorus:
P4 + 1OH2S04 - t 4H 3P04 + 10S02 + 4H20
This is the common variety and is obtained by the methods
described above. This form is chemically very active. It reduces solutions of copper, silver and gold salts to
Properties: (i) White phosphorus is a molecular, corresponding metals.
transparent waxy solid, (sp. gr. 1.8) with the formula P4. P4 + lOCuS0 4 + 16H2O-t lOCu + 4H 3P04 + IOH2S04
(ii) The pure form is white but attains yellow.colour on long When the solution is heated, cuprous phosphide is formed.
standing due to the formation of a thin film of the red variety Heat
3P4 + 12CuS04 + 24H2a--:-::=:t4Cu3P+ 8H3P03 + 12H2S04
on the surface.
(iii) It is a soft metal and can be cut easily with knife. P4 + 20AgN03 + 16H20 - t 20Ag + 4H3P04 + 20HN03
(iv) It has characteristic garlic smell and is poisonous in (xv) When heated in inert atmosphere at 240°C, it changes
nature. O.IS g is the fatal dose. Vapours are also injurio.\ls. into red variety.
Persons working with phosphorus develop a disease in which
Yellow P 240.2S0°C) Red P
the jaw bones decay. This disease is known as phossy jaw.
Inert atm.
(v) It is insoluble in water but readily soluble in carbon
disulphide. Str:ucture: The vapour density of white phosphorus
(vi) It melts at 44°C into a yellow liquid. It boils at 280°C. between SOO-700°C, is 62 which corresponds to the molecular
(vii) In contact with air, it undergoes slow combustion and formula P4. The four phosphorus atoms lie at the comers of
glows in dark. This property is called phosphorescence. a regular tetrahedron. Each phosphorus atom is linked to each
(viii) Its ignition temperature is low (about 30°C). It readily of the other three atoms by covalent bonds. The P-P bond
. catches fire giving dense fumes of phosphorus pentoxide. It is, length is equal to 2.21 A. The bond angle is equal to 60° which
therefore, kept in water. suggests that the molecule is under strain and hence active in
nature.
P4 + S02 - t P4010 or 2P20S
Properties: - (a) It is dark red powder with specific gravity

2.1.
(b) It is odourless and non-poisonous in nature.
(c) It is insoluble in water as well as in carbon disulphlde.
(d) It does not show phosphorescence.
(e) It sublimes in absence -of air at 290°C.
(f) Its ignition temperature is high, i.e., 260°C.
(g) Chemically, it is not active in nature. It bums when
heated above 260°C to form phosphorus pentoxide.
(h) It does not react with caustic alkalies.
(i) _ It combines with halogens, sulphur and metals when
heated.
Fig. 10.10
2P + 5Cl 2 ~ 2PCl s
Red phosphorus 2P + 3S
Heat
-----7
Preparation: Red phosphorus is obtained by heating P+3Na ~ Na3P
yellow phosphorus, between 240-250°C, in presence of an
(j) Ifchanges to· whlte··phosphorus when it is . vaporised---· ..- ..
inert gas for several hours. The heating is done in an egg
and the vapours are condensed.
shaped iron vessel provided with a upright tube closed by
Structure of red phosphorus: The exact structure of
safety valve. The thermometers placed in iron tubes help to
red phosphorus is not yet known. It is regarded as a polymer
regulate the temperature.
consisting of chains -of P4 tetrahedral linked together possibly
Yellow phosphorus is taken in egg shaped vessel and air
in the manner as shown in Fig. 10,12.
inside is replaced by coal gas or carbon dioxide. A trace of
iodine is added which helps in the transformation. The vessel
is carefully heated to 250°C. The temperature is not allowed
to rise above 250°C otherwise the reaction goes out of control.
In case the pressure inside the vessel becomes too high the
safety valve is lifted to allow the escape of some vapours. The Fig. 10.12 Proposed molecular structure of red phosphorus
heating is done for several days. Red phosphorus obtained is COMPARISON BETWEEN WHITE AND RED PHOSPHORUS
powdered. It possesses yellow phosphorus as impurity. This
is removed by boiling with caustic soda solution. Red phos- Property White phosphorus Red phosphorus
phorus is not affected by caustic soda and remains undissolved. I. Physical state Soft waxy solid. Brittle powder.
This is thoroughly washed with water and finally dried. Red 2. Colour White when pure. Red.
phosphorus is much less reactive than white phosphorus and Attains yellow colour
can be stored in the presence of air. on standing.
3. Odour Garlic Odourless:
Safety valve 4. Specific gravity 1.8 2.1
5. Melting point 44°C Sublimes in absence of
Thermometer air at 290°C.
6. Ignition temperature Low, 30°C High, 26O"C.-
7. Solubility -in water Insoluble. Insoluble.
8. Solubility in CS 2 Soluble. Insoluble.
9. Physiological action Poisonous. Non-poisonous.
10. Chemical activity Very active. Less active.
II. Stability Unstable. Stable.
12. Phosphorescence Glows in dark. Does not glow in dark.
13. Burning in air Forms P40,o. Forms P40 IO .
14. Reaction with NaOH Evolves phosphine: No action.
15. Action of CI 2 Combines spontane- Reacts on heating to
ously to form PCI) form PCl 3 and PCl s.
Furnace and PCl s.
16. Reaction with hot Forms H3P04 .
HN0 3
Fig. 10.11 17. Molecular formula P 4 Complex polymer.
Uses of phospl1QIUS: (i) Red phosphorus is largely used dropped into it. Coal gas, oil gas or carbon dioxide is then
in the match industry. It is relatively nontoxic and is used in the bubbled through the flask to displace the air from the apparatus.
striking surface of safety matches. Red phosphorus or scarlet The flask is then heated. PH 3 is evolved. It is driven out along
phosphorus is preferred to yellow variety. with a current of inert gas. As soon as the bubbles of the gas
(ii) Yellow phosphorus is used as a rat poison. come in contact with air, they catch fire spontaneously forming
(iii) Red phosphorus is used for the preparation of HBr and rings of smoke known as vortex rings. This combustion is due
HI. to the presence of highly inflammable phosphorus dihydride
(iv) Radioactive phosphorus (p32 ) is used in the treatment (P 2H4 )·
of leukemia and other blood disorders. 2P2H4 + 702'~ 4HP03 + 2H20
(v) It is used for making incendiary bombs and smoke Metaphosphoric
acid
screens.
(vi) It is used in the manufacture of phosphor bronze, an P2H4 can be removed from phosphine by the following
alloy of phosphorus, copper and tin. methods:
(vii) It is used in the manufacture of compounds like (i) By passing the evolved gas through a freezing mixture
hypophosphites (medicine), phosphorus chlorides employed in which condenses P2~. .
industry, calcium phosphide used in making Holme's signals (ii) By passing the gas through HI. PH 3 is absorbed forming
and orthophosphori.~ acid~. pn()sphon!uIll iggiqe... This on,. treatment with. caustic potash_.-,- - .
gives pure phosphine.
1 COMPOUNDS OF PHOSPHORUS PH4I + KOH ~ KI + H20 + PH 3
~~ 1. Phosphine, PH3 Note: Pure phosphine can be obtained by using alcoholic potassium
hydroxide in place of aqueous NaOH solution. Phosphine can also
It is analogous to ammonia. It was discovered by Gen-
be prepared by the application of following reactions:
gembre in 1783. It is also known as hydrogen phosphide or (i) By heating phosphorus acid.
phosphoretted hydrogen. \ . 4H 3P0 3 ~ 3H 3P04 + PH)
Laboratory preparation: It is prepared by boiling yellow
(ii) By treating phosphonium iodide with 30% KOH solution.
phosphorus with a concentrated solution of sodium hydroxide
in an inert atmosphere. PH 41 + KOH ~ KI + H20 + PH)
P4 + 3NaOH + 3H20 ~ 3NaH2P02 + PH3 The evolved gas is first passed through HCI (decomposes P2~)
Sodium hypophosphite and then through NaOH (HI absorbed). This gives pure PH3.
(iii) By treating aluminium phosphide with dilute H2S04.
Besides PH3, small amounts of hydrogen (H 2) and phos-
phorus dihydride (P2~) are also formed. 2AIP + 3H2S04 ~ AI2(S04h + 2PH3
(iv) By doing hydrolysis of calcium phosphide with water or dil.
, P4 + 4NaOH + 4H20 ~ 4NaH2P02 + 2H2 . HC!.
3P4 + 8NaOH + 8H20 ~ 8NaH2P02 + 2P2H4 Ca3P2 + 6H 20 ~ 3Ca(OH)z + 2PH 3
A concentrated solution of sodium hydroxide i~ taken in a
Physical properties:
round bottom flask. Few pieces of yellow phosphorus are
(a) It is a colourless gas having unpleasant garlic-like odour
Oil gas or rotten fish odour.
(b) It is heavier than air and sparingly soluble in water.
(c) It liquefies at -89°C and solidifies at -134°C.
(d) It is poisonous in nature.
Chemical properties:
(a) Decomposition: When heated out of contact of air to
MO°C or when electric sparks are passed through, phosphine
decomposes into red phosphorus and hydrogen.
4PH 3 ~ P4 + 6H2
(b) Combustibility: A pure sample of phosphine is not
spontaneously inflammable. It bums in air or oxygen when
heated at 150°C.
2PH3 + 402 ~ P20 S + 3H20
The spontaneous inflammability of phosphine at the time of
preparation is due to the presence of highly inflammable
Fig. 10.13 phosphorus dihydride, P2H4. This property is used in making
Holme's signal. A mixture of calcium carbide and calcium When PH3 is passed through cuprous chloride solution in
phosphide is placed in metallic containers. Two holes are made HCI, it forms an addition compound.
and the container is thrown into the sea. Water enters and CU2Cl2 + 2PH3 -----7 2CuCI'PH3
produces acetylene and phosphine respectively. iThe gaseous (g) ~ormation of phospbides: (i) When phosphine is
mixture catches fire spontaneously due to the presence of passed through copper sulphate solution, a black precipitate of
P2i4. The acetylene produces a bright luminous flame which cupric phosphide is formed.
serves as a signal to the approaching ship,
3CUS04 + 2PH 3 -----7 CU3P2 + 3H2S04
(c) Action of ehlorine: Phosphine burns in the atmos-
phere of chlorine and forms phosphorus pentachloride. (ii) A black precipitate of silver phosphide is formed when
phosphine is circulated through silver nitrate solution.
PH3 + 4Cl2 -----7 PCIs + 3HCI
3AgN03 + PH3 -----7 Ag 3P + 3HN03
(d) Basic nature: Phosphine is neutral to litmus. (iii) When absorbed in mercuric chloride solution, mercuric
However, it is a weak base, even weaker than ammonia. It phosphide is formed.
reacts with Hel, HBr or HI to form phosphonium compounds.
3HgCl 2 + 2PH 3 -----7 Hg3P2 + 6HCI
PH 3 + HCI-----7 PH 4CI (Phosphonium chloride)
(h) The mixture of PH 3 and N 20 or PH 3 and NO explodes
PH3 + HBr -----7 PH 4Br (Phosphonium bromide) in presence of electric spark.
PH 3 + HI-----7 PH 41 !(Phosphonium iodide) PH 3 + 4N20~-----7 H 3P0 4 + 4~2
(e) Action of nitric acid: In contact with nitric acid Structure of phosphine: Phosphine is· a . covalent
phosphine begins to burn. molecule. It has pyramidal structure like ammonia.
[2HN03 -----7 H20 + 2N02 + 0] x 8
2PH3 + 80 -----7 P20 5 + 3H20
2PH3 + 16HN03 -----7 P 20 5 + 16N~
+ IlH 20 H H H
(0 Addition compounds: It forms addition compounds The bond angle H-P-H is 93°.
with anhydrous AICl 3 and SnCI4. Uses: (i) For making Holme's signals.
AICl 3 + 2PH 3 -----7 AIC13·2PH3 (ii) -For making smoke screens.
SnCl4 + 2PH 3 -----7 SnCI4'2PH3 (iii) For making metallic phosphides.
COMPARISON OF PHOSPHINE AND AMMONIA

Property Ammonia Phosphine
L Physical state Colourless gas. Colourless gas.
2. Odour Characteristic pungent smell. Unpleasant odour of rotten fish.
3. Molecular formula NH3 PH 3
4. Solubility Highly soluble in water. Sparingly soluble in water.
5. Density Lighter than air. Heavier than air.
6. Physiological action Non-poisonous. Poisonous.
7. Stability Decomposes at l300°C. Decomposes at 440°C.
8. Combustibility n burns in oxygen. It bums with white bright flame.
4NH3 + 502 ~ 4NO + 6H20 2PH 3 + 402~ P20S + 3H20
9. Basic character Basic in nature. Forms ammonium salts with acids. Weakly basic. Forms phosphonium salts with HCI, HBr and
NH3 .+ HCI NH4Cl HI. '.
PH3 + HC~ PH4CI
10. Stability. of salts Fairly stable. Less stable.
II. Action of chlorine Forms N z, NCI 3 and NH4CL Forms PCl 3 and PCls.
12. Action of AgN03 Forms soluble complex, Ag(NH 3hN03. Forms black precipitate Ag3P.
13. Action of CUS04 Forms soluble complex of blue colour, CU(NH3)4S04' Forms black precipitate of copper phosphide, CU3P2'
14. Hydrogen bonding Present. Absent.
15. Solvent property . Ammonia is a good solvent for many substances. It does not act as a solvent.
16. Action of hot sodium Forms sodamide. Forms phosphide.
2Na + 2NH3 ~ 2NaNHz + H2 6Na + 2Na3P + 3H2
17. Structure Pyramidal. Pyramidal.
Bond angle H-N-H = 107° , Bond angle H-P-H =93"
Elements of Group VA or IS (Elements of Nitrogen and Phosphorus Family) 491
2. Oxides of Phosphorus to three oxygen atoms and each oxygen atom is bonded to two
phosphorus atoms. The bond length P-O is 1.638 A.
Phosphorus forms three important oxides. These exist in
..
dimeric forms.
(0 Phosphorus trioxide, P203 or. P406 . ~/p, .
(ii) Phosphorus tetroxide, P204 or P408
(iii) Phosphorus pentoxide, P20S or P4010
{i} Phosphorus trioxide, P406

!.6 "\
.\-\-§~:
It is formed by burning phosphorus in limited supply of air.
P4 + 30 2 ~ P40 6 ..
:O--p-.-o:.. ..
The pentoxide, formed in small amount, is removed by
Fig. 10.14
passing through glass wool. The vapours of trioxide pass
through the glass wool and are condensed in a receiver cooled It has 6 P-O-P bonds, 12 sigma bonds and 16 lone pairs
by a freezing mixture. of electrons (one lone pair on each P atom and two lone pairs
Vapours of phosphorus at low pressure react with N 20 at of electrons on each oxygen atom).
600°C. to. form P203"
{ii} Phosphorus pentoxide, P4010
P4 + 6N 20 600°C) 2P 20 3 + 6N 2
It is prepared by heating phosphorus in a free supply of air
Properties: (a) It is a waxy solid having garlic odour.
or oxygen.
(b) It is poisonous in nature.
(c) It is soluble in benzene or chloroform. P4 + 502 ~ P40 lO
(d) When heated above 210°C, it forms red phosphorus It is further purified by sublimation.
and another oxide, P408' Phosphorus bums in CO2 at 100°C to form P20S'
4P406~. 3P40 8 + 4P
Phosphorus Red 2P + SC02 ~ P20 S + SCO
tetroxide
Properties: (a) It is a white crystalline compound.
When heated at about 440°C, it dissociates to phosphorus (b) It is odourless when pure. The usual garlic odour is due
dioxide. to presence of small amount of P406 as impurity.
2P20 3 ~ 3P02 + P (c) It is a white solid that sublimes at 360°C.
(e) In contact with air, it is oxidised to phosphorus pentoxide. (d) It has great affinity for water. The final product is
P40 6 + 202 ~ P40 lO orthophosphoric acid. It is, therefore, termed phosphoric
(f) It bums in chlorine forming oxy-chlorides. anhydride.
P40 6 + 4Ch ~ 2POCl 3 +. 2P02CI.
Phosphorus Metaphosphorus. .2~P207~
Metaphosphoric Pyrophosphoric 2H 2 0
oxy-chloride oxy-chloride
acid acid
(g) In cold water, it dissolves slowly forming phosphorus 4H3P0 4
acid. Orthophosphoric
P40 6 + 6H 20(cold) ~ 4H3P03 acid
With hot water, a violent reaction occurs forming i.e.,
orthophosphoric acid and phosphine.
It is, thus, used as a powerful dehydrating or drying agent.
P40 6 + 6H20(hot) ~ 3H3P04 + PH3 It removes water from inorganic and organic compounds like
The above reaction is actually the conversion of phosphorus H2S04, HN03, RCOOH, RCONHz, etc.
acid into orthophosphoric acid and phosphine. 2H2S04 + P4010 ~ 2S03 + 4HP03
4H3P0 3 ~ 3H3P04 + PH3 4HN03 + P4010 ~ 2N20S + 4HP03
4CH3COOH + P4010 ~ 2(CH3COhO +4HP03
This oxide is known as acid anhydride of phosphorus
2CH3CONH2 + P4010 ~ 2CH3CN + 4HP03
acid.
It also chars wood, paper, sugar, etc.
Structure of phosphorus trioxide: Its vapour density
(e) When heated strongly with carbon, it forms red phos-
corresponds to the formula P406' In the molecule, the
phorus.
phosphorus atoms lie at tetrahedral positions with respect to
each other and the 6 oxygen atoms are inserted· in between P40 lO + IOC ~ lOCO + 4P
Red phosphorus
them (Fig. 10.14). Each phosphorus atom is covalently bonded
(f) When fused with basic oxides, it fOlIDS phosphates. All these acids contain phosphorus atom/atoms Hnked
6CaO + P401Q ~ 2Ca3(P04h tetrahedrally to four other atoms or groups. Each of them has
at least one P~O unit and one P-OH group. The OH group
(g) 30% H20 2 react on P20 S in acetonitrile solution at low
is ionisable but H atom Hnked directly to P is non-ionisable.
temperature to fonn peroxy monophosphoric acid.
Thus, the number of OH groups present decides the basicity
P20S + 2H20 2 + H 20 ~ 2H 3PO S , of the acid.
(h) Mixture of P20 S and 02 in vapour state combine in
presence of electric discharge to fonn P206 called phosphorus (i) Hypophosphorus acid, H3P02
peroxide.
Preparation: When yellow phosphorus is boiled with
I baryta solution, barium hypophosphite is fonned which is filtered
P20 S + 2: O2 ~ P20 6
off.
Uses: (i) It is the most effective drying or dehydrating The barium salt is treated with calculated quantity of sulphuric
agent below 100°e. acid. The insoluble barium sulphate is filtered out and
(ii) It is used to manufacture phosphoriC acid, an oxoacid. hypophosphorus acid is obtained in the filtrate: The filtrate
Structure of phosphorus pentoxid~: Its vapour den- when evaporated leaves the syrupy mass, which can be
sity corresponds to fonnula P40IQ. The istructure is similar crystallised by careful cooling below O°e.
3Ba(OHh + 8P + 6H20 ,~. 3BatH2P02h~+ 2PH3
·0·
'f Barium hypophosphite
. ~!'-.. .
, I:O~i Insoluble Fiitrate
. u" . "'-0\: Properties: (a) It is a colourless crystalline solid. It melts

at 26.3°e. It is soluble in water.
(b) It is a monobasic acid. It ionises as :
:~<-\ vJ~: H3POZ ~ H+ + H2P02 ; Ka = lO- M
z
Its salts are known as hypophosphites.
..
:O~~,......-./0. .
!:0: ' (c) When strongly heated, it evolves phosphine.
2H 3PO Z ~ H3P04 + PH 3
.. (d) It acts as a reducing agent.
(i) It precipitates silver and gold from their solutions.
Fig. 10.15
H 3PO Z + 2HzO ~ H3P04 + 4H
to P40 6 (Fig. 10.14) with a difference that each phosphorus [AgN03 + H ~ Ag + HN03] x 4
atom is linked with an additional oxygen atom with the help of
a coordinate linkage involving a lone pair of electrons present 4AgN03 + H3POZ + 2HzO ~ 4Ag + H3P04 + 4HN0 3
on each phosphorus atom (Fig. 10.15). (ii) Mercuric chloride is reduced to mercurous chloride and
It has 16 sigma bonds, 41& bonds and 24 lone pairs of finally to metallic mercury.
electrons on oxygen atoms. H3POZ + 2HzO ~ H 3P04 + 4H
2HgClz + 2H ~ HgzCl z + 2HCI
~ 3. Oxyacids of Phosphorus
HgzClz + 2H ~ 2Hg + 2HCl
Phosphorus forms a number of oxyacids. Common oxy-
acids are given below: 2HgCl z + H3POZ + 2HzO ~ 2Hg + H 3P04 + 4HCI
Oxidation (iii) Copper sulphate is reduced to cuprous hydride.
Name of oxyacid Formula Basicity
state of P 4CUS04 + 3HzPOz + 6HzO~ 2CuzHz + 3H3P0 4 + 4HzS04
Hypophosphmus acid H3 P0 2 1 +1 (iv) Chlorine or iodine is reduced to hydracid.
Phosphorus acid H 3P0 3 2 +3
H3PO Z + 2HzO ~ H 3P0 4 + 4H
Orthophosphoric acid H 3 P0 4 3 +5
4H + 2Clz ~ 4HCl
Metaphosphoric acid HP0 3 I +5
Hypophosphoric acid H4 P 2 0 6 4 +4 H3PO Z + 2HzO + 2Cl z ~ H 3P0 4 + 4HCI
Pyrophosphoric acid I
H 4 P2 0 7 4 +5 Uses: Some of its salts such as sodium, potassium and
calcium hypophosphites are used in medicine as nerve tonics.
Structure: H3P0 2 is a monobasic acid, i.e., it has only . Structure: It is dibasic acid, i.e., two hydrogen atoms
one ionisable hydrogen atom or one OHgroup is present. It is are ionisable or two hydroxyl groups are present. Thus, the
given the following structure: structure is :
o o
t t
H-P-OH H-P-OH
I I
H OH
Phosphorus lies in sp3 hybrid state. The phosphorus lies in sp3 hybrid state.
(ii) Phosphorus acid, HaPOa (iii) Orthophosphoric acid, HaP04

Preparation: (i) It is obtained by dissolving phosphorus This acid is commonly called as phosphoric acid.
trioxide in water. Preparation: (i) It is formed when phosphorus pentoxide
P40 6 + 6H20 ----* 4H3P03 is boiled with hot water.
(ii) It is also obtained by hydrolysis of phosphorus P40 lO + 6H20 ----* 4H3P04
trichloride. (ii) OrthophosPlloric.a,gd is a,iSQ foWed when_PC..4 ___ _
PCl3 + 3H20 ~ H3P0 3 + 3HCl (phosphorus pentachloride) is boiled with water.
Chlorine is passed over molten white phosphorus under
PCls + 4H20 ----* H3P0 4 + 5HCI
water when phosphorus trichloride formed undergoes hydro-
lysis. (iii) Laboratory preparation: The best method for its
2P + 3Cl 2 2PCl3 preparation in the laboratory is to heat red phosphorus with
The solution is heated until the temperature becomes 180°C. concentrated nitric acid in a flask with a reflux condenser.
On cooling crystals of phosphorus acid are obtained. P + 5HN03 ----* H3P04 + H 20 + 5N02
Properties: (a) It is colourless crystalline compound. It The reaction is usually carried out in presence of a crystal
melts at 73°C. It is highly soluble in water. of iodine. The iodine acts as a catalyst.
(b) When heated, it forms orthophosphoric acid and P + 31 ----* PI3
phosphine.
200°C PI3 + 3H20 ----* H 3P03 + 3HI
4H3P03 ----7 3H3P04 + PH3 3HI + 3HN0 3 ----* 3H20 + 3N0 2 + 3i.
(c) It is a strong acid. It is dibasic in nature. H3P03 + 2HN0 3 ----* H 3P04 + H 20 + 2N02
H3P0 3 ~ H+ + H2P03" ~ 2H+ + HP0 3 P + 5HN03 ----* H3P0 4 + 5N02 + H20
Kl 10-1 ; K2 == 2 X 10-7 The solution is concentrated till it becomes syrupy at about
It thus forms two series of salts such as NaH2P03 and 170°C. It is cooled over conc. H 2S04 in vacuum desiccator
Na2HP03 known as primary phosphites and secondary when crystals of orthophosphoric acid are formed.
phosphites respectively. Manufacture : It is prepared on large scale from bone ash
(d) It acts as a strong reducing agent. The potential equation or phosphorite mineral.
is: (a) By decomposing calcium phosphate present in bone ash
or phosphorite mineral with conc. H2S04'.
H3P03 + H20 ----* H3P0 4 + 2H
Ca3(P04h .+ 3H2S04 ----* 3CaS04 + 2H3P0 4
It reduces CUS04 to Cu, AgN0 3 to Ag, HgCl 2 to Hg2Clz,
Iz to HI and acidified KMn04 solution. On standing calcium sulphate settles down and the clear
supernatant liquid separates out. The liquid is concentrated
CUS04 + 2H ----* Cu + H2S04
when about 85% concentrated orthophosphoric acid is obtained.
AgN0 3 + H ----* Ag + HN03 (b) The bone ash is dissolved in minimum amount of nitric
2HgCl 2 + 2H ----* Hg2CIZ + 2HCI acid and lead acetate is added as to precipitate lead phosphate.
12 +2H ----* 2HI The lead salt is then decomposed by passing H2S.
2KMn04 + 3H2S04 ----* K2S04 + 2MnS04 + 3H20 + 50 Pb3(P04h + 3H2S ----* 3PbS + 2H3P0 4
Insoluble Solution
[H3P03 + 0 --:7. H3P04] x 5
(c) Bone ash or calcium phosphate is converted into
2K'Mn04 + 3H2S04 + 5H3P03 ----* phosphorus pentoxide when heated with silica in electric
K2S04 + 2MnS04 + 5H3P0 4 + 3H 20 furnace.
2Ca3(P04h + 6Si02 ----7 6CaSi03 + P4010 (f) Reaction with bromides and iodides: Hydrobromic
P40 lO is then dissolved in hot water. and hydroiodic acids are liberated from bromides and iodides
respectively. This is the laboratory preparation of HBr and
P40 JO + 6H 20 ----7 4H3P04
HI.
Properties: (a) It is a transparent deliquescent cryst-
3NaBr + H3P04 ---7 Na3P04 + 3HBr
alline solid. It melts at 42.3°C. It absorbs water and forms
colourless syrupy mass. It is highly soluble in water. 3NaI + H 3P04 ---7 Na3P04 + 3HI
It is usually sold as an aqueous solution. (g) Reaction with magnesium salt: Magnesium salts
(b) Heating effect: When heated at 250°C, it is converted combine with orthophosphoric acid in presence of ammonium
into pyrophosphoric acid. chloride and ammonium hydroxide to form a white precipitate
of magnesium ammonium phosphate.
2H3P04 250°C) H4 P20 7 + H20
On further heating, it is converted into metaphosphoric MgS04 + NH4Cl + H3P04---7 Mg(NH4)P04 + H2S04 + HCI
acid. This reaction is used to test Mg2+ ion.
(h) On heating orthophosphoric acid in presence of nitric
acid with ammonium molybdate, a canary yellow precipitate of
ammonium phosphomolybdate is formed.
or
When strongly heated at red heat, it forms P40 IO . H3P04 + 21HN03 + 12(NH4hMo04---7
4H3P04 ----7 P40 lO + 6H20 (~hP0412Mo03 + 2lNH4N0 3 + 12H20
Ammonium phospho-
(c) Acidic nature: It is a tribasic acid, i.e., all the three molybdate
hydrogen atoms are ionisable. It forms three series of salts.
This reaction is used to test pot ion.
H3P04 H+ + H2P04 ~ 2H+ + HP01- ~ 3H+ + pot (i) Orthophosphoric acid, H3P04 undergoes cOIidensation
NuH zP04 NuzHP04 Na3P04
(Primary. saJtr (Secondary salt) (Normal or
reaction to form other phosphoric acids. For example, two
tertiary· salt) orthophosphoric acid molecules condense to form diphosphoric
Possible sodium salts are sodium dihydrogen phosphate acid or pyrophosphoric acid.
(NaH2P04), disodium hydrogen phosphate (Na2HP04), and o 0
. trisodium phosphate (Na3P04)' II r----.., II 0
Primary salt on heating forms a salt of metaphosphoric H-O-P-O-H
I + H-O-P-O-H
L _ _ _ _ ..J I
-H2 )
acid.
Heat o 0
NaH2P04 ~ NaP03 + H20 I I
Sooium dihydrogen Sodium meta-
phosphate phosphate
H H
o 0
Secondary salt on heating forms a salt of pyrophosphoric II II
acid. H-O-P-O-P-O-H
1 1
Disod. hydrogen Sodium pyrophos-
o 0
phosphate phate 1 1
Normal salt is not affected by heating. H H
In case, ammonium ion is present in the salt it behaves as Two series of these phosphoric acids exist (all having in the
hydrogen. +5 oxidation state). One series consist of the linear poly-
phosphoric acids, which are acids with the general formula
2MgNH4P04 Mg2P207 + 2NH3 + H20
Heat
Hn + 2Pn03n + I formed from linear chains of P-O bonds.
N~HP04 ~ NaP03 + NH3 + H20
(d) Reaction with AgN03 : A yellow precipitate of silver o 0
phosphate is formed. II II
H-O-P-O-P-O-H
3AgN03 + H3P04 ---7 Ag 3P04 + 3HN03 1 ·1
Yellow ppt.
o 0
(e) Reaction with BaCI2 : A white precipitate of barium I I
phosphate is formed in neutral or alkaline solution.· H H
3BaCl2 + 2H3P04 ----7 Ba3(P04)z + 6HCI Diphosphoric acid
White ppt.
000 Properties: It is a white crystalline solid, soluble in water.
II II II In-aqueous solution, it is converted into orthophosphoric acid.
H-O-P-O-P-O-P-O-H
I I I ~P207 + H 20 ~ 2H3P04
000 On strong heating, it is converted into metaphosphoric acid.
I I I
Red heat
H H H H4P 20 7 ) 2HP03 + H20
Triphosphoric acid
It is a tetrabasic acid and forms two series of salts.
The other series consists of the metaphosphoric acids, which
~P207 + 2NaOH ~ Na2H2P207 + 2H20
are acids with the general formula (HP0 3 )n- When a linear
polyphosphoric acid chain is very long, the formula becomes H4P20 7 + 4NaOH ~ Na4P2~ + 4H 20
(HP0 3)n, with n very large, and the acid is called pOlymetaphos- It gives a white precipitate with AgN03.
phori~ acid.
4AgN0 3 + 14P20 7 ~ Ag 4P20 7 + 4HN03
Sodium triphosphate, Na5P301Q, one of the most commonly
Structure: It is a tetrabasic acid, i.e., 4 hydroxyl groups
used polyphosphate, is manufactured by adding sufficient
are present. The structure follows directly from the fact that
sodium carbonate to orthophosphoric acid to give a solution of
the acid can be prepared by removing one water molecule
the salts NaH2P02 and Na2.HP()4~ When this solutionisspraYed
from tWo mo)eclilesofortnopnospnoncaCid:--' -
into a hot kiln, the orthophosphate ions condense to give sodium
triphosphate. o 0 0 0
Uses: Orthophosphoricacid is used: i i -H,O i i
HO-P-OH + HO-P-OH ~ HO-P-O-P-OH
(a) for making metaphosphoric and poly phosphoric acids.
I I I I
(b) for preparation of J:[Br and HI in the laboratory. OH OH OH OH
(c) as a stabilizer for H 20 2. Each phosphorus atom lies in tetrafiedral environment. (sp3
(d) for soft drinks. hybrid state.)
(e) for manufacture of phosphate fertilizers.
(f) Orthophosphoric acid as polyphosphates and metaphos-
phates are used in detergents, where they act as water softeners
by complexing with metal ions in the water.
Structure: Orthophosphoric acid is a tribasic acid, i.e.,
3 .hydroxyl groups are present. The structure of the acid is
thus represented as:
o
i
HO-P-OH (v) Metaphosphoric acid, HP03
I
OH Preparation: It is prepared by heating orthophosphoric
acid or pyrophosphoric acid or diammonium hydrogen
Phosphorus atom lies in sp3 hybrid state.
orthophosphate.
(iv) Pyrophosphoric acid, H4P20 7 600·C
H 3P04 ~ HP03 + H20;
Preparation: It is prepared by heating orthophosphoric 600°C
H4P 20 7 ~ 2HP03 + H20
acid at 250-260°C.
(NH4hHP04~ HP0 3 + 2NH3 + H 20
. 2H3P04 ~ ~P207 + H20 It is also prepared by dissolving P20 5 with small amount of
A pure sample of the acid is formed by heating an water at OOc.
equimolecular mixture of orthophosphoric acid and phosphorus P20 5 + H 20 ~ 2HP03
oxychloride.
Properties: It is a transparent grassy solid. The acid is,
5H3P04 + POCl 3 ~ 3H4P20 7 + 3HCI therefore, known as glacial phosphoric acid. It dissolves in
water with cracking sound. On boiling the aqueous solution,
On cooling at -lOoC, crystals of the acid are obtained.
it is converted into orthophosphoric acid.
496 O.R.B. Inorganic Chemistry for Competitions
HP03 + H20 ~ H 3P04 The polymerised form is represented as:

It reacts with AgN03 forming a white precipitate.
000
AgN0 3 + HP0 3 ~ AgP03 + HN03 t t t
BaCl2 gives a white precipitate which is insoluble in acetic
acid. "o/I"o/i"o/I"o/
OH OH OH
BaCl2 + 2HP03 ~ Ba(P03h + 2HCl
(HP03)1I
It forms salts with alkalies. The salts are called metaphos-
phates. Sodium metaphosphate when heated with metal oxides M 4. (i) Phosphorus Trichloride, PCI3
forms mixed phosphates. The mixed phosphates of heavy
Preparation: It is formed when dry chlorine is passed
metals have characteristic colours; hence used in qualitative
over red or white phosphorus heated gently in a retort over a
analysis.
water bath. The vapours of trichloride are condensed in a
NaP0 3 + CuO ~ NaCuP0 4 receiver cooled in a freezing mixture.
Uses: It is used : P4 + 6Cl 2 ~ 4PCl3
(i) as a dehydrating agent. Properties: It is colourless fuming liquid. It reacts
(ii) as awatcr soft~neJJc<l1go9.) inthefolm"of a I>QlY-'PeF, violently. with water formingpll()sphorus acid.
(NaP0 3)6' PCl3 + 3HOH ~ H 3P03 + 3HCI
(iii) in the manufacture of dental cements. It reacts with concentrated H 2S04 forming chloro-sulphonic
Structure: It is a monobasic acid, i.e., it consists one OH acid.
group. As it is formed by dehydration of H3P04, it can be 4H2S04 + 2PC13~ 2HS0 3CI + P20 S +2S02 + 4HCI + H 20
represented as HO-P-O. Chloro-sulphonic
-k acid
o or 2H2S04 + PCl3 ~ HS0 3CI +HP03 + S02 + 2HCI
It reacts with organic compounds containing hydroxyl
OH
group,
I 3C 2H sOH + PCl 3 ~ 3C2HsCI + H 3P03
HO-P-OH -=---) HO-P-O
Ethyl alcohol Ethyl chloride
J, J,
o o 3CH3COOH + PCl3 ~3CH3COCI + H 3P03
Acetic acid Acetyl chloride
Metaphosphoric acid or its salts are not present in the form
3C6H sS02,OH + PCl 3 ~ 3C6H sS02CI + H 3P03
of simple molecules but are often polymerised, (HP0 3)".
Benzene sulphonic Benzene sulphonyl
Structure of dimeric metaphosphoric acid may be given acid chloride
as:
It directly combines with C1 2, O2 and S, This indicates that
it is an unsaturated compound.
PCl3 + Cl 2 ~ PCls
2PC13 + O 2 ~ 2POCl 3
Structure of trimeric meta phosphoric acid can be represented PCl3 + S ~ PSCl3
in cyclic form. It acts as a reducing agent.
PCl 3 + S02Cl2 ~ PCls + S02
PCl3 + S03 ~ POCl3 + S02
3PCl 3 + SOCl2 ~ POCI3 + PSCl3 +.PCls
3PCl3 + S2Cl2 ~ PCIs + 2PSCl3
It reacts with finely divided metals when hot.
12Ag + 4PC13 ~
12AgCI + P4
6Na + PCl3 ~ 3NaCI + Na3P
Uses: It is used in the manufacture of POCl3 and in the ARSENIOUS OXIDE OR ARSENIC
preparation of organic compounds. TRIOXIDE
Structure: Its structure is similar to ammonia. P atom
undergoes sihybridization. In the tetrahedral configuration, This is the most important compound of arsenic and is
technically called as white arsenic.
one of the position is occupied by a lone pair. Thus, it is
Preparation: On a large scale, it is obtained by roasting
pyramidal in shape.
..
CI-P-CI
arsenopyrite ore, FeAsS, in air.
I 2FeAsS + 502 ~ AS 20 3 + Fe203 + 2S02

CI It is also formed when arsenic is· heated in air or oxygen.
II (ii) Phosphorus Pentachloride, PCl s 4As + 302 ~ 2As20 3
Properties: (a) It is a white poisonous powder. A very
Preparation: It is obtained by action of an excess of dry small dose of 50 mg or so may prove fatal, It undergoes
chlorine gas on phosphorus trichloride. sublimation .
PCl3 + Cl2 ~ PCIs . (b) It is sparingly soluble in water. It reacts with water to
It may be obtained by the action of sulphuryl chloride form arsenious acid. The oxide is, therefore, known as arsenious
(S02Ch) on phosphorus or phosphorus trichloride. anhydride.
-.AsZQ 3 , + 3H20.·,,---:L2H3AsOs -~.---.-.- ..
P4 + 10S02Cl2 ~ 4PCIs + 10S02
The acid is unstable and is known in solution. Its salts,
PCl3 + S02Cl2 ~ PCIs + S02 known as arsenites, are quite stable.
Properties: It is almost colourless crystalline solid with (c) It is an amphoteric oxide.
pungent odour when pure. On heating it sublimes at 160°C. AS20 3 + 6NaOH ~ 2Na3As03 + 3H20
When heated it dissociates into PCl3 and C12. Sodium arsenite
PCIs ~ PC13 + C12 AszOs + 6HCI ~ 2AsCl 3 + 3H20

Arsenic chloride
It undergoes hydrolysis violently by water..
(d) When treated with hydrogen sulphide, arsenic sulphide
PCIs + H20 ~ POCl3 + 2HCl
(yellow precipitate) is formed.
PCIs + 4H 20 ~ H 3P04 + 5HCI As203 + 3H2S ~ AS2S3 + 3H20
It reacts with hydroxy compounds and replaces hydroxyl (e) It acts as a reducing agent as it is changed to pentoxide
groups to chlorine atoms. (or arsenic acid, As20s + 3H20 ~ 2H3As04)
C2HSOH + PCIs ~ C2HSCI + POCl3 + HCI (i) AS20s + 212 + 2H20 ~ AS20S + AHI
CH 3COOH + PCIs ~ CH3COCI + POCl3 + HCI (n) [2HN03 ~ H20 + 2N02 + 0] x 2
AS203 + 20 ~ ASzOs
SO(OHh + 2PCIs ~ S02Cl2 + 2POCl3 + 2HCI
Sulphuric acid SUlphuryl chloride AS20 3 + 4HN03 ~ AS20S + 4N02 + 2H20
Many metals are converted into chlorides when heated with (ill) [2KMn04 + 3H2S04 ~
PCIs· K2S04 + 2MnS04 + 3H20 + 50] x 2
PCIs + Zn ~ ZnCl2 + PCl3 [AS203 + 20 ~ As20 S] x 5
Uses: It is used as chlorinating agent in organic chemistry. 4KMn04 + 6H2S04 + 5As203 ~
Structure: X-ray studies have revealed that solid PCIs 2K2S04 ·+ 4MnS04 + 5As20S + 6H20
consists of ionic lattices, i.e., tetrahedral [PC4t cations and (iv) [H202 ~ H20 + OJ x 2
octahedral [PC16f anions. In vapour state, it has trigonal AS 20 3 + 20 ~ AS20S
bipyramid shape in which P has gone sid hybridization. (See AS203 + 2H202 ~ As20s + 2H20
page 99)
(v) [03 ~ 02 + 0] x 2
+ As 20s + 20 ~ As 20 S
CI
<r~~:,:::;<rl
1 P I
As 20s + 203 ~ ASzOs + 202
(1) It is reduced to arsenic by acidified stannous chloride.
:~~: [SnC12 + 2HCl ~ SnC4 + 2H] x 3
CI----+----Cl
AS203 + 6H ~ 2As + 3H20
CI
Tetrahedral Octahedral
cation anion
Uses: (i) It is llsed as a weed killer and as an insecticide. ,(iv) It should not be injurious to plants.
(ii) In very small doses, it is used as medicine and for killing (v) It should not disturb pH of the soil.
rats. (vi) It should be cheap .
. (iii) It is used for making pyrex glass.
(iv) As a reducing agent in volumetric analysis. Classification of fertilizers :
(v) It is employed in dyeing and calicoprinting. Fertilizers are classified according to the elements (N, P
(vi) It is used for preS;ervation of hides and skins. and K) which they supply to the soil :
(i) Nitrogenous fertilizers
FERTILIZERS (ii) Phosphatic fertilizers
For the normal and healthy growth of plants, more than twelve (iii) Potash fertilizers
elements such as carbon, oxygen, hydrogen, nitrogen, (iv) Phosphatic cum nitrogen fertilizers
phosphorus, potassium, calcium, magnesium, iron,zinc, (v) NPK fertilizers.
manganese, molybdenum, sulphur, etc., are essential. These
are called plant nutrients. Out of these elements, carbon, ~~ Nitrogenous Fertilizers
hydrogen, oxygen and a part of nitrogen are drawn from the
The important nitrogenous compounds used as fertilizers
inexhaustible air and water. The remaining elements including
are:
nitrogen are supplied by sQil.NitrQgen,pho~phorus and
potassium are regarded as essential plant nutrients and are (i) Ammonium "nitrate'
consumed in large quantities. Other elements are required in (ii) Ammonium sulphate,
minute quantities by plants and are termed as secondary (iii) Calcium cyanamide,
nutrients. The soil is never deficient in secondary nutrients. (iv) Calcium ammonium nitrate,
However, after a few years of continuous cultivation, the soil (v) Basic calcium nitrate,
becomes poorer and poorer in materials supplying nitrogen, (vi) Urea.
phosphorus and potassium to plants. If the soil is not
compensated' what it has lost in time, it would become less (i) AmmoniUm nitrate
productive and ultimately infertile. Thus, in Qrder to maintain Ammonium nitrate is prepared from ammonia. Ammonia
soil fertility, it is necessary to add materials containing nitrogen, from the Haber process is burned in oxygen over a platinum
phosphorus and potassium in the form of manures. Manures catalyst to obtain niric oxide, NO;
are of two types:
4NH3 + 50 2 ~ 4NO + 6H 20
(1) Natural manures and (2) Artificial manures.
1. Natural manures: It includes animal waste such as The nitric oxide, reacts readily with oxygen from the air to
blood, bones, horns, leather waste, fish scrap, excreta, night form nitrogen dioxide, N0 2;
soil, sewage, sludge, tankage, guano, etc., and decayed plants 2NO + O2 ~ 2N02
such as cotton seed meal, wood or tobacco stem ashes, oil
N02 in turn reacts with water to yield nitric acid HN0 3 and
cakes and green growing plants buried in the soil, etc. nitrous acid, HN02. The nitrous acid, being unstable, is
2. Chemical manures or artificial manures or decomposed with heat and the resulting nitric oxide, NO, can
fertilizers: These are chemical compounds containing be volatilized and recycled,
nitrogen, phosphorus or potassium obtained by artificial means.
These chemical compounds are generally called fertilizers. 2N0 2 + H 20 ~ HN03 + HN02
"The chemical substances which are added to the soil as 3HN02 ~ HN0 3 + H20 + 2NO
to make up the deficiency of essential elements are called
Additional ammonia then reacts with the nitric acid to produce
fertilizers" •
ammonium nitrate (NH4N0 3);
E~ery chemical compound of nitrogen, phosphorus and
potastium cannot be used as a fertilizer. The chemical substance HN0 3 + NH3 ~ NH4 N03
which can be used as a fertilizer must have the fol1owing Solid ammonium nitrate should be handled carefully though
characteristics: pure ammonium nitrate is quite stable in farming operation, it
(i) It must be soluble in water. is an oxidising agent and can explode on heating when mixed
(ii) It should be easily assimilated by plants. in bulk with reducing materials. Pure ammonium nitrate applied
(iii) It should be fairly stable. to the soil poses no explosive threat at all.
Ammonium sulphate contains 24-25% ammonia. This
Ammonium ammonia cannot be easily utilised by plants. It is converted into
nitrate nitrates by nitrifying bacteria in the soil and nitrates are taken
up easily by plants from the soiL It should not be frequently
used otherwise the soil becomes acidic. It should be generally .
used after the seeds have germinated.
(NH ) SO Basic ... ) NH Nitrifying) Nitrates
4 2 4 compounds in soil 3 bacteria
(iii) Calcium cyanamide, CaCN 2 (Nitrolim)

It is manufactured by heating calcium carbide with nitrogen
at 1100°C in an electric furnace. The product is usually dark
grey in colour due to the presence of graphite and is sold in the
market in the name of nitrolim.
Urea
CaC2 + Nz ----,} CaCN2 + C
Calcium
cyanamide
In soil, it is converted into urea which then decomposes into
Fig. 10.16 Nitrogen fertilizers from anhydrous ammonia
ammonia. Ammonia is finally convelted into nitrates by nitrifying
bacteria.
(ii) Ammonium sulphate, (NH4)2S04 CaCN 2 + HzO + COz ----,} CN'NH 2 + CaC03
Cyanamide
The following two processes are used for its manufacture:
(a) Ammonia liquor obtained from dry distillation CN'NH2 + HzO ----,} CO(NHzh
Urea
of coal: Ammonia liquor obtained during distillation of coal
consists various ammonium compounds. In order to recover CO(NHzh + HzO ----,} 2NH3 + C02
ammonia, the liquor is mixed with lime and heated in stills by It is a slow fertilizer and its effects on fertility are of more
steam. The mixture of ammonia and steam so produced is permanent nature. It is added to the soil before sowing and not
passed through a lead lined tank containing 60% H2S04, when when the plants are actually growing.
crystals of (NH 4hS04 separate on cooling.
(NH4hC03 + Ca(OHh ----,} CaC03 + 2NH3 + 2H 20
(Iv) Calcium ammonium nitrate,
2NH4CI + Ca(OHh ----,} CaCl2 + 2NH3 + 2H 20
Ca(N0312·NH4N03 (CAN)
It is known as Nangal fertilizer in India. Ammonia is obtained
Heal by Haber process. A part of ammonia is converted into nitric
NH4HS ----,} NH3 + H2S
acid by Ostwald's process. Excess of nitric acid and ammonia.
2NH3 + H 2S04 ----,} (NH4hS04 are then made to react with each other to give ammonium
(b) Ammonia obtain;;J(i from Haber process: The nitrate.
synthetic ammonia obtained from Haber process is also conver-
NH3 + HN03 ----,} NH4N0 3
ted into ammonium sulphate by absorbing it in sulphuric acid.
The solution is concentrated and treated with powdered
Sindri process limestone as to neutralise the free acid present in the solution.
. 2HN03 + CaC03 ----,} Ca(N03}z + H20 + CO;
Ammonium sulphate is manufactured at Sindri (Jharkhand)
by passing synthetic ammonia into a suspension of finely Ca(N03 h + NH 4N0 3 ----,} Ca(N03h'~N03
CAN
powdered CaS04 (Gypsum) in water through which a stream
of carbon dioxide is also passed. CAN is hygroscopic. The pellets are, therefore, coated with
calcium silicate as to protect from moisture. Ammonium nitrate
2NH3 + H20 + C02 ----,} (NH4hC03 is explosive but CAN does not explode. This fertilizer is superior
CaS04 + (NH4hC03 ----,} (NH4hS04 + CaC03 to ammonium sulphate as it is more soluble in water and does
The insoluble CaC03 is filtered off. The solution on not make the soil acidic.
evaporation under vacuum and cooling yields crystals of
ammonium sulphate. Ammonium sulphate is generally called (v) Basic calcium nitrate, Ca(N03l2'CaO
Sindri fertilizer in India. It is formed by reacting limestone with nitric acid.
CaC03 + 2HN03 ----7 Ca(N03h + H20 + CO2 soluble in water and thus do not serve as source of phosphorus
It is then mixed with lime. for plants. These are, therefore, converted into soluble materials
which can act as good fertilizers.
Ca(N03h + CaO ----7 Ca(N03hCaO
Basic calcium nitrate
Being highly deliquescent, it is packed in water proof bags. Phosphate
rock
Basic calcium nitrate is also called Norwegian saltpetre or
nitrate of lime. It is preferred to the normal calcium nitrate . .Monoammomum phosphate
Sulphuric Ammoma 12-5-0
as a fertilizer since it is less deliquescent. acid - Phosphoric ·or
(excess) acid Diammonium phosphate
Phosphate
18-46-0
rock Triple s1}perphosphate
Urea is one of the world's most important chemicals because 46%P20 S
of its wide use as fertilizer.
It is manufactured by reacting ammonia and carbon dioxide Sulphuric and phosphoric acid Ammonium
under high atmospheric pressure near 200"C. Ammonium
• • • • • • • • • • • phosphate-sulphate
14-39-0 .
carbamate (NH2COO~) formed as an intermediate product
16-20-0
changes into urea.
o Nitric acid
- jP II
C02 + 2NH3 ~ H2N-C, ~ H2N- C -NH2 + H20 14-22% N 10-22 P20,
'O-NH!
(Anunonium carbamate Urea Sulphuric acid
an intermediate product)
• • • • • • • • • •1.1 Normal superphosphate
19-20"10 P20 S
A slurry of water, urea and ammonium nitrate is often applied
to crops under the name of "liquid nitrogen". Such a solution
can contain upto 30% nitrogen and is easy to store and apply.
when applied to the surface of the ground around plants urea Fig. 10.17 Phosphatic fertilizers from phosphate rock
is subjected to considerable nitrogen loss. When urea hydrolyses The important phosphatic fertilizers are:
(is decomposed by water) ammonia is formed, out of it some (i) Calcium superphosphate
ammonia is lost to the air and some is absorbed by moist soil (ii) Nitrophosphate
particles. As much as half of the nitrogen applied can be lost (iii) Triple phosphate
in this way. (iv) Phosphatic slag
Out of the nitrogen fertilizers, urea has the highest nitrogen
content equal to 46.6%. It has no explosive property and there (i) Calcium superphosphate or
is no risk in the storage. It does not alter the pH of the soil. It superphosphate of lime
can be used for all types of crops. However, there is one
Ca(H 2P04)2"H 20 + 2(CaS04"2H 20)
disadvantage, urea is not so stable as other nitrogenous
fertilizers. It decomposes even at lower temperatures in humid Calcium phosphate, Ca3(P04)z, is not very useful to a
atmosphere. It is highly soluble in water and hence requires· growing plant because of its very low solubility. When calcium
airtight packing. phosphate is treated with sulphuric acid it becomes more soluble
Note : Inorganic nitrate fertilizers are water soluble and contribute and is called "superphosphate".
significantly to nitrate pollution in the ground water of farming
Ca3(P04h +2H 2S04 ----7 Ca(H2P04h +2CaS04
regions. Since excess nitrates in drinking water andfood supplies Phosphate rock ' v '
cause blood disorders and contribute to the formation of Superphosphate
carcinogenic nitrosoamines,,; the present opinion is to keep the It is prepared on a large scale by treating phosphorite or
nittateout of the ground water or to remove it in the purification
bone ash with calculated quantity of 70% H2S04.
of drinking water.
Ca3(P04h+2H2S04 +SH 20----7
II Phosphatic Fertilizers Phosphorite
~a(H2P04h' H2~ + 2CaS0 4 .2H2~
The minerals of phosphorus such as phosphorite, Superphosphate of lime
[Ca3(P04h] and apatite, [3Ca3(P04h·CaF2] are sparingly Superphosphate of lime has 16-20% of P20 5.
"Carcinogens are chemicals, that cause cancer.

(ii) Nitrophosphate 4P + 502 ----? P40 lO }

It is prepared in the same way as superphosphate from 6CaO + P40 lO ----? 2Ca3(P04hThomas slag
phosphorite mineral using nitric acid instead of sulphuric acid. CaO + Si02 ~ CaSi03 · . .
The slag being lighter rises on the top of molten metal and
Ca3(P04h + 4HN03 ~~a(H2P04h +2Ca(N0 3h, is easily separated.. It is cooled. The solid mass thus obtained
. v
Nitrophosphate or is ground to a fine powder and used as fertilizer. It has 14-18 %
Calcium superphosphate nitrate
of P205.
The advantage of this fertilizer is that in addition to
phosphorus, it contains nitrogen as welL Thus, this is a mixed ~ Potash Fertilizers
fertilizer.
Potassium nitrate, potassium chloride and potassium sul-
(iii) Triple superphosphate of lime phate .are used as fertilizers.
This is another form of superphosphate. It is obtained by ~ NPK Fertilizers

the action of orthophosphoric acid, H3P04 (70%) with
phosphate mineraL Fertilizers containing N, P and K in suitable adjusted
proportions are known as NPK fertilizers. These are obtained
Ca3(P04h + 4H3P04 ----? 3Ca(H2P04h by mixing nitrogenous, phosphatic and potash fertilizers in
Triple phosphate has calcium hydrogen phosphate but it suitable proportions. Expression like 4--8-2 used for a mixed
does not have calcium sulphate that is why percentage of P20 5 fertilizer indicates that it contains 4% N2, 8% P20 5 and
in triple superphosphate in about three times to calcium super- 2%K20.
phosphate, and hence called triple superphosphate. It has In India, plants for the manufacture of fertilizers are
about 42-46% of P20:f. established/situated at,
1. Sindri (Jharkband)
(Iv) Phosphatic slag or Thomas slag: 2. Trombay (Maharashtra)
It is a by-pro<;luct of steel industry. When iron ore is burnt 3. Nangl (Punjab)
with limestone in the presence of air, calcium phosphate and 4. Rourkela (Orissa) and
calcium silicate appear as slag. 5. Namroop (Assam)
Example 1. Complete and balance the following reac- Solution:

tions: (i) 2HN03 ~ 2NO + H20 + 30
(i) Copper reacts with HN0 3 to give NO and N0 2 in molar
ratio of 2 : I. [I.I.T. 1992]
3Cu + 30 + 6HN03 ----? 3Cu(N03h + 3H20
(U) Red phosphorus is reacted with iodine in presence of 3Cu + 8HN03 ----? 3CU(N03h + 2NO + 4H20 ... (i)
water. [I.I.T. 1992]
2HN03 ----? 2N02 + H20 + 0
(iii) Ammonium sulphate is heated with a mixture of nitric
oxide and nitrogen dioxide. Cu + 0 + 2HN03 ----? Cu(N03h + H20
(iv) White phosphorus is boiled with a strong solution of Cu + 4HN03 ----? Cu(N03h + 2N02 + 2H20 ... (ii)
sodium hydroxide in an inert atmosphere. [I.I.T.1993]
(v) The preparation of ammonium sulphate from gypsum, To get NO and N0 2 in the ratio of 2 : 1, the eqn. (i) be
ammonia and carbon dioxide. [I.I.T.1990] multiplied by two and added in eqn. (li).
(vi) Nitrogen is obtained by the reaction of ammonia with 7Cu + 20HN03 ----?7CU(N03h + 4NO + 2N02 + 10H20
KMn04' [I.I.T. 1991]
(li) 2P + 312 ----? 2PI3
(vii) Aqueous solution of sodium nitrate is heated with zinc
dust and caustic soda. [U.T. 1990] 2PI3 + 3H20 ----? H3P03 + 3HI
(viii) Phosphorus reacts with cone. HN0 3 to give phos- (iii) NO + N02 ----? N203
phoric acid. [I.I.T.19911 (NH4hS04 ----? 2NH3 + H2S04
(ix) The preparation of phosphine from CaO and white
2NH3 + N20 3 ----? 2N2 + 3H20
phosphorus. [l.l.T. 1990]
(x) Sodium nitrite is produced by absorbing oxides of
nitrogen in aqueous solution of sodium carbonate. [I.I.T. 1991]
(iv) P4 + 3NaOH + 3H20 ~ 3NaH 2P0 2 + PH3 is the highest. Thus, it acts only as an oxidising agent. In
Sodium hyponitrous acid, HN0 2, nitrogen is in +3 oxidation state. Thus, it
phosphite
can be lowered or raised. Hence, HN02 acts both a<; an oxidising
(v) 2NH3 + H 20 + CO 2 ~ (NH4hC03 and a reducing agent.
(v) Nitrogen dioxide is present in HN0 3 which imparts
CaS04 + (NH4hC03 ~ (N~hS04 + C\C0 3 yellow colour to the nitric acid. N0 2 is usually formed by
(vi) 2KMn04 + H20 ~ 2KOH + 2Mn02 + 30 decomposition of HNO) in sunlight.
2NH3 + 30 ~ N2 + 3H20
4HN0 3 - - - - - t 4N0 2 + 2H20 + O2
2KMn04 + 2NH3 ~ 2KOH + 2Mn02 + N2 + 2H 20
Example 3. Explain the following with proper reason:
(vii) [Zn + 2NaOH ~ Na2Zn02 + 2H] X 4
(i) Nitrogen is a gas while other members of Vth group are
NaN0 3 + 8H ~ NaOH+ NH3 + 2H 20
, solids.
4Zn +7NaOH + NaN03~ NH3+4Na2Zn02+2H20 (ii) A bottle of liquor ammonia should be cooled before-
opening.
(viii) [2HN03 ~ H 20 + 2N02 + 0] X 10
(iii) Ammonia has a higher boiling point than phosphine.
P 4 + 100 + 6H20 ~ 4H3P0 4 [M.L.N.R.1993]
P4+ 20HN03 ~ 4H3P0,4+20N02+4H20 (iv) PFs is known but NFs is not. [M.L.N.R.1992]
(v) The experimentally determined N-F bond length in
(ix) (CaO + H 20 ~ Ca(OHh] X 3 NF3 is greater than the sum of single bond covalent radii of
8P + 3Ca(OHh + 6H 20 ~ 3Ca(H2P0 2h + 2PH3 Nand F [I.I.T.1995]
Solution:
8P + 3CaO + 9H20 ~ 3Ca(H2P0 2h + 2PH3 0) The nitrogen atom is small in size. It can undergo lateral
(x) Na2C03 + NO + N0 2 ~ 2NaN0 2 + CO 2 overlapping forming multiple bonds, i.e., nitrogen molecule
consists one sigma and two 1t-bonds The discrete
Example 2. Answer the following: molecules are held together by weak van der Waals' forces.
(i) Why concentrated H 2S0 4, anhydrous CaCl 2 or P4010 Thus, nitrogen is a gas. As the size increases, the lateral overlap
cannot be used as dehydrating agents for ammonia? is not strong and multiple bonds are not formed. Four atoms
(ii) Why nitrous oxide supports combustion more vigorously link together by single covalent bonds in tetrahedral form. The
than air? molecular masses become high and hence the rest of the
(iii) Why red phosphorus is denser and chemically less members of Vth group are solids.
reactive than white phosphorus? (ii) Liquor ammonia has high vapour pressure at room
(iv) Nitric acid acts as oxidising agent while nitrous acid temperature. It is cooled before opening as to reduce the vapour
can act both as an oxidising and a reducing agent. pressure inside the bottle in order to prevent bumping.
(v) Why comme rcial nitric acid is gene rally yellow in colour? (iii) Nitrogen being more electronegative, hydrogen bonding
Solution: is observed in ammonia, i.e., association of molecules occurs
(i) Conc. H 2S04, anhydrous CaCl 2 and P40 lO directly react through hydrogen bonding. This property is absent in
with ammonia. phosphine.
H2S04 + 2NH3 (NH4hS04 (iv) Nitrogen cannot extend its valency from 3 to 5 due to
CaCl 2 + 8NH3 CaClz'8NH3 absence of d-orbitals while phosphorus shows pentacovalency
P40 lO + 12NH3 + 6H20 ~ 4(NH4 hP04 as d-orbitals are present in it.
(v) The bond length is high due to r~ptilsion of the bonded
(ij) Air has oxygen about 1I5th of the volume while N20 on pair by both nitrogen and fluorine atoms. This is due to their
decomposition produces oxygen about l/3rd of the volume. smaller size and high electron density.
Total volume
Air 4 voL N2 + I vol. O 2; O 2 = - - - - - Example 4. A colourless inorganic sait ..(Ayqlecomposes
5 completely at about 250°C to give only two products (B) and
02 = Total voL of N2 and O 2 (C), leaving no residue. The oxide (C) is a liquid at room
2N2 + 02 ;
2 vol. I vol. 3 temperature and neutral to litmus paper while the gas (B) is a
(iii) Red phosphorus is regarded as a polymer consisting of neutral oxide. White phosphorus burns in excess of (B) to
chains of P 4 tetrahedra linked together. This makes red produce a strong white dehydrating agent. Write balanced
phospholllS denser and less reactive. equations for the reactions involved in this process.
(iv) In HN0 3 , the oxidation state of nitrogen is +5. Nitrogen [I.1.T. 1996]
can only be converted into lower oxidation states as +5 state
Elements of Group VA or 15 (Elements of Nitrogen and Phosphorus Family)
Solution :. Example 7. Answer the following:

Both (B) and (C) are neutral oxides. (B) helps in the (a) Why elemental phosphorus does not exist as Pzlike N2?
combustion of white phosphorus. Thus, (B) can be nitrous (b) How NO?: and PO?: ions are differ structurally?
oxide, N20. (A) is liquid at room temperature, thus it can be (c) NCl3 gets readily hydrolysed while NF3 does not, why?
water, H20. (d) Oxides of nitrogen have open chain structures while
The inorganic salt (A) is ammonium nitrate, NH 4N0 3 which those ofphosphorus have closed chain or cage structures. Why
on decomposition gives N 20 and H20. is it so? Illustrate with one structural example for each type of
NH 4N0 3 ----t N20 + 2H20 the oxides.
(A) (8) (C) Solntion:
ION 20 + P4 ----t P40 lO + lON 2 (a) Nitrogen because of small size has a tendency to form
Dehydrating mUltiple bonds and thus exist as a diatomic molecule, N==N.
agent Phosphorus has a comparatively larger size and it has no
---Example5~AI1 aqueous solution- o/a gas (X)- shows tendency to·£orm multiple-bonds-and-thusdoes not fDrmdiatornie----
following reactions: molecule, P=P. However, it prefers to form P4 molecules in
(i) It turns red litmus blue. which each P is linked to three other P atoms by three single
(ii) When added in excess to a copper sulphate solution, a covalent bonds and four P atoms lie at the corners of a regular
deep blue colour is obtained. tetrahedron.
(iii) On addition to ferric chloride solution a brownish (b) NO), ion exists as'afreeiori: Ithas b:igonal planafshape
precipitate soluble in HN0 3 is obtained. as N is in sp2 hybridized state.
Identify (X) and give equations for the reactions in step (ii) P03" ion does not exist as free ion but in the polymeric form
and (iii). [Roorkee 199U in which various PO)' units are linked through P-O-P bonds
Solution: to form either linear or cyclic structures. The P is in s/
The gas (X) is NH3· hybridized state.
Its aqueous solution is NH40H which turns red litmus to (c) In NCI 3, CI has vacant d-orbitals to accept lone pair of
blue. electrons from oxygen atom of H 20 molecule. Thus, hydrolysis
Step (ii) is possible. fu NF3, no d-orbitals are present.
CUS04 + 2NH40H ----t Cu(OHh + (NH4hS04 (d) Nitrogen on account of small size and high electro-
negativity has a strong tendency to form multiple bonds (pIt-
Cu(OHh + (NH 4hS04 + 2NH 40H -7 [Cu(NH3)4]S04+4H20
Tetramine pIt bonds) with oxygen and form oxides with open chain
copper (II) sulphate structures. Phosphorus has no tendency to form pIt '- pIt bonds
(blue colour)
with oxygen due to its large size and prefers to form single
FeCl3 + 3NH40H ----t Fe(OHh + 3NH4Cl bonds. As a result, closed chain or cage structure results.
Brownish ppt.
o
Fe(OHh + 3HN0 3 ----t Fe(N03 h + 3H20
Soluble
i
Example 6. Give the names and formulae of the /0-\-0\
compounds described below: o
o~p"" .-Y--, p-+o
(a) A chromium compound which on heating gives nitrogen 'N-O-N~
0
I 0-//
o-p-o
and an oxide of chromium. O~ "'0
(b) A compound of N, Hand 0 which is used as a freezing ~
o
salt and decomposes on heating giving a neutral oxide of
nitrogen.
(c) A compound of N, H, C and 0 which is used as a Example 8. (a) NF3 does not have donor properties like
fertilizer. ammonia. Explain.
Solution: (b) PCls acts as a chlorinating agent in organic reactions.
(a) Chromium compound is ammonium dichromate, Give reason.
(NH4)2Cr 20 7·
t r
(c) PCls exists as [PCI4 [PCI6 but PBrs exists as
[JD~r4]+~r-. l?xfllain.
(NH 4h Cr20 7 ~ N2 + Cr203 + 4H20
(b) The compound is ammonium nitrate, NH 4N0 3. Solution:
(a) NF3 has a pyramidal shape like NH3 with one lone pair
~N03 ----t NzO + 2H zO
Neutral oxide of electrons on N-atom.
(C) The compound is urea, NHZCONH2.
+5 +3
PCls + H 2 - - ) PCl 3 + 2HCI
+s +3
2PCls + Sn--) 2PCh + SnCl 4
The lone pair on N is in opposite direction to the N-F bond (b) H3P03 on heating is converted into H3P04 (oxidation
moments and therefore, it has a very little dipole moment. state +5) andPH 3 (oxidation state-3). Thus, this is a dispropor-
Thus, lone pair is not very effective and does not show donor tionation reaction.
properties. Howeve~, NH3 has high dipole moment because its +3 +S-3
4H 3P0 3 --) 3H 3P0 4 + PH 3
lone pair is in the same direction as the N-H bond moments. Phosphorus acid Orthophosphoric acid Phosphine
Electron density is high and thus, donor properties are observed. (C) In all the hydrides of group 15 elements, the central
(b) The structure of PCls is trigonal bipyramid. The axial atom undergoes sp3 -hybridisation. The three hybrid orbitals
P-CI bonds are slightly larger than the equatorial P-CI bonds. form sigma bonds with three hydrogen atoms and the fourth
molecule isl !illlS, lesss_tal>le. It breaks upto lose two contains a -lone pair of-electronS"; The lone pair·bond-pair - _. .
chlorine atoms present on axial positions and, thus, acts as a repulsions are larger than bond pair-bond pair repulsion. In
chlorinating agent. ammonia both forces are equally present in opposite directions,
(c) The formation of both PCls and PBrs is due to ~p3d_ hence the bond angle decreases from 109"28' to 107°5'.
hybridization of phosphorus, i.e., both have a trigonal bipyramidal
However, as we go from N to Sb, the size increases and the-
geometrY which is not a regular structure and,thus, is not very
repulsions between bond pair-bond pair go ondecreasing ana
stable. To attain more stable structure, PCls splits up into
thus the bond angles keep on decreasing from NH3 to SbH3.
tetrahedral and octahedral structures.
(d) The central atoms in both NH3 and Bill3 contain a lone
2PCIs ~ [PCl 4t [PCI6 r pair of electrons and thus, both should behave as Lewis bases.
Tetrahedral Octahedral But the size of Bi atom is much larger than the nitrogen atom.
But PBrs does not split up in the same fashion.- The anion The electron density on nitrogen atom is much higher in
[PBr6r is not possible due to large size of Br atoms. PBrs, comparison to Bi atom. Consequently, the tendency to donate
therefore, splits up into stable tetrahedral structure as, • the electron pair by N in NH3 is much higher than the tendency-
PBrs ~ [PBr4 t Br- of Bi in BiH3 . Therefore, NH3 is basic while Bill3 is feebly
Tetrahedral basic.
Example 9. (a) Can PCls act as an oxidising as well as Example 10. Illustrate, how does copper metal give
a reducing agent? Justify. different products on reaction with HN0 3.
(b) Give the disproportionation reaction of H 3P03. Solution:
(c) The HNH angle value is higher than HPH, HAsH and Nitric acid acts as an oxidising agent as well as an acid
HSbH angles. Why? when it reacts with copper. Dilute HN0 3 evolves nitric oxide
(d) Why NH3 is basic !Vhile BiH3 is only feebly basic? while concentrated HN0 3 gives nitrogen dioxide.
Explain. 2HN03 (Dilute) --) H 20 + 2NO + 3[0]
Solution: [Cu + 0--) CuO] x 3
(a) Phosphorus can exhibit a maximum oxidation state of [CUO + 2HN03 --) Cu(N03h + H20] x 3
+5. In PCls, the oxidation state of phosphorus is +5. Thus, it
3Cu + 8HN03 (Dilute) --) 3Cu(N0 3h + 2NO + 4H20
cannot increase its oxidation state beyond +5 and consequently
2HN03 (Cone.) --) H20 + 2N02 + [0]
it is unable to act as a reducing agent. However, it can act as
CU+ O~ CuO
an oxidising agent by undergoing decrease in oxidation state.
CuO + 2HN03 - - ) Cu(N03h + H20
For example,
SUMMARY AND IMPORTANT POINTS TO REMEMBER

J. VA or 15th group of the periodic table consists of six ns np
elements-nitrogen, phosphorus, arsenic, antimony, bismuth
and ununpentium. These elements are collectively known as [TI] lililil
pnictogens and their compounds pnictides. These elements are not so reactive as half filled orbitals are
1. These are p-block elements as the last differentiating electron present which are fairly stable. Nitrogen behaves as a noble
is accommodated on np shell. They have general confi- element under ordinary conditions.
guration of ninp3 configuration, All the p-orbitals of the 3. VAgroup is a mixed group of metals, metalloids and non- metals.
outer shell are singly occupied. Metallic nature increases as the atomic number increases.
N P As Sb Bi phorus is eleventh most abundant element in combined state.
~ '-.r---'
Non-metals Metalloids Metal It is never found free in nature. P is essential for life of both
animals and plants. It is present in DNA, RNA, ADP, ATP,
Nitrogen and phosphorus combine with electropositive
etc. As, Sb and Bi are not abundant.
elements and form nitrides and phosphides. Bismuth and
9. Nitrogen is chemically inert under ordinary conditions as it
antimony form alloys.
4. Nitrogen is a gas, the phosphorus is a waxy solid and can has very high dissociation energy. At high temperatures, it
can react with other elements. Phosphorus (white form) is
pass into vapour state readily. The remaining elements are
extremely reactive. The strained structure of P4 is responsible
solids and possess metallic lustre.
Nitrogen is a diatomic molecule, N ===N. The molecule has one for this. The heavier elements are less reactive.
sigma and two 1t-bonds. The dissociation energy is very large Only nitrogen in this group is capable of forming p1t-p1t
(225 kcal mol-I) and thus, is a stable and inert under ordinary multiple bonds within itself and with carbon, oxygen, etc.,
conditions. on account of small size. Phosphorus and other members do
p, _As JU1d~Sb-,allexisL as discrete tetratomic tetrahedral not form p1t:P1t mUltiple honds but they show multiple--
molecules, viz., P4, AS 4 and Sb4 as these are not capable of bonding of d1t-p1t. .
forming multiple bonds. The angle between X-X-X is 60°. 10. (a) Oxides of type X203, X204 and X205 are formed by the
5. In VA or 15th group: elements of group 15.
(a) density of the elements increases down the group. (b) Greater is the electronegativity more is the acidic nature
(b) melting points increase from nitrogen to As and then of its oxides. ..
decreases from As to Bi. (c) Acidic nature of each type decreases from N to Bi.
The lower values are due to formation of three covalent
~ ~S203 Sb203, Bi203
bonds instead of five covalent bonds due to inert pair
Acidic Amphoteric Basic
effect.
(c) atomic radii increase down the group. (However, it shows feeble acidic character with strong
(d) ionisation energy decreases regularly on moving down alkali.)
the group. NzOs P20 S ASzOs Sb20s BizOs .
AcidiC nafiIre decreaSes ... )
The ionisation energy of N is very high due to small size.
Acidic nature of M 20 4 oxides also decreases from N204
(e) electronegativity decreases gradually on moving down
to Bi20 4 .
the group.
(d) Thermal stability decreases in each series from N to Bi.
(f) all the elements except bismuth show allotropy.
(e) In the oxides of a particular element, the acidic nature
(g) N, P and As exhibit the property of catenation but this
increases as the percentage of oxygen increases or the
property is much less than IVA elements.
oxidation state increases.
6. All the members can show +5 oxidation state toward oxygen.
11. (a) All the members of group 15 form oxyacids or oxoacids.
Nitrogen and phosphorus generally exhibit -3 oxidation state
(b) The oxyacids of nitrogen are : hyponitrous acid (H2N20z),
due to high electronegativity. +3 oxidation state is observed .
nitroxylic acid (H2N20 4), nitrous acid (HN02), nitric acid
when only p electrons are used. Its stability increases due
. (HN0 3), peroxynitric acid (HN04)'
to inert pair effect.
Nitrous acid is unstable, weak monobasic acid, forms
Nitrogen besides -3, +3 and +5 oxidation states, exhibits a
stable salts. This acts as an oxidising and a reducing agent.
large number of oxidation states from -3 to +5. -3 in NH3,
-2 in NHz·NH z, -1 in NHzOH, 0 in Nz, + 1 in NzO, +2 in NO, Nitric acid is a stable, strong monobasic acid. It is a strong
+3 in N 20 3, +4 in N Z0 4 or N0 2 and +5 in N20 5 and HN0 3. oxidising agent.
7. These elements attain stable configuration by forming three (c) Phosphorus forms two types of oxyacids, one having P
covalent bonds. Except nitrogen, all other elements have in + 1 or +3 oxidation state, i.e., phosphorus acids and
d-orbitals in the valence shell. As a result, one of the two ns- other having Pin +4 or +5 oxidation state, i.e., phosphoric
electrons may be promoted to nd-orbitals to have five unpaired acids. Phosphorus acids act as reducing agents as they
orbitals in the valence shell. These can be utilised to form five tend to disproportionate. The important oxyacids of phos-
bonds. However, nitrogen can show a maximum covalency of phorus are : hypophosphorus acid (H3POz), phosphorus
4 when it donates the ns-electron pair to Lewis acids. acid (H 3P03), orthophosphoric acid (H3PO~, metaphos-
phoric acid (HP03), hypophosphoric acid (H4P206) and
Sb and Bi can lose three electrons to form M 3+ ions. Both
pyrophosphoric acid (~P207)' The number of OH group
SbF3 and BiF3 are ionic solids. M3+ ions are not stable in
or groups in oxoacids of phosphorus decides the basicity
solution. They are rapidly hydrolysed as SbO+ and BiO+ ions.
of the acid.
However, M3+ ions are stable in strong acids.
Acid H 3P0 2 H 3P0 3 H 3P0 4 HP0 3 I4P206 H4P207
8. Nitrogen is found in free as well as combined state. It forms
Basicity 1 2 3 1 4 4
75% by mass and 78% by vol. of atmosphere. In combined
Each oxoacid of phosphorus contains at least one P=O
state, it occurs as nitrates, proteins and amino acids. Phos-
unit and one P-OH unit.
506 G.R.B. Inorganic Chemistry for Competitions~
(d) Arsenic forrns two oxyacids-arsenious acid (H 3As03) 16. Scheele showed that air is a mixture of two gases : fIre air
and arsenic acid (H3As04). Antirnony forms only one (oxygen) and foul air (nitrogen). D.Rutherford narned foul air
acid H3Sb03. Bisrnuth also forrns one stable oxoacid, as mephitic air (killer of life). Later on the elernent was found
HBi03 rneta-bisrnuthic acid. to be present in nitre and thus, the narne nitrogen was
(e) The strength and stability of oxoacids having the ele- proposed.
rnent in sarne oxidation state decreases down the group. 17. Nitrogen can be obtained either frorn air or frorn the nitrogen
12. All the mernbers of this group form hydrides of the type cornpounds. In the laboratory, it is obtained by heating a
MH3· rnixture of arnrnoniurn chloride and sodiurn nitrite (NH4N02)
(a) All the hydrides are colourless gases. or amrnonium dichromate. Pure nitrogen is obtained by
(b) Their smell becornes rnore and rnore disagreeable frorn N passing ammonia vapours on heated CuO. It is also formed
to Bi. by action of nitrous acid on urea.
(c) The poisonous nature increases frorn NH3 to BiH3. 18. Nitrogen is a colourless, odourless and tasteless gas. It is
(d) NH3 is highly soluble in water but other hydrides are less not poisonous but animals do not survive in its atrnosphere
soluble. ~_due~to absence of ox.ygen. Itisnon-combustihleand.dQ~_
(e) The basic character decreases frorn NH3 to BiH3. not help in cornbustion. It cornbines with oxygen, hydrogen,
(t) Thermal stability decreases frorn NH3 to BiH3 . BiH3 boron, silicon and certain rnetals under specific conditions.
decornposes at roorn ternperature. It cornbines with CaC2 to form nitrolirn (CaCN 2+ C) at lOOOOC,
(g) The reducing nature increases. This shows M-H bond which is used as a fertilizer.
strength decreases frorn NH3 to BiH3. 19. Nitrogen forms three hydrides:(i) ammonia (NH3Wi) hy.dra~__
(h) The shape of these hydrides is pyramidal. The formation zine (NH2·NH2) and (iii)hydrazoic acid (N3H). Ammonia is
is due to sp3 hybridization. The bond angle is never equal obtained on a srnall scale by the action of caustic soda or
to ideal angle 109°28'. The actual angle in NH3 is 106°5 '. lirne on arnrnonium compounds, by reacting nitrides with
(i) Hydrogen bonding is present in NH3. No hydrogen water, by doing reduction of nitrates and nitrites with zinc
bonding is present in other hydrides. . and caustic soda, by heating ammonium cornpounds and by
action of NaOH on urea.
13. Except nitrogen, the rest of the elernents of group 15 form
20. For drying of NH3, quicklime (CaO) is used. Other dehydra-
two series of halides MCl 3 and MCls . However. all form
ting agents like H2S04, CaC1 2 and P20 S cannot be used as
trihalides but one or rnore pentahalides are forrned. Nitrogen
they react with NH3.
does not form pentahalides due to absence of d-orbitals.
21. On large scale, ammonia is manufactured :
(a) All the trihalides are stable except NCI 3, NBr3 and NI3'
(i) by Haber process,(ii) by Bosch's process (iii) by cyanamide
The unstable nature is due to low polarity of N-X and
process or as a by-product during coal distillation.
a large difference in the size of N and Cl.
22. NH3 is lighter than air and is highly soluble in water due to
(b) The trihalides have distorted tetrahedral structure
hydrogen bonding. It can be easily liquefied at roorn tempera-
involving sp3 hybridization.
ture by application of pressure. Liquid NH3 has a large heat
(c) The trihalides act as Lewis bases. This tendency
of vaporisation. It is, therefore, used in ice plants.
decreases frorn N to Bi.
Ammonia is a Lewis base as it donates an electron pair. It
(d) Except NF3 and PF3. all the trihalides are hydrolysed by forms ammonium salts with acids. It is oxidised to nitrogen.
water. When chlorine in excess, an explosive substance NCl 3 is
(e) Except N and Bi. other rnernbers form pentahalides formed. Iodine flakes when rubbed with liquor arnrnonia form
especially fluorides. a dark brown precipitate of ammoniated nitrogen iodide
(f) Pentahalides have a trigonal bipyrarnid shape (sp3 d (NH3NI3) which explodes readily on drying.
hybridization). Aqueous ammonia (N140H) foml rnany rnetal hydroxides.
(g) Pentahalides decornpose on heating into lower halides. Sorne of thern rernain in solution in the form of cornplex
(h) Pentahalides are hydrolysed by water. cornpounds.
(i) X-ray studies have shown that solid PCls is an ionic 23. Alkaline solution of K2Hg4 (Nessler's reagent) gives brown
cornpound cornposed of [PCI4t[PCl 6f. Solid PBrs exists precipitate with NH3 called iodide of Millon's base
as [PBr4t Br-. . (H2NHgOHgI).
14. With the exception of nitrogen, aU other elernents of group 24. Ammonia is used for the manufacture of nitric acid, sodium
IS forrn sulphides. The sulphides of arsenic and antirnony bicarbonate and ammoniurn compounds. Ammonium sulphate,
are soluble in yellow arnrnoniurn sulphide or ammoniurn amrnonium calcium nitrate, etc., are used as fertilizers.
sulphide and form thio-cornpounds. Ammoniurn nitrate is used in certain explosives. Ammoniurn
15. Nitrogen differs frorn the rest of the farnily rnernbers on hydroxide is used in laboratory. It is also used for the
account of following factors : rnanufacture of urea and for making artifIcial silk. Liquid NH3
(a) srnall size of nitrogen atorn. is used in refrigeration.
(b) high value of electronegativity. 25. Nitrogen forms fIve oxides: (i) N20, nitrous oxide (laughing
(c) absence of d-orbitals in the valency shell. gas) (ii) NO, nitric oxide (iii) N203, nitrogen trioxide (iv) N02
(d) tendency to form rnultiple bonds. . or N204, nitrogen dioxide (v) N20 S, nitrogen pentoxide.
Elements of Group VA or 15 (Elements 0/ Nitrogen and Phosphorus Family)
(a) Except N20 S, all oxides of nitrogen are gases at room as N0 2, NO, N20, N2 or NH 3. It also oxidises a number of
temperature. compounds.
(b) N20 and NO are neutral oxides while N20 3, N0 2 and N20 S
Concentration of Metal Main products
are acidic oxides. The acidic nature increases as percen-
nitric acid
tage of oxygen increases.
(c) N20 is a colourless gas with pleasant odour and sweet Mg, Mn H2 + metal nitrate
Very Dilute HN03
taste. When inhaled in moderate quantity, it produces
Fe, Zn, Sn NH4N0 3 + metal nitrate
hysterical laughter, hence named as laughing gas.
N20 is a linear and unsymmetrical molecule. Ph, Cu, Ag, Hg NO + metal nitrate
•• + + •• - Dilute HN03
[:N=N 0: f--->:N N-O: ] Fe, Zn N20 + metal nitrate
It is used as anaesthetic in dental or other minor surgical
Zn, Fe, Ph, Cu, Ag N02 + metal nitrate
operations in form of a mixture of N 20 and 02'
(d) NO is ~a~cGkmrlessgas, slightly heavier than airdt is Conc.HN0 3 SnN0:z +~H2Sn0:r
paramagnetic indicating the presence of unpaired Metastannic acid
electron in the molecule ( : N ••• 0: ).
Cone. HN03 Fe, Co, Ni, Cr, AI rendered passive
In the liquid and solid states, it forms a loose dimer, N 20 2.
(e) N20 3 condenses to a blue coloured liquid at ~30°C. The 28. Noble metals like gold, platinum, iridium, rhodium, etc.,
liquid when warmed decomposes int()NO and N02. It is dissolve in aqua-regia (3 parts conc. HCl plus one part conc.
called nitrous anhydride as forms nitrous acid with water. HN03). Aqua-regia forms nascent chlorine which attacks
It is represented as O=N--O-N-O. noble metals.
(f) N02 is a brown coloured gas with pungent odour. The 29. The replacement of one or more hydrogen atoms of an
liquid and solid is entirely N20 4 (dimer) at low organic compound by a nitro group (-N02) is known as
temperature. The molecule is V-shaped with O-N-O nitration. The nitration occurs in presence of conc. H2S04
bond angle 132 and N-O bond length 1.19 A. The
Q with the formation of nitronium ion, NOr.
molecule is an odd electron molecule. HN03 + 2H2S04 ~ NO~ + 2HSO;;: + H30+
(g) N20 S is a white crystalline solid. It is formed by action
Proteins are attacked by HN0 3 forming a yellow nitro
ofP 20 S with conc. HN0 3 .1t reacts with water and forms
compound called xanthoprotein.
nitric acid. It is, thus, known as nitric anhydride. It exists
A number of organic compounds are oxidised. Sawdust
as a symmetrical molecule in gaseous state, 02NON02'
catches fire when HN0 3 is poured over it. Turpentine oil
X-rays studies reveal that solid N20 S is ionic in nature,
bursts into flame when treated with fuming HN03· Cane sugar
i.e., nitronium nitrate NO~N03'
is oxidised to oxalic acid.
26. Nitrous acid is unknown in free state' but known only in
30. HN0 3 is used in the manufacture of explosives like T.N.T.,
solutions, It forms two series of organic derivatives, the
picric acid, nitroglycerine, etc. It is also used in the manu-
nitrites (R-ONO) and nitro compounds (R-N02)' It is,
facture of fertilizers, artificial silk, dyes, drugs, perfumes,
thus, considered to be tautomeric mixture of two forms
sulphuric acid, nitrates, etc. It is a laboratory reagent used
(HON=O and H
/l
N",). as a solvent for metals.
o 31. The name phosphorus has been derived from the property
27. HN0 3, nitric acid was earlier called as aqua/ortis (meaning of glowing in the dark.
strong water). It is a monobasic acid. It reacts with basic (Greek word, phos = light and phero I carry.)
oxides, carbonates, bicarbonates and hydroxides forming Phosphorus is extracted either from phosphorite or bone ash
corresponding salts. It usually acquires yellow colour, due by the application of either retort process (old process) or
to its decomposition by sunlight into N02. The yellow colour electrothermal process (modern process). In the modern
can be removed by warming it to 6O-80°C and bubbling dry process, phosphorite is mixed with carbon and silica. The
air through it. It has extremely corrosive action on skin and mixture is introduced into the electric furnace and heated at
causes painful sores. l400-l6000C. Vapours of phosphorus are condensed under
It acts as a strong oxidising agent. Non-metals are converted water. It is further purified by melting under acidified K2Cr207
into highest oxyacids by hot and conc. HN03 . N02 gas is and is redistilled.
evolved (S to H 2S04; P to H 3P04; C to H2C03 ; 12 to HI0 3; 32. Phosphorus exists in a number of allotropic forms. These are:
As to H3 As04; Sb to H3Sb04 and Sn to H2Sn03)' Most of
(a) yellow or white phosphorus
the metals except noble metals are attacked by HN0 3. It plays
(b) red phosphorus
double role in action on metals, i.e., it acts as an acid as well
(c) scarlet phosphorus
as an oxidising agent. Before the hydrogen is allowed to
escape,nitric acid is reduced into number of products such (d) black phosphorus
The main allotropic forms are yellow and red. o

The yellow form is the common variety. This form is . , t .
chemically active. It is a transparent waxy solid and can be ·b~p-.d· ·O.-;-;-P-.O·
.• I/R~'I •. .• 1/0"-'1 ..
easily cut with knife. It has garlic odour and is poisonous in :0 ~p '0' p~ 0: :0 ~p ...~ ----p~ 0:
nature. Vapours are also injurious. Persons working with .. I."·"
•.O·-P-·O.
..
.1
.
.. •• 1 .0.
. '- .
1
.o·-p-·o.
••
phosphorus develop a disease known as phossy jaw. • -!- •

This form undergoes slow combustion in contact with air and ..
:0:
glows in dark. This property is called chemiluminescence. It
readily catches fIre giving dense fumes ofP20 S and therefore,
P4010 is most effective drying or dehydrating agent.
kept in water.
When heated in inert atmosphere at 24O"C, it changes into 36. Following are some important compounds :
red variety. It is odourless and non-poisonous in nature. It (i) Scheele's green CuHAs0 3
(li) Graham salt (NaP03)6
does not sho""p!!osphorescence. It is not active in nature.
.. (iii) Paris-green-· (CH3C00)2CU:3Cu(A-sO:zh
It is regarded as a polymer consisting of P4 tetrahedrllIchains.
(iv) Pearl white BiOCl
33. Yellow phosphorus is used as a rat poison. Red phosphorus
is used in match industry and for making of HBr and HI. (v) Nitrophosphate Ca(H2P02h + 2Ca(N03h
(vi) Superphosphate of lime Ca(H2P04hH20 + 2CaS04·2H20
Radioactive phosphorus (p32) is used in the treatment of
(vii) Thomas slag 2Ca3(P04h·CaSi03
leukemia and other blood disorders. It is used for making
(viii) Sindri fertilizer (NH4hS04
incendiary bombs and smoke screens.
(ix) Nangal fertilizer (CAN) Ca(N0 3h·NH4N0 3
34. Phosphine is prepared by boiling yellow phosphorus with a
(x) Amatol 80% NH~03 + 20% T.N.T.
concentrated solution of sodium hydroxide in inert atmos-
(xi) Ammonal NH4N03 + Al powder
phere. Besides PH3, small amounts of H2 and P2~ are also
(small quantity) •
formed. As soon as the bubbles of the gas come in contact
(xii) Swarts reagent SbF3
with air, they catch fITe fonriing rings of smoke known as
(xiii) Tartaremetic (Potassium antimonyl tartarate)
vortex rings. This combustion is due to presence of P2H4.
(xiv) Angeli's salt Na2N203·H20
Pure phosphine can be obtained by using alcoholic potassium
37. Arsenic trioxide is called white arsenic and is a poison. Traces
hydroxide in place of aqueous NaOH. It is a colourless gas,
of arsenic are detected by Marsh test.
heavier than air, garlic like odour and poisonous in nature.
Pure PH3 does not spontaneously inflame. It burns in air or
38. Hydrazine is called diacid base and can form salts with one
or two equivalents of an acid. Hydrazine (NH2·NH2) and its
oxygen at 15O"C. The spontaneous inflammability at the time
derivatives are used as rocket-fuels.
of preparation (due to presence of P2~) is used in making
Holme's signals. The phosphine is less basic and more Hydrazoic acid (N3H) is a fairly strong acid, stronger than
reducing than NH3. The bond angle H-P-H is 93°. acetic acid but weaker than mineral acids. N3, azide is a
35. Phosphorus forms three important oxides. These exist in pseudohalogen ion. Hydrazoic acid acts both as oxidising
dimeric forms. and a reducing agent.
(i) Phosphorus trioxide (P406) 39. Both NF3 and NH3 have pyramidal structures with bond
(ii) Phosphorus tetroxide (P408) angles 102° and 107° respectively. Their dipole moments are
(iii) Phosphorus pentoxide (P401O) different-NF3 (0.24 D) and NH3 (1.48 D). The difference is
In the molecule of P406, the phosphorus atoms lie at the due to the fact that while the dipole moment due to N-F
tetrahedral position with each other and the 6 oxygen atoms bonds in NF3 are in opposite direction to the direction of
are inserted between them. Each P is bonded covalently to dipole moment of the lone pair on N-atom which partIy cancel
three O-atoms and each oxygen atom is bonded to two out, the dipole moments of N-H bonds in NH3 are in the
phosphorus atoms. same direction of the dipole moment of the lone pair on N
The structures of P408 and P4010 are similar to P406 with a , which add up.
difference that in P408 two alternate P-atoms are also linked 40. fu case of phosphorus tribalides, PX3 (X ;:; F, CI, Br, I) the
with an additional oxygen atom each and in P4010 each bond angle increases from PF3 to PI3.
phosphorus atom is linked with an additional oxygen atom 41. Hydroxylamine, NH20H, is a hydroxy hydride of nitrogen. It
by a coordinate linkage. is a derivative of ammonia. It is a weaker base than NH3. It
behaves as a mild reducing agent as well as an oxidising
:O....P-O: agent.
.pl/R~pl, 42. Some ammonium compounds decompose without evolving
• ·0· •
I:" .1 NH3·
. ..
.O'-p-·O. . ~~~N2+2H20
~03~N20+2H20
<NH4hCr2~ ~ N z + Cr2~ + 4H20
--
- PRACTICE PROBLEMS ~ ~Ip~~'~ ''"~

- .:.
~, ~~"-..... .- ;;
• Subjective Type Questions (iv) A mixture of NaN02 and NH4CI

(v) Ammonium dichromate
1. Answer the following: (vi) Orthophosphoric acid
(i) Why nitrogen is less reactive at room temperature? (vii) Phosphorus acid
(ii) NFs is not known. Why? (viii) Hypophosphorus acid
(iii) Why BiH3 is strongest reducing agent? (Ix) Copper nitrate
(iv) Which oxide of nitrogen becomes brown when released (x) Silver nitrate
in air? 7. Complete and balance the following reactions:
(v) Name two neutral oxides of nitrogen.
(i) KN0 3 + FeS04 + H2S04(conc.)~ ..... .
2. Answer the following:
(ii) Mg + HN0 3 ~ ..... .
(i) Why does PCl3 fume in air?
. - (iii) CuTHN03---rNOu+n..... ~+::.::.
(Ii) WhicheIemeiit of group 15 IS found in abunrumce in
nature? Heat
(iv) Pb(N03h - - - - t PbO +. ...... + ..... .
(iii) In which is the bond angle higher, PH! ion or PH 3
molecule? (v) CUS04 + NH40H(excess)~ .... ..
(iv) Are all the five bonds in PCIs molecule equivalent? (vi) NH3(excess) + C12~ ...... + ..... .
(v) Name three allotropic fonns of phosphorus. Which is (vii) NH3 + C12(excess) ~ .... ..
most reactive? (viii) AgO + ~OH ~ ..... .
(vi) What does the word cryogen mean?
(ix) Ag(NH 3hCI + HN03~ ......
3. Give reason:
Heat
(a) Why is ammonia highly soluble in water? (x) Ca3(P04h + Si02 + C - - - - t CaSi03 + CO + ..... .
(b) Nitrogen dioxide is paramagnetic in gaseous state. (xi) CaCN2 + H20(steam)~ CaC03 + ......
(c) Why does NH3 act as a Lewis base?
(xii) Ca3(P04h + H3P04 ~ ..... .
(d) Why conc. H2S04 cannot be used as dehydrating agent
(xiii) NH3 + NaOCI ~ ...... + NaO + H20 [I.I.T. 1993]
forNH3?
(xiv) P4010 + PCls ~ ..... . [I.I.T. 1998]
(e) Ammonia has higher boiling point than phosphine.
4. Explain briefly, why: 8. What happens when?
(a) White phosphorus is more reactive than red phosphorus? (i) A mixture of air and ammonia is passed over heated
(b) Hydrazine is unstable? platinum gauze. [M.L.N.R. 1990]
(c) Trihalides of nitrogen cannot be oxidised to pentahalides? (ii) Gold is treated with aqua-regia. [I.I.T. 1997]
(d) NO is paramagnetic whereas NO+ is diamagnetic? (iii) Water is added to calcium phosphide.
(e) Does H3P0 3 act as a reducing agent butH3P04 does not? (iv) Calcium phosphate is heated with a mixture of sand and
5. Give the names and formulae of the compounds described carbon.
below: (v) Phosphorus reacts with nitric acid to give equimolar
(i) A compound of N, H and 0 which on heating gives ratio of nitric oxide and nitrogen dioxide. .
laughing gas. (vi) Zinc is treated with very very dilute nitric acid.
(ii) A compound of N, Hand 0 which on heating gives (vii) Phosphine is treated with an acidified CUS04 solution.
nitrogen gas. [M.L.N.R.199O]
(iii) A compound of Ca, P and 0 which is found in bones. (viii) Iodine reacts with concentrated nitric acid.
(iv) A compound of Nand H which is used as refrigerant. [M.L.N.R. 1992]
(v) A compound of Nand H which behaves like an acid. (ix) Orthophosphoric acid is heated with nitric acid and
(vi) A compound ofN and H which is used as a rocket fuel. ammonium molybdate.
. (vii) A compound of N, H, S and 0 which is used as a (x) Disodium hydrogen phosphate is added to ammonical
fertilizer. solution of magnesium sulphate.
(viii) A compound of N, H and 0 which is used for making (xi) Magnesium is burnt in air and the product is treated
oximes. with water.
. (ix) Two neutral oxides of nitrog~n. (xii) Phosphine is passed through AgN03 solution .
(x) The oxyacid of phosphorus is used for the preparation (xiii) Phosphoric acid reacts with CaS(P04)3F. [LI.T. 1998]
of HBr and HI from bromides and iodides respectively. 9. How will you prepare?
6. Describe the action of heat on the following compounds: (i) Ammonia from calcium carbide.
(i) Ammonium nitrate (ii) Nitrogen from ammonium chloride.
(ii) Ammonium nitrite (iii) Phosphine from phosphorus.
fiii) \nll1111I1iI1l11,'hlnl'idc
(iv) Phosphorus from bone ash. (c) Draw the structure of P4010 and identify the number of
(v) Nitn;>us oxide from dilute nitric acid. single and double P-O bonds. [I.I.T. 1996]
(vi) Nitrogen dioxide from concentrated nitric acid. (d) Draw the structure of P406 and identify the number of
(vii) Ammonium nitrate from nitric acid. single P-O bonds.
(viii) Yellow phosphorus from orthophosphoric acid. (e) Write down the Lewis electron dot formula of the
(Ix) Metaphosphoric acid from orthophosphoric acid. following:
(x) Hydrogen from nitric acid. NO, N20 S, HN0 2, RN0 3, PH4I, H3PO b H3P04.
10•. Answer the following: (f) Write down the shapes of the following:
(i) How many unpaired electrons are present in the
valency shell of VA group elements? NH 3• NHt. N20, PCI 3, PCls, NO), PO.t.
. (ii) How many covalent bonds nitrogen can form? 15. Write short notes on the following:
(iii) What are the minimum and maximum oxidation states (a) Nitrogen fertilizers
of nitrogen? (b) Phosphorus fertilizers
(iv) Which oxyacid of nitFogen behaves-both as an~oxidis (c) Mixedfertilizers
ing and a reducing agent? (d) Action of nitric acid on metals
(v) Why NH3 exists as liquid whereas other hydrides of (e) Action of nitric acid on non-metals
the same group exist as gases? (f) Nitrogen cycle
(vi) Which oxide of nitrogen is paramagnetic and coloured? (g) Nitrogen fixation
(vii) What are the possible oxidation states for nitrogen? (h) Oxidation states of nitrogen
Give an example of each. (i) Oxides of nitrogen
(viii) What is the basicity of hypophosphorus acid? (j) Nitrates
(ix) Which allotropic form of phosphorus is more active? (k) Holme's signal
(x) What is the shape of phosphorus molecule? (I) Uses of nitric acid
11. Arrange the following as directed: (m) Passivity
(i) N, P, As, Sb and Bi (increasing order of stability of +5 16. Describe the principle of manufacture with conditions of the
oxidation state) following compounds:
(ii) NCb, PCI 3, AsCI), SbCI) and BiCl3 (order of ease of (i) Ammonia by Haber process.
hydrolysis) (ii) Nitric acid by Ostwald's process.
(iii) NH 3, PH3, AsH3 and SbH3 (increasing order of basic (iii) White phosphorus from bone ash by electrothermic
nature) method.
(iv) NH3, PH3. AsH3, SbH3 and BiH3 (increasing order of (iv) Ammonium sulphate from gypsum. [I.I.T. 1990]
stability) (v) Superphosphate of lime.
12. HowwUlyouobtain? (vi) Nitrolim.
(a) N2 from a mixture of N2 and CO. (vii) Urea.
(b) NH4Cl from a mixture of NH4Cl and KCI. 17. Explain the following with relevent reason:
(i) Nitric acid turns yellow in sunlight.
(c) Nitrogen from a mixture of N2 and 02.
[Ans. HN03 decomposes to form yellow N20 4 in sunlight.
(d) NH3 from a mixture of N2 and NH 3.
Sunlight
(e) PH3 from a mixture of PH3 and NH3. 4RN03 ) 2H20 + 2N20 4 + O2]
(f) N2 from a mixture of N2 and CO 2, (n) Why nitrate and nitrite cannot be distinguished by the
13. Write down the formulae of the following: action of conc. H2S04 ?
(i) Sal ammoniac [Ans. Because both liberate brown fumes of N02 on heating
(n) Laughing gas with cone. H 2S0 4 ,]
(iii) Superphosphate of lime (iii) Why N02 cannot be dried by means of NaOH
(iv) Triple superphosphate solution?
(v) Nitrophosphate [Ans. N0 2 is an acidic gas. It is absorbed in NaOH.}
(vi) Leuna saltpetre (iv) On heating Pb(N0 3h produces a pale yellow gas which
(vii) Nitrochalk on strong heating produces a brown gas.
(viii) Sindri fertilizer [Ans. Lead nitrate first produces N204 which is pale
(ix) CAN yellow. On further heating, it decomposes into nitrogen
(x) Nitrolim dioxide (brown in colour).
14. (a) Write the two resonance structures of N20 that satisfy
"
the octet rule. [1.l.T.1990; M.L.N.R. 1993] A pule A brown
(b) Give the structural formulae of phosphorus acid (H 3P03) yellow gas gas
and pyrophosphoric acid (H 4P20 7).
(v) Water has the highest boiling point among NH 3, PH}, (xvi) Pure PH 3 does not bum in air but impure sample ofPH 3
HClandH 20. bums in air.
[Ans. Maximum hydrogen bonding is present in water as [Ans. P2~' the liquid hydride is always present in impure
oxygen is the most electronegative among N, P, CI and phosphine. It catches fire as soon as it comes in
0.] contact with air.]
(vi) Nitric acid mostly forms oxides of nitrogen on reacting (xvii) Phosphorus does not fonn phosphorus penta-iodide.
[Ans. Due to large size of iodine, the effective overlapping
with metals while other acids react with metals to evolve
between the orbitals of P and I is not possible to form
hydrogen. covalent bonds.]
[Ans. In addition to being an acid, nitric acid is a strong
(xviii) Phosphorus acid is a dibasic acid.
oxidising agent. Before hydrogen is evolved, it reduces
[Ans. Phosphorus acid molecule, H3P0 3, possesses two
nitric acid into nitrogen oxides.]
hydroxyl groups, i.e., two replaceable hydrogen atoms.
(vii) Phosphine is prepared in an inert atmosphere of carbon o
dioxide or hydrogen. 1\
[AriS.Phosphine,beingl1ighly inflammable, bums ill air. It HO-P-OH
is therefore prepared in inert atmosphere.] I
(viii) Red phosphorus is used for making matches. H
[Ans. Red phosphorus is non-poisonous and has a high (xix) Urea is a better nitrogenous fertilizer than ammonium
ignition point] sulphate.
[Ans. Urea on hydrolysis gives NH3 and CO 2, NH3 is
(ix) Phosphorus pentoxide is used in the preparation of assimilated by plants and CO 2 goes to atmosphere,
N20 S' i.e., no residue is left in soil. Ammonium sulphate on
[Ans. P40lO is a strong dehydrating agent It removes water hydrolysis gives NH3 and H2S04, NH3 is assimilated
molecules from nitric acid to form N20 S' while H2S04 is retained in soil making it acidic.]
P40 lO + l2HN03 ---7 4H3P04 + 6N 20 S (xx) (SiH 3hN is a weaker base than (CH 3hN. [UT.1995]
or P40 lO + 4HN0 3 ---7 4HP0 3 + 2N20 S] [Ans. In (SiH 3hN, the lone pair of electrons on nitrogen is
used up in p1t-d1t back bonding. Such a p1t-d1t bonding
(x) Ammonia is used for refrigeration. is not possible in (CH 3hN due to absence of
[Ans. Ammonia has high heat of vaporisation.] d-orbitals in carbon. This accounts for more basic
(xi) The electronegativity of both nitrogen and chlorine is nature of (CH3hN than (SiH3hN.]
the same. But nitrogen is inert at room temperature (xxi) Mg3N2 when reacted with water gives off NH3 but HCI
whereas chlorine is highly reactive. is not obtained from MgCl 2 on reaction with water at
[Ans. Nitrogen molecule consists a strong triple bond room temperature. [I.I.T. 1995]
where'ls a chlorine molecule has only a single bond.] [Ans. MgCI2 is a salt of a strong acid and a strong base so
its hydrolysis is not possible whereas Mg3Nz is a
(xii) Ammonia acts as a ligand. salt ofa strong base, Mg(OHh. and a weak acid, NH 3,
[Ans. Due to the presence of a lone pair of electrons on so it gets hydrolysed to give NH3']
nitrogen which it can donate to acceptor (a metal ion)
(xxii) Aqua-regia dissolves gold.
and thus acts as a ligand.]
[Ans. Aqua-regia is a mixture of cone. HN0 3 and conc. HC!.
(xiii) Burning magnesium continues to bum in nitric oxide Both react to give nascent chlorine which attacks gold
while burning sulphur is extinguished. and forms gold chloride which dissolves.]
[An.s. The reaction between Mg and O 2 is highly exo-
(xxiii) Calcium cyanamide is used as a fertilizer.
thermic. i.e., the heat evolved is enough to decompose
[Ans. In soil, it is converted into urea which then decom-
NO into N2 and O 2 while the heat evolved during
poses into ammonia. This is assimilated by plants.
burning of sulphur is not sufficient to break NO.]
CaCN 2 + H20 + CO2 ---7 CN'NH2 + CaC0 3
(xiv) NF3 is not hydrolysed but NCl 3 is readily hydrolysed. Cyanamide
[Ans. Neither nitrogen nor fluorine possess vacant d-orbitals
CN'NH2 + H20 ---7 NH 2CONH 2
to form extra bond with lone pair of electrons on Urea
oxygen of water molecule. However. NCI J has vacant NH2CONH 2 + H20 ---7 2NH3 + CO 2 J
d-orbitals on chlorine atom.
(xxiv) Nitric oxide turns brown in air.
NCI 3 + 3H20 ---7 NH3 + 3HClO] [Ans. Nitric oxide directly reacts with oxygen of the air
(xv) Aluminium containers can be used for strong concen- forming brown fumes of N02.
trated HN0 3. 2NO + O 2 ---7 2NO z]
[Ans. Aluminium is rendered passive by conc. HN0 3 due (xxv) Copper dissolves in HN03 but not in HCl.
to formation of a fine film of its oxide on its surface.
[Ans. HN0 3 is an oxidising agent which converts copper
This film does not allow the dissolution of aluminium
metal in acid and thus AI-containers can be used to into CuO which dissolves in HN03 in the form of
store conc. HN0 3 .] copper nitrate.]
18. (i) An inorganic iodide (A) on heating with a solution of Bi(N03h + H20 --) [Bi(OH)(N03hl + HN0 3
KOH gives a gas (B) and the solution of a compound 2HN0 3 - - ) H20 + 2N02 + 0
(C). 2KI + 2HN03 + 0 --) 2KN0 3 + H20 + 12
(il) The gas (B) on ignition in air gives a compound (D) (Dark brown
ppt.)
and water.
(iii) Copper sulphate is reduced to the metal on passing (B) Yellow solution
. through the solution.
21. A colourless solid (A) liberates a brown gas (B) on
(iv) A precipitate of the compound (E) is fonned on
acidification, a colourless alkaline gas (C) on treatment with
reaction of (C) with copper sulphate solution.
NaOH and a colourless non-reactive gas (D) on heating. If
Identify (A) to (E) and give chemical equations for reactions
heating of the solid (A) is continued, it completely disappears.
at steps (i) to (iv). [Roorkee 1994J
Identify (A) to (D).
[Hint: Gas (B) on ignition gives water, therefore, hydrogen is
present in the gas.
[Ans. (A) = ~N02; (B) = N02; (C) = NH3; (D) = Nil
An inorganic iodide with alkali (KOH) gives a gas (B), 22. A compound (A) on heating with an excess of caustic soda
a hydrogen compOurid,so {Ar maybe NH41 or PH41. As solution-liberates- a gas . (B) which -gives whitefumeson----
NH3 does not reduce CUS04. therefore, the compound exposure to HCl. Heating is continued to expel the gas
(A) is PH4I. completely. The resultant alkaline solution again liberates the
(i) P~I + KOH --) PH3 + KI + H20 same gas (B) with zinc powder. However, the compound (A)
(A) (B) (C) when heated alone, does not give nitrogen. Identify (A) and
(ii) 4PH 3 + 802 --) P40lO + 6HzO (B).
[Ans. (A) = ~N03; (B) = NH3]
P4010 + 2H 20 --) 4HP03
(D)
23. An inorganic compound (A) when heated decomposes
Metaphosphoric completely to give only two gases (B) and (C). (B) is a neutral
acid gas, fairly soluble in water and itself decomposes on heating
(iii) 3CUS04 + 2PH3 --) CU3P2 + 3HzS04 to two different gases (D) and (E).
J, (A) when warmed with NaOH gives another gas (F) which
3Cu + 2P turns mercurous nitrate paper black. After sometime the gas
(F) ceases to evolve, however its supply is restored by
(iv) 2CUS04 + 4KI --) CU2I2 + 2K2S04 + 12]
(C) (E)
treating residual solution with aluminium powder. Identify (A)
to (F) and give necessary equations.
19. An orange solid (A) on heating gave a green residue (B), a [Ans.. (A) ~N03; (B) = N20; (C) = H20; (D) ::: N2 ;
colourless gas CC) and water vapour. The dry gas (C) on (E) = O2 ; (F) = NH3
passing over heated magnesium gave a white solid (D). (D)
on reaction with water gave a gas (E) which fonned dense
white fumes with HCl. Identify (A) to (E) and give the Heat
2N 20 2Nz + 02
~
reactions. [I.LT.I992]
~03 + NaOH NaN03 + NH3 + H20
[Hint: Formation of dense white fumes with HCl indicates that
the gas (E) is NH3· AI + NaOH + H20 --) NaAl02 + 3H
Ammonia is formed by hydrolysis of solid (D). Thus, (D) NaN03 + 8H --) NaOH + NH3 + 2H20]
should be Mg3N2. 24. In the following reaction,
Formation of (D) indicates that gas (C) is N 2 . Thus, (A) is
A+2B+HzO ~ C+2D
ammonium dichromate. '
(A ::: HNOz, B ::: HZS0 3, C NH20H). Identify D.
(NH4hCr207 --) N2 + Cr203 + 4H20
Orange (A) (C) Green (8) rUT. 1999]
[Ans. HN0 2 + 2H2S0 3 + H 20 --) NH20H + 2H2S04]
3Mg + N2 Mg3N2 (D)
(A) (B) (C) (D)
Mg3N2 + 6H 20 3Mg(OH)z + 2NH3 25. (i) Sodium salt of an acid (A) is fonned on boiling white
(El
NH3 + HCI --) ~CI ] phosphorus with NaOH solution.
Dense white (n) On passing chlorine through phosphorus kept fused
fumes
under water, another acid (B) is fonned which on strong
20. Gradual addition of KI solution to Bi(N03h solution initially heating gives metaphosphorus acid.
produces a dark brown precipitate which dissolves in excess (m) Phosphorus on treatment with cone. HN03 gives an
ofKI to give a clear yellow solution. Write chemical equations acid (C) which is also fonned by the action of dilute
for the above reactions. [LI.T. 1996] H2S04 on powdered phosphorite rock.
[Hint: Bi(N03h undergoes hydrolysis forming nitric acid. Nitric (iv) (A) on treatment with a solution of HgClz first gives a
acid liberates iodine from KI which dissolves in excess of white precipitate of compound (D) and then a grey
KI giving clear yellow solution. precipitate of (E).
Identify (A) to (E) and write balanced equations for the • Matching Type Questions
reactions at steps (i) to (iv). [Roorkee 2001]
[Hint: (i) P4 + 3NaOH + 3H20 ---7 3NaHzP0 2 + PH 3 Match the foUowing:
Sodium hypo phosphite [A] (a) Mephitic air (i) Phosphorus acid
Thus, acid (A) is H3P02, i.e., hypophosphorus acid. (b) Laughing gas (ii) Hydrazoic acid
(ti) 2P + 3Cl2 ---7 2PCl3 (c) Anhydride of HN03 (iii) Orthophosphoric acid
2PCl 3 + 6H zO ---7 2H 3P03 + 6HCl (d) Anhydride of HN02 (iv) Ammonia
(8)
(e) Anhydride of HP03 (v) Nitrogen dioxide
Phosphorus acid
(f) Dibasic acid (vi) Nitrogen pentoxide
H3P03 ~ HP02 + H 20 (g) Tribasic acid (vii) Phosphorus pentoxide
(iii) P4 + 20HN03 4H3P04 + 20NOz + 4H20 (h) Acid hydride of nitrogen (viii) Nitrous oxide
(C) (i) Basic hydride of nitrogen (]x) Nitrogen
Orthophosphoric acid
(j) Brown coloured gas (x) Nitrogen trioxide
Ca3(P04)z + 3H2S04 ---7 2H3P04 + 3CaS04 [B] (a) CAN (i) Freezing salt
(Pln.lsllh<irite (0) Npl( (ii):Manufacture of NH3
rock)
(c) Ammonium sulphate (iii) Nl4N03 +CaC03
(iv) H3POz + 2H20 ---7 H3P04 + 4H (d) Nitrolim (iv) Arsenious oxide
2HgClz + 2H ---7 Hg2CIZ + 2HCI (e) Anuuoniumnitrate (v) Manufacture of HN03
(D)
(f) Salammoniac (vi) NH4N03 + CNl4)zSQc
White ppl.
(g) Explosivernixture (vii) Nangalfertilizer
Hg2CIZ + 2H ---7 2Hg + 2HCI] (h) Haber process (viii) Sindri fertilizer
(E)
Grey ppt.
(i) Ostwald's process (IX) Calcium cyanamide
0) Poisonous oxide (x) Ammonium chloride
(k) Leuna saltpetre (xi) Mixed fertilizer
(1) Nitrochalk (xii) Amatol
Answers : Subjective Type Questions (b) In hydrazine, there is N-N single bond with lone pair of
1. (i) The dissociation energy of nitrogen molecule is very high i.e., electrons on each atom. Due to small size of nitrogen,
941.4 kJ mol-I. there is considerable repulsion between these non-bonding
(ti) Nitrogen cannot extend its valency from 3 to 5 due to absence electrons.
of d-orbitals. (c) Because of non-availability of d-orbitals, nitrogen can not
(iii) BiH3 is least stable as Bi is bigger in size in comparison to accommodate more than 8 electrons in its valence shell and
the size of hydrogen. therefore, its trihalides cannot be oxidised to pentahalides.
(iv) Nitric oxide, 2NO + Oz ---7 2NOz (d)t Nitric oxide is paramagnetic because of the presence of odd
Colourless Brown . '~Hectron. When this electron is lost, NO+ is formed which is
(v) Nitrous oxide, N20 and nitric oxide, NO diamagnetic.
2. (i) PCl3 combines with moisture of air and undergoes hydrolysis (e) H3P03 contains one P-H bond and acts as a reducing agent.
giving fumes of HC!. H3P0 4 does not contain P-H bond.
PCl3 + 3HzO H3P03 + 3HCl 5. (i) NH4N03 (ammonium nitrate); (li) NH4NOZ (ammonium nitrite);
(ti) Phosphorus (iii) Ca3(P04h (calcium phosphate); (iv) NH3 (ammonia); (v) N3H
(iii) PH! ion (hydrazoic acid); (vi) N zH4 (hydrazine); (vii) (N~hS04
(iv) No, Two axial P-Cl bonds are less stable than three equatorial (ammonium sulphate); (viii) NHzOH (hydroxylamine); (ix) N20
P-CI bonds. This is observed when PCls is heated. and NO; (x) H3P04 (orthophosphoric acid);
PCIs ---7 PCl3 + Cl2 6. (i) NH 4N0 3 ---7 N20 + 2HzO
(v) White or yellow, red and black. White phosphorus is most (li) NH 4N0 2 ---7 N z + 2H20
reactive. (tii) NH 4CI ~ NH3 + HCl
(vi) Freeze
(iv) NaN02 + Nl4CI ---7 Nl4N02 + NaCI
3. (a) Due to hydrogen bonding.
(b) Due to the presence of odd electron on nitrogen atom. NH 4N0 2 ---7 N z + 2H20
(c) Due to the presence of lone pair of electrons on nitrogen atom
NaN02 + NH4Cl ---7 N2 + NaCI + 2H20
which can be donated.
(d) NH3 combines with H2S04 and forms ammonium sulphate. (v) (NH4hCr207 ---7 N z + Cr203 + 4H20
(e) Hydrogen bonding in NH3 makes it as an associated
molecule.
4. (a) White phosphorus is more reactive due to higher angular strain
in its molecule.
514 GR.B, Inorganic Chemistry for Competitions
(iii) Ca3P2 + 6H zO ~ 3Ca(OH)z + 2PH3

(iv) 2Ca3(P04h + 6SiO z ~ 6CaSi03 + P40 lO
(vii) 4H 3P0 3 ~ 3H3P04 + PH3 + lOCO
(viii) 2H3P0 2 ~ H3P04 + PH3
2Ca3(P04h + 6Si02 + lOC ~ P4 + lOCO + 6CaSi0 3
(ix) 2Cu(N03h ~ 2CuO + 2N02 + O 2 (v) [2HN0 3 ~ NO + NO z + H20 + 20J xS
(x) 2AgN03 ~ 2Ag + 2N02 + O2
P4 + 100 ~ P4010
7. (i) 2KN03 + H2S04 ~ 2RN0 3 + K2S04 P4010 + 6H20 ~ 4H3P04
2HN0 3 ~ 2NO + H20 + 30 P4 + IORN03 + H20 ~ 4H3P04 + 5NO + SNOz
[2FeS04 + H2S04 + O~ Fe2(S04h + H20] x 3 (vi) [Zn + 2HN03 ~ Zn(N03h + 2H] x 4
[FeS04 + NO ~ FeS04,NO] x 2 RN0 3 + 8H ~ NH3 + 3H zO
2KN03 + 8FeS04 + 4H2S04 ~ HN0 3 + NH3 ~ ~N03
3Fe2(S04h + 2FeS04,NO + K2S04 + 4H 20
.. Brown-ring-
(Vii) 3CUS04 +2PH3~ TU3-r2 + ~H2S04
(ii) Mg + 2RN03 ~ Mg(N03h + H2
(viii) . [2HN0 3 ~ H20 + 2N02 + 0] x S
(iii) 2HN0 3 ~ H20 + 2NO + 30
3Cu + 30 + 6HN03 ~ 3CU(N03h + 3H20 12 + SO ~ 120 S
120 5 + H20 ~ 2HI03
3Cu + 8HN03 ~ 3CU(N03h + 2NO + 4H20
. (iv) 2Pb(N0 3h ~ 2PbO + 4N02 + O2
(v)CUS04 + 2NH40H ~ Cu(OHh + (NH4)zS04 + 12~hMo04~
Cu(OH)z + <NH4hS04 + 2~OH~ Cu(NH3)4S04 + 4H20 (NH4hP04,12Mo0 3 + 21~N03 + 12H20

(vi) 2NH3 + 3CIz ~ Nz + 6HCI (x) Na2HP04 + MgS04 + NH40H ~
6NH3 + 6HCl ~ 6NH4CI Mg~P04 + Na2S04 + H20

3H 20
8NH3 + 3CI2 ~ 6NH4CI + N2 (xi) 3Mg + Nz ~ Mg3NZ - - ) 3MgO + 2NH3
(Excess)
(xii) 3AgN03 + PH3 ~ Ag 3P +-3HN03 .
(vii) NH3 + 3CI2 ~ NCl 3 + 3HCI
(Excess) (xiii) Cas(P04hF + 7H3P04 + SH20~SCa(H2P04h·H20 + HF
(viii) AgCI + ~OH ~ AgOH + ~CI 9. (i) CaC2 CaCN 2 NH3
AgOH + ~CI + NH40~ ~ Ag(NH3hCI + 2H20 (ll) ~CI + NaNOz ~ NH 4NO z ~ N2
AgCI + 2N~OH ~ Ag(NH3)zCI + 2H20 Heat
(iii) P4 + Ba(OH)z - - ) PH3.
(ix) Ag(NH3)zCI + 2HN0 3~ AgCI + 2NH4N03
Digested PO Heat
(iv) Bone Ash + Conc. H2S0 4 l H3 4--)
(x) 2Ca3(P04h + 6Si0 2 ~ 6CaSi0 3 + P40 lO
Syrupy mass
P40 lO + IOC ~ lOCO + P4 Heat
HP03--) P4
Coke
(xi) CaCN 2 + 3H20 ~ CaC03 + (v) Zn + HN0 3(Dilute) ~ N20

(xii) Ca3(P04h + 4H3P04 ~ 3Ca(H2P04h . (vi) Cu + HN0 3(Conc,) ~ NO z
(vii) By passing NH3 through 60% HN0 3.
(xiii) 2NH3 + 3NaOCI ~ Nz + 3NaCI + 3H20
NH3 + RN03 ~ ~N03
Glue.
or NH3 + NaOCI - - ) NH2Cl + NaOH
(viii) HPO 3 ~P
Coke 4
NH3 + NHzCI ~ NHz~2 + HCI
NaOH + HCI ~ NaCI + H2O (ix) . HPO~HPO
3 4 600"C 3
2NH3 + NaOCI ~ NHZ'NH2 + NaCI + H2O
(x) Mg + HN03(2%) - - ) Hydrogen,
(xiv) P40 lO + 6PCIs ~ lOPOCl3 10. (i) Three; (ii) Four-3 covalent and one coordinate; (iii) -3 and +S;
Pt (iv) Nitrous acid; (v) Due to intennolecular hydrogen bonding in
8. (i) 4NH3 + S02 ) 4NO + 6H2O
750-900°C NH3; (vi) N02; (vii) -3. -2, -I, ,0, +1, +2, +3, +4, +S NH3
j •
(ii) [RN03 + 3HCI ~ NOCI + 2H20 + 2CI] x 3 (-3), NH2NH2 (-2), NH20H (-1), N3H (-3)' N2 (0), N20 (+1),
[Au + 3CI ~ AuCI3] x 2 NO (+2), N203(+3), N20 4 (+4), N20 S (+S); (viii) one; (ix) yellow
or white phosphorus; (x) tetrahedral.
[AuCI 3 + HCI ~ HAuCI 4] x 2
11. (i) Bi < Sb < As < P < N
2Au + 3RN03 + IlHCI ~ 2HAuC4 + 3NOCI + 6H 2O
(ii) NCl 3 < PCl3 < AsCl 3 < SbCl3 < BiCl 3
Elements of Group VA or 15 (Elements of Nitrogen and Phosphorus Family) 515--
(iii) SbH3 < AsH3 < PH 3 < NH3 (ix) Ca(N0 3)z·NH 4N0 3,
(iv) BiH3 < SbH 3 < AsH3 < PH 3 < NH3 (x) CaCN2 + C.
12. (i) By bubbling through ammonical cuprous chloride in which - + •• + •• -
14. (a) :N=N=O:~:N=N-O:
CO is absorbed but not N2.
(ii) By sublimation, NH4Cl sublimes leaving KCl as residue. o o 0
(iii) By bubbling through alkaline solution of pyrogallol in which II II II
oxygen is absorbed but not N2. (b) HO-P--'-OH HO-P-O-P-OH
(iv) By bubbling through H2S0 4 when NH3 is absorbed but not I I I
H HO OH
N2. Ammonia is recovered by heating the solution of (H 3P0 3 )
<NH4)zS04 with excess of NaOH.
(v) By bubbling through water in whichNH3 dissolves but not (c) Single bonds = 12
Double bonds = 4
PH 3·
(d) Single bonds = 12
(vi) By bubbling through water under high pressure or through
(e) Consult chapter on chemical bonding.
_N aOH_solution in_whichCnzdissohTes. but_noLNz.
(f) NH3 (Pytarnidal); NH4 (Tettatiedtal); N20 (Liliear); PCl-3-
13. (i) NH 4Cl, (Pyramidal); PCls in gaseous state (Triangular bipyramid); NO]
(ii) N20, (Triangular planar); POt- (Tetrahedral).
(iii) Ca(H 2P04)z·H20 + 2CaS04·2H20, 15. See text.
(iv) Ca(H 2P0 4)z, 16. See text.
(v) Ca(H2P04)z + 2Ca(N03)z, .Answers : Matching Type Questions
(vi) <NH4)zS04 + NH 4N0 3, [A] (a-ix); (~viii); (c-vi); (d-x); (e-vii); (f-i); (g-iii);
(vii) NRtN0 3 + CaC03, (h-ii); (i-iv); (j-v). [B](a-vii); (b--xi); (c-viii); (d-ix);
(e-i); (f-x); (g-xii); (h-ii); (i'-v); (j-iv); (k-vi); (I-iii).
(viii) (NH4)zS04,
IUUSTRATIONS· OF OBJECTIVE QUESTIONS

1. Ammonium nitrate is formed in : 4. Ammonia will be obtained in :
(a) Zn + v.dil. HN03 ~ (b) Fe + v.dil. HN0 3 ~ (a) CaCN2 + H20 ~ (b) NH4H2P04 Heat)
(c) Sn + dil. HN03 ~ (d) All (C) both (d) none
ADS. (d) ADS. (c)
[Hint: 4M + lOHN0 3 ---7 4M(N03)z + NRtN0 3 + 3H20] [Hint: CaCN2 + 3H20 ---7 CaC03 + 2NH 3;
2. A diatomic gas will be obtained in : NH 4H 2P0 4 ---7 NH3 + HP0 3 + H20]
(a) KN0 3 + K Heat) (b) NH4N03 Heat)
5. 230°C 640°C
NaH2P04 ~Na3(P309) ~(NaP03)n ~ (D)
(c) both (d) none compound (D) is : Glassy solid·
ADS. (a) (a) Bunsen's salt (b) Graham's salt
[Hint : 2KN03 + 10K ---7 6K20 + N2; (c) Reimann's salt - (d) Werner's salt
NH 4N0 3 ---7 N20 + 2H 20] ADS. (b)
3. Consider the following reaction, [ C;nt : (D) is sodium hexametaphosphate, (NaP0 3)6, which is
N02 + NaOH ~ (A) + (B) + H20 called Graham's salt.]
which of the following is correct? 6. The compound (SiH 3hN is expected to be:
(a) both (A) and (B) on heating with Na form N2 (a) pyramidal and more basic than (CH3hN
(b) both (A) and (B) on treatment with Zn and NaOH produce (b) planar and less basic than (CH3hN
NH3 (c) pyramidal and less basic than (CH3hN
(c) both are correct • (d) planar and mOre basic than (CH3hN
(d) none is correct ADS. (b)
ADS. (c) [Hint : (SiH 3hN is planar and less basic than (CH 3hN because
lone pair of N atom is used to form drt-p1t back bonding
[Hint: 2N0 2 + 2NaOH---7 NaN03+ NaN02+H20;
(A) (8) with Si-atom.]
2NaN0 3 + 10Na ---76Na20 + N2; 7. Which one of the following compounds on strong heating
NaN0 3 + 8H ZnlNaOH j NaOH + NH3 + 2H 20 ; evolves ammonia gas?
2NaN0 2 + '6Na ---7 4Na20 + N2; (a) CNH4hCr2~
NaN0 2 + 6H ZnINaOH) NaOH + NH3 + H 20 ] (c) NJ4N02
5.16 GR.B. Inorganic Chemistry for Competitions
ADS. Cd) 11. Which of the following metals, Fe, Zn, Pb, Ag and Pt do not
[Hint: (NH4hCr207 ---7 N2 ; NRtN0 3 ---7 N20; give metal nitrate on treatment with concentrated HN03?
NRtN02 ---7 N2 ; (NH4hS04 ---7 NH3] (a) Fe and Zn (b) Fe and Pt
(c) Pb, Ag and Pt (d) Fe, Ag and Pt
8. H3P04. 250·C) (X) ADS. (b)
12. The correct order of bond angle of NO!, N02 and NOi is:
~ 1
6000C
[J.E.E. (Orissa) 2006; C.B.S.E. 2008]
(Y) strongly) (Z) (a) NO! < N02 < N02 (b) NO! N0 2< N02
heated
(X), (Y) and (2) are : (c) NO! > N02 > N02 (d) NO! > N0 2 < N0 2
(a) ~P207' HP0 3 and P40 lO ADS. (c)
(b) HP03, H4P20 7 and P40lO [Hint: 180"
(c) H4P206, H 3P03 and P40 6 .. £2L
:O-N-Q:
(d) H 4P20 6 , HP03 and P406
··Ans:(a)
[Hint·. H 34
PO 250"C ) H 427
p. ° 600"C ) HPO strongly
3 heated)
p4'0 10 ] 13. Which of the following halides is most acidic?
(a) PC13 (b) SbC13
9. Solid PCls exists as :
(c) BiCl3 (d) CC4
(a) dimerP2CllO (b) [PC4t [pc16r
ADS. (a)
(c) (PC:I3)(CI2) (d) PCls as.such .
[Hint : In CCI4, carbon atom dOes not have d~orbita1s
ADS. (b)
accommodate a lone pair of electrons and hence is not a
10. How many P-O bonds and how many lone pairs
Lewis acid. In PC13. SbCl3 and BiCl3 central atom has
respectively are present in P406 molecule?
empty d-orbitals in each case but electronegativity of P is
(a) 12,4 (b) 8,8
maximum, hence PCl3 is strongest acid.]
(c) 12,16 (d) 12,12
ADS. (c) 14. Among the following ions, p1t dn overlap is present in:
[Hint : The structure of P406 is the number of P-O bonds and (a) NO) (b) PO~-
lone pairs are shown. These are 12 and 16 respectively.] (c) CO~- (d) N02:
Ans. (b)
./p-- .
'Q~ / .~
I '0' p'
:p~~
.o._-p-_.o!
. .. .
•
... -
Elements of Group VA or 15 (Elements of Nitrogen and Phosphorus Family) 5t7~
\
-
Set I : This set contains questions with single correct answer.
1. Which one of the following pairs is obtained on heating (a) it brings tears to eyes 0
ammonium dichromate? [J.E.E. (W.B.) 2008J (b) it has high vapour pressure 0
(a) N2 and H2O 0 (b) N20 and H2O 0 (c) it is corrosive liquid 0
(c) N02 and H 2O 0 (d) NO and N0 2 0 (d) it is mild explosive 0
2 By mixing ammonium chloride to potassium nitrite and 14. Which one of the following oxides of nitrogen is a coloured
heating, we get: gas?
(a) ammonium nitrate 0 (b) I<:l'ffit(N03h 0 (a) N20 2 0 (b) N~ 0
(c) nitrogen 0 (d) nitrogen dioxide 0 (c) NO 0 (d) N~ 0
3. The salt which on heating gives a mixture of two gases is: 15. Which one of the following is notan-acidsalt'?-
(a) NaN03 0 (b) KN03 0 (a) NaH2P02 0 (b) NaH2P03 0
(c) Pb(N03h [J (d) ~O3 0 (c) NaH2P04 0 (d) Na2HP04 0
4. Atomicity of phosphorus is: 16. Ammonia reacts with Nessler's reagent to give:
(a) 1 0 (b) 2 0 (a) deep blue precipitate 0 (b) white precipitate 0
El~
(c) 3 0 (d) 4 0 (c) green precipitate 0 (d) brown precipitate
5. Superphosphate of lime is: 17. Silver chloride dissolves in excess of N1L+OH. The cation
(a) Ca3(P04h·CaS04 0 present in solution is:
(a) Ag+ 0 (b) [Ag(NH3)4t 0
(b) Ca(H2P04h 0
(c) [Ag(NH3ht 0 (d) [Ag(NH3)6t 0
(c) Ca(H2P04h·CaS04 0
18. When NH40H is added to copper sulphate solution, blue
(d) Ca(H2P04h·H2Q.2CaS04·2H2O 0 colour is obtained due to formation of:
6. Laughing gas is: (a) Cu(NH3)4S04 0 (b) Cu<NH4S04h 0
(a) NO 0 (b) N20 0 (c) Cu(OHh 0 (d) CUO 0
(c) N20 3 0 (d) N20 S 0 19. By adding ofP20s to HN03:
7. Nitrous oxide is prepared in the laboratory by: (a) precipitate of yellow colour is formed 0
(a) combination of nitrogen and oxygen 0 (b) phosphorus gets free 0
(b) reduction of NO 0 (c) oxide of nitrogen is formed 0
(c) reduction of nitric acid 0 (d) ammonia is evolved 0
(d) thermal decomposition of NH~03 0 20. Phosphorus is manufactured by heating in an electric furnace
8. Ammonia is not used: the mixture of:
(a) an anaesthesia 0 (a) bone ash and coke [}
(b) in medicine 0 (b) bone ash and silica 0
(c) in cold storages 0 (c) bone ash, silica and coke 0
(d) for preparation of artificial silk 0 (d) bone ash, NaCI and coke 0
9. Which one of the following is used for drying of ammonia? 21. Which one of the compound is not known?
(a) cone. H2SO4 0 (b) Cao 0 (a) NOs 0 (b) Pas 0
(c) P20 5 0 (d) anhydrous CaCl2 0 (c) AsCls 0 (d) N03 0
10. Phosphorus is kept in: 22. Nitrolim is obtained by passing nitrogen over:
(a) kerosene 0 (b) alcohol 0 (a) heated mixture of Al 20 3 and carbon 0
(c) water 0 (d) ammonia 0 (b) carborundum 0
11. A hydride of nitrogen which is acidic in nature: (c) calcium carbide 0 (d) heated aluminium 0
(a) N3H 0 (b) N2~ 0 23. The largest bond angle is in:
(c) NH3 0 (d) N4~ 0 (a) AsH3 0 (b) NH3 0
12. Which one of the following is not used for the manufacture (c) H2O 0 (d) PH3 0
of ammonia? 24. A certain element forms a solid oxide which dissolves in
(a) Haber process 0 water to form an acidic solution. The element is:
(b) Cyanamide process 0 (a) S 0 (b)Mg 0
(c) Ammonical mother liquor 0 (c) Na 0 (d) P 0
(d) Solvay ammonia process 0 25. A colourless gas X forms a brown coloured gas when mixed
13. It is recommended that ammonia bottles be opened after The
with air. gas X is:
cooling in ice for sometime. This is because: (a) NH3 0 (b) ID 0
(c) N20 0 (d) N~ 0
26. Which one of the following is used as anaesthetic? 41. Amongst the trihalides of nitrogen, which one is least basic?
(a) NH3 D (b) N20 D (a) NF3 D (b) N03 D
(c) NO D (d) N02 D (c) NBr3 D (d) NI3 D
27. The catalyst used in the manufacture of ammonia by Haber 42. Which one of the following is the strongest base? .
process is: (a) ASI-l3 D (b) SbH3 D
(a) Pt D . (b) Fe D (c) PH~ D (d) NH3 /
D
(c) Mo D (d) V20 S D 43. Skin becomes yellow in conc. HN03 because:
28. The catalyst used in the manufacture of NO by Ostwald's (a) the proteins are converted into xanthoproteins D
process is: (b) HN0 3 acts as a dehydrating agent .[]
(a) Pt D (b) Fe D (c) nitrocellulosl'! is formed D
(c) Mo D- (d) Cu D (d) HN0 3 acts ~s an oxidising agent D
29. The correct order of acidic nature of oxides is : 44. The number of p-4)-p and P---OH bonds present
(a) N20 S < N20 3 < N0 2 < NO < N20 D respectively in pyrophosphoric acid molecule are :
(b) N28<N8<N20 3 <-NOz-<N20S .D . (a) 2,2 . . . - - .. ---D-(bH,-8 ------ -D-
(c) N20 S < N20 < N20 3 < NO < N0 2 D (c) 1,4 [J (d) 1,2 D
(d) NO < N20 < N20 3 < N0 2 < N20 S -0 45. . Nitrates of all metals are:
30. Nitrogen dioxide cannot be obtained by heating: (a) insoluble in water D (b) soluble in water D
(a) KN03 D (b) Pb(N03h D (c) unstable D (d) coloured D
(c) Ca(N03h D (d) AgN0 3 D 46. A gaseous mixture contains O2 and N2 in the ratio of 1 : 4 by~
31. Ammonia solution dissolves fairly: mass. The ratio of their molecules is:
(a) Hg20 2 D (b) PbCl2 D (a) I: 4 D (b) I : 8 D
(c) AgI D (d) Cu(OHh D (c) 3 : 6 D (d) 7: 32 D
32. When ammonia is heated with CO 2 under pressure, the 47. Which of the following will combine with Fe (II) ion to form
product is: a brown complex compound?
(a) CNH4hC03 . 0 (b) NH2CONH2 D (a) N20 D (b) NO D
(c) NH2COO~ D (d) Nl4HC03 D (c) N20 3 D (d) N02 D
33. The percentage of nitrogen in. urea is about: 48. Red phosphorus is made by heating yellow phosphorus in
(a) 70 D (b) 63 D the presence of an inert gas at temperature:
(a) 60°C D (b) 200°C D
(c) 47 D (d) 28 D
(c) 240°C D (d) lOO°C D
34. A wl)ite precipitate is obtained on hydrolysis of:
49. Phosphorus is used in:
(a) PCls D (b) N03 D
(a) photography D (b) cement industry D
(c) BiCl3 D (d) AsCl 3 D
(c) rubber industry D (d) match industry D
35. Industrial preparation of nitric acid by ostwald's process
50. When phosphine is bubbled through a solution of silver
involves:
nitrate, ...... is precipitated.
(a) oxidation of NH3 D (b) reduction of NH3 D
(a) silver 0 (b) silver phosphide D
(c) hydrogenation of NH3D (d) hydrolysis of NH3 D
(c) silver oxide D (d) none of these D
36. When treated with nitric acid which of the following liberates
51. When orthophosphoric acid is heated at 240°C, the main
hydrogen?
product formed is:
(a) zinc D . (b) copper D
(a) HP03 D (b) H3P0 2 D
(c) magnesium D (d) mercury D
(c) H3P03 D Cd) ~P2~ D
37. Concentrated nitric acid oxidises cane sugar to: 52. Complete manure is that which supplies:
(a) CO 2 and H20 D (b) CO and H20 D (<1) ~, K ?!!d N D (b) N, K and P D
(c) CO, CO 2 and H20 D (d) oxalic acid and water D (c) ·S and N D (d) S, N and P D
38. White phosphorus reacts with caustic soda. The products 53. Superphosphate of lime is obtained by treating:
are PH3 and NaH2P0 2. This reaction is an example of: (a) calcium phosphate with HCI D
(B.H.U. 2007] (b) calcium phosphide with HCI D
(a) oxidation D (b) reduction D (c) calcium phosphate with H2S04 D
(c) neutralisation D (d) disproportionation D (d) calcium phosphate with NaOH D
39. White phosphorus may be removed from red phosphorus by: 54. PH3 produces smoky rings when it comes in contact with
(a) sublimation D (b) distillation D air. This is because:
(c) dissolving in CS2 D (d) heating in air D (a) it is inflammable D
40. Which one of the acids is a dibasic acid? (b) it combines with water vapour D
{P.E.T. (Kerala) 2019J (c) it combines with nitrogen D
D (b) H3P02 D (d) it contains impurity of P2~ D
D (d) H 3P04 D
Elements of Group VA or 15 (Elements oiNitrogen and Phospl1prus Family) ·Sl9--
55. The metal which becomes passive in contact with conc. (c) conc. HN0 3 + NO z 0
HN0 3 is: (d) conc. HN03 + cone. H ZS0 4 0
(a) copper 0 (b) aluminium 0 68, The number of steps, in which orthophosphoric acid is
(c) zinc 0 (d) silver 0 ionised, are:
56. Which gas is obtained when urea reacts with nitrous acid? (a) 1 0 (b) 2 0
(a) N z 0 (b) NO 0 (c) 3 0 (d) 4 0
(c) NzO . 0 (d) NO z 0 69. Phosphorus is usually extracted from:
57. Nitrogen percentage is the highest in the fertilizer: (a) phosphorite 0 (b) apatite 0
(a) ammonium sulphate 0 (b) CAN 0 (c) chlorapatite 0 (d) triphylite 0
(c) urea 0 (d) calcium cyanamide 0 70. PCIs is kept in well stoppered bottles because:
58. When zinc reacts with very dilute nitric acid it produces: (a) it is highly volatile 0
(a) NJ4N03 0 (b) NO 0 (b) it reacts readily with moisture 0
(c) NOz 0 (d) Hz 0 (c) it reacts with oxygen 0 (d) it is explosive 0
59. WhiGh of thefollowing-properties-ofwhite phosphorus are . ''71. Tbe aOOydrid~_QfJ:hP()4
shared by red phosphorus? (a) PZ0 3 0 (b) PZ0 4 0
(a) It phosphorescences in air 0 (c) PzOs 0 (d) P03 0
(b) It burns when heated in air 0 72. Phosphate + conc. HN03 + (NH4)zMo04 soln. ~ Yellow
(c) It dissolves in CS z 0 precipitate. The composition of yellow precipitate is:
(d) It reacts with NaOH to give PH3 0 (a) (Nl4hP04'.Mo03 .0 (b) (Nl4hP(kl2MoCh.t::J
00. The number of P~O~P bridges in the structure of P40 lO (c) (Nl4)zP04,12Mo03 0 (d) ~P04·Mo03 0
and P406 are respectively : 73. Which one of the materials is not used as a fertilizer of
(a) 5,5 0 (b) 5,6 0 phosphorus?
(c) 6,6 0 (d) 6,5 0 (a) Superphosphate of lime 0
61. Arsenic' is detected by: (b) Phosphatic slag 0
(a) ring test 0 (b) Lucas test 0 (c) Guano 0
(c) lake test 0 (d) Marsh test 0 (d) Phosphorite mineral 0
62. Nitrogen molecule is chemically less active because of its: 74. Which one of the following statements is wrong?
. (a) small atomic energy 0 (a) Ammonia is more poisonous than phosphine 0
(b) high dissociation energy 0 (b) Ammonia is more basic than phosphine 0
(c) high electro negativity [j (c) Ammonia is more stable than phosphine 0
(d) stable electronic configuration 0 (d) Ammonia is more soluble in water than phosphine 0
63. Which of the following statements is not true? 75. One of the acids listed below is formed from PZ0 3 and the
(a) Nitrogen differs markedly from the other members of its rest are formed from PzOs. The acid formed from PZ0 3 is:
family 0 (a) HP03 0 (b) 14Pz~ 0
(b) Nitrogen has five valency electrons 0 (c) H 3P04 0 (d) H3P03 0
(c) Nitrogen does not show a greater covalency than three 76, Concentrated nitric acid reacts with iodine to give:
o (a) HI 0 (b) HOI 0
(d) Nitrogen shows great stability as a free element o (c) HOI02 0 (d) HOI03 0
64. Liq1:lid ammonia is used in refrigerators because: 77. Addition of cone. HN0 3 to cone. H ZS04 gives :
(a) it has high dipole moment o (a) SO~- 0 (b) S03 0
(b) it has high solubility in water o (c) N0 3 0 (d) NO~ 0
(c) of its basicity o [Hint : HNO) + H2S04 ~ Noi + HS04 + H20]
(d) it has high heat of evaporation o 78. The reaction between NH'2 and NzO gives :
65. The yellow colour often shown by nitric acid can be (a) NO 0 (b) NzOs 0
removed by: (c) NH 2NHz 0 (d) N3 0
(a) bubbling air through the warm acid 0 [Hint: NHi + N20 ~ N3 + H20
(b) boiling the acid 0 NaNH2 + H20 ~ NaOH + NH 3]
(c) passing ammonia through acid 0 79. Red phosphorus is less reactive than yellow phosphorus
(d) adding a little Mg powder 0 because:
66. One mole of which of the following acids neutralises the least (a) its colour is red 0
number of moles of KOH? (b) it is highly polymerised 0
(a) H3P04 0 (b) 14Pz~ o (c) it is tetratomic 0
(c) H3P03 0 (d) H3POz o (d) it is hard 0
67. Aqua-regia is: 80, Which of the following oxides of nitrogen is the anhydride
(a) conc. HN0 3 + 2 conc. HCl o of nitrous acid?'
(b) cone. HN0 3 + 3 conc. HCl o
(a) NO 0 (b) N20 3 o 94. Which of the following fluorides does not exist?
(c) N20 4 0 (d) N20S o (a) NFs 0 (b) PFs 0
81. Which of the following trihalide cannot be hydrolysed? (c) AsFs 0 (d) SbFs 0
(a) PF3 0 (b) PC13 0 9S. When ammonia is passed over heated CuO, it is oxidised to:
(c) AsCl3 0 (d) SbCI3 0 (a) HN02 0 (b) N20 0
lHint : PF 3 because P-F bond is stronger than P-O bonQ.] (c) N2 0 (d) N02 0
82. The number of vacant orbitals in the valence shell of phos- 96. The CN- ion and N2 are isoelectronic. But in contrast to
phorus is : CN-, N2 is chemically inert because of:
(a) S o (b) 3 o (a) low bond energy 0
(c) 2 o (d) 0 o (b) absence of bond polarity 0
lHint : 5d-orbitals] (c) unsymmetrical electron distribution 0
83. Which of the following is not a base? (d) presence of more number of electrons in bonding
(a) N3H 0 (b) N214 0 orbitals 0
(c) NH20H 0 (dUCH3hN 0 W.-Nitrogendioxide-isreleasedon-heating:-· - -- - - .-
84. One mole of calcium phosphide on reaction with excess of (a) Nl4N03 0 (b) KN03 o
water gives: (c) NaN02 0 (d) Pb(N03h o
. (a) one mole of phosphine o 98. Which oxide does not act as a reducing agent?
(b) two moles of phosphoric acid o (a) NO 0 (b) N02
(e) two moles of phosphorus pentoxide o (c) N20 0 (d)N20 S
(d) two moles of phosphine o 99. Of the following, which has three electron bond in its
8S. The number of nitrogen to oxygen bonds in N20S is : structure?
(a) 3 0 (b) 4 o (a) Nitrous oxide 0 (b) Dinitrogen trioxide . 0
(c) S 0 (d) 6 o (c) Nitric oxide 0 (d) Nitrogen pentoxide 0
o 1 yO 100. When AgN0 3 is heated strongly, the products formed are:
lHint: ~N2.0~N~] (a) NO and N02
(c) N0 2 and 02
0 (b) N0 2 and N20
0 (d) NO and 02
0
0
o 2 0>:0
86. Which one of the following cations does not form complex 101. Aqueous solution of ammonia consists of:
with ammonia? (a) if 0 (b) Olr 0
(a) Ag+ o (b)"Cu2+ o (c) NR! 0 (d) NR! and OW 0
2
(c) Cd + o (d) Pb2+ o 102. Each of the following is true of white and red phosphorus
87. When concentrated nitric acid is heated, it decomposes to except:
give: (a) both are soluble in CS2 o
(a) oxygen and nitrogen 0 (b) consist of same kind of atoms o
(b) nitric oxide 0 (c) can be oxidised by heating in air o
(c) oxygen 0 (d) can be converted to one another o
(d) nitrogen dioxide and oxygen 0 103. NH3 has much higher boiling point than PH3, because:
88. In P4010, the number of oxygen atoms bonded to each (a) NH3 has much higher molecular mass 0
phosphorus atom is: (b) NH3 forms hydrogen bonds 0
(a) 2.5 o (b) 3 o (c) NH3 contains ionic bonds while PH3 contains covalent
(c) 4 o (d) S o bonds 0
89. When bismuth chloride is poured into a large volume of (d) NH3 undergoes umbrella inversion 0
water, the white precipitate produced is: 104. PCl3 reacts with water to form:
(a) Bi(OHh 0 (b) Bi2~ 0 . (a) PH3 0 (b) H 3P0 3 andHCI o
(c) Bi20 s 0 (d) BiOO 0 (c) POCl3 0 (d) H3P04 o
90. Which of the following elements is metallic? lOS. By the action of cone. H 2S04, phosphorus changes to:
(a) P 0 (b) As 0 (a) phosphorus acid 0 (b) metaphosphoric acid 0
(c) Sb 0 (d) Bi 0 (c) orthophosphoric acid 0 (d) pyrophosphoric acid 0
91. Which one has the lowest boiling point? ms. Mixture used in Holme's signal is:
(a) NH3 0 (b) PH3 o (a) CaC2 and CaCl2 0 (b) CaCl2 and Ca3P2 o
(c) AsH3 0 (d) SbH3 o (c) CaC2 and Ca3N2 0 (d) CaC2 and Ca3P2 o
92. The most stable hydride is: 107. Blasting of TNT is done by mixing:
(a) NH3 0 (b) PH3 o (a) Nl40 0 (b) Nl4N03 0
(c) AsH3 0 (d) SbH3 o (c) Nl4N~ 0 (d) CNH4hS04 0
93. Which is most explosive? 108. Among the oxyacids given below, the correct decreasing
(a) NCl3 0 (b) PC13 o order of acid strength is :
(c) As03 0 (d) all o (i) H3As04 (ii) H3Sb04 (iii) HN0 3 (iv) H3P04
(a) (iv) > (iii) > (ii) > (i) 0 (b) (iii) > (iv) > (i) > (li) 0 120. A metal X on heating in nitrogen gas gives Y. Yon treatment
(c) (iii) > (ii) > (iv) > (i) 0 (d) (iii) > (i) > (ii) > (iv) 0 with H20 gives a colourless gas which when passed through
109. Among the following oxides, the lowest acidic is: CUS04 solution gives a blue colour. Y is: [D.C.E. 2000]
(a) P406 0 (b) P40 lO 0 (a) Mg(N03h 0 (b) Mg3N2 0
(c) AS 40 6 0 (d) AS4010 0 (c) NH3 0 (d) MgO 0
110. The basic character of the hydrides of Vth group elements 12L In which of the following the bond angle is maximum?
decreases in the order: [C.B.S.E. 2001]
(a) NH3 > PH3 > AsH3 > SbH3 0 (a) NH3 0 (b) NHt 0
(b) SbH3 > AsH3 >PH3 > NH3 0 (c) PCh 0 . (d) S02 0
(c) NH3> SbH3 > PH3 > AsH3 0 122. Nitrogen forms N2 but phosphorus is converted into P4 from
(d) SbH3 > PH3 > AsH3 > NH3 0 P2. The reason for this is: [C.B.S.E. 20011
111. Solid PCl5 exists as : (a) triple bond is present between phosphorus atoms 0
[pC14t [PClil-
(a) 0 i'!Ld.i;mer P~<:2111L 0 (b) p1C-p1C bonding is weak 0
(c) [PCI3][CI2] 0 (d)PCls as such 0 (c) p1c~p1C bonamg~is s t r o n g u - - - - -
112. Which of the following species is paramagnetic? (d) multiple bond is formed easily 0
(a) oi- 0 (b) NO 0 123. In NO) ion, the number of bond pair and lone pair of
electrons on nitrogen atoms are:
(c) CO 0 (d) rn- 0
113. The BCl3 is a planar moleculewhereas,NCl:, is pyramidal [C.B.S.E. 2002; A;F.M;C. 2002)
because: (a) 2,2 0 (b) 3,1 0
(a) N-Cl bond is more covalent than B-CI bond 0 (c) 1,3 0 (d) 4,0 0
(b) B-Cl bond is more polar than N-CI bond 0 124. A pale blue liquid which is obtained by reacting equimolar
(c) hitrogen atom is smaller than boron 0 mixture of two gases at -30°C is: [U.T.2008]
(d) BCl3 has no lone pair but NCl 3 has a lone pair of electron (a) N2~ o (b) N20 0
o (c) N204 0 (d) N20 S 0
114. Nitrogen can be purified from the impurities of oxides of -30°C
[Hint: NO + NO z ~ N Z0 3 (Pale blue)]
nitrogen and anunonia by passing through: 125. The element which forms oxides in all the oxidation states
(a) a solution of K2Cr207 acidified with H 2S04 0 from + 1 to +5, is: [A.I.I.M.S. 2004]
(b) concentrated HCI 0 (a) N 0
(b) P 0
(c) alkaline solution of pyrogallol 0
(c) As 0 (d) Sb 0
(d) a solution of K O H D
115. In white phosphorus (P4) molecule which one is not correct? . 126. (NH4hCr207 on heating liberates a gas. The same gas will
be obtained by : [I.LT.2004]
(a) Six P-P single bonds are present 0 .
(b) Four P-P single bonds are present 0 (a) heating ~02 0
(c) Four lone pairs of electron are present 0 (b) heating N~03 0
(d) P P P bond angle is 60° 0 (c) treating Mg3N2 with H20 0
116. Which of the following is the correct statement for PH3? (d) heating H20 2 on NaN0 2 0
(a) It is less basic than NH3 0 127. Which one of the following oxides of nitrogen is solid?
(b) It is less poisonous than NH3 0 [A.F.M.C. 2004]
(c) Electronegativity of PH3 is greater than NH3 0 (a) N~ 0 (b) N20 0
(d) It does not show reducing properties 0 (c) N2~ 0 (d) N20 S 0
117. The number of P-O-P bonds in cyclic metaphosphoric 128. In the electrothermal process, the compound displaced by
acid is: silica from calcium phosphate is : [C.E.T. (Karnataka) 2004]
(a) zero 0 (b) two 0 (a) calcium phosphide 0
(c) three [] (d) four 0 (b) phosphine 0
118. The hybridization of atomic orbitals of nitrogen in NOt, NOi (c) phosphorus 0
and NH;t are: [1.I.T. (8) 2000] (d) phosphorus pentoxide 0
(a) sp, sp3 and si respectively 0 129. N2 forms NCl3 whereas P can fonn both PCl3 and PCl5.
(b) sp, si and sp3 respectively 0 Why? [J.E.E. (Orissa) 2004}
(c) si, sp and sp3 respectively 0 (a) P has d-orbitals which can be used for bonding but N2
(d) si, sp3 and sp respectively 0 does not have 0
119. Ammonia can be dried by: CUT. is) 20(0) (b) N atom is larger than P in size 0
(a) cone. H2S04 0 (b) P40 lO 0 (c) P is more reactive towards Cl than N 0
(c) Cao 0 (d) anhydrous Ca02 0 (d) None of the above 0
130. Which is used to produce smoke screens? [A.F.M.C. 2005] 140. Match List-I with List-II and select the correct answer:
(a) Zinc sulphide 0 (b) Calcium phosphide 0 [J.E.E. (Orissa) 2008]
(c) Zinc phosphide 0 (d) Sodium carbonate 0 List-I List-II
131. The percentage of p-character in the orbitals forming P-P (Molecules) (Boiling points)
bonds in P 4 is: [l.I.T. 2007] (A) NH3 (1) 290 K
(a) 25 0 (b) 33 0 (B)PH3 (2) 211 K
(c) 50 0 (d) 75 0 (C) AsH3 (3) I86K
132. Which of the following is the correct order of increasing (D) SbH3 (4) 264 K
enthalpy of vaporisation? [P.M.T. (Kcrala) 2OQ7] (E) BiH3 (5) 240 K
(a) NH3 < PH3 < AsH3 0 (b) AsH3 < PH3 < NB3 0 (a) A-3, B-2, C-5, D-4, B-1 0
(c) PH3 < AsH3 < NH3 0 (d) NH3<AsH3 < PH3 0 (b) A-5, B-3, C-2, D-4, B-1 0
(e) AsH 3 < NH3 < PH3 0 (c) A-I, B-4, C-5, D-2, E-3 0
133. Chlorine reacts with excess of ammonia to form: (d) A-I, B-2, C-3, 0-4, E-5 0
141. Phosphine, acetylene and ammonia can be formed---b:y---
(a) ~O 0 (b) N2+HCI 0 treating water with: [J.E.E. (Orissa) 2008]
(c)N2 +NH4Cl 0 (d)N2 +NCI3 0 (a) Mg 3PZ, A4C 3, Li3N 0
(e) NCl 3 + HCI 0 (b) Ca3PZ, CaCz, Mg3N z 0
134. The following are some statements related to VA group (c) Ca3P2,CaCZ,CaCN2
hydrides, (d) Ca3P2, MgzC, NH~03~B
(i) Reducing property increases from NH3 to BiH3 142. The number of P-O bonds and lone pair of electrons
(ii) Tendency to donate lone pair decreases from NH3 to present in P 406 molecule are, respectively:
BiH3 [E.A.M.C.E.T. 2008]
(iii) Thermal stability of hydrides decreases from NH3 to . (a) 12,16 0 (b) 12,12 0
BiH3 (c) 8,8 0 (d) 12,4 0
(iv) Bond angle decreases from NH3 to BiH3 143. Hydrolysis of NCl 3 gives NH3 and X. Which of the following
The correct statements are: [E.A.M.C.E.T. (Engg.) 2007] is X? [A.F.M.C. 2008]
. (a) (i), (ii), (iii) and (iv) 0 (b) (i), (iii) and (iv) 0 (a) HCl04 0 (b) H003 0
(c) (i), (ii) and (iv) 0 (d) (i) and (iv) 0 (c) HClO. 0 (d) HOOz 0
135. Which is in the decreasing order of boiling points of 144. The shape of PCl3 molecule is: [A.F.M.C. 2008]
V group hydrides? - [E.A.M.C.E.T. (Med.) 2007] (a) trigonal bipyramidal 0 (b) tetrahedral 0
(a) NH3 > PH3 > AsH3 > SbH3 0 (c) pyramidal 0 (d) square planar 0
(b) SbH3 > AsH3 > PH3 > N H 3 D 145. Which of the following is not correct? [C.P.M.T. 2008]
(c) PR3 > NH3 > AsH3 > SbH3 0 (a) Hydrolysis of NCl 3 gives NH3 and HClO 0
(d) SbH3 > NH3 > AsH3 > PH3 0 (b) NH3 is less stable than PH3 0
136. N 20 is isoelectronic with CO2 and N3, which is the structure (c) NH3 is a weak reducing agent compared to PH3 0
ofN20? . [J.E.E. (Orissa) 2007] (d) Nitric oxide in solid state exhibits diamagnetic property
o
(a) N/O"'N 0 (b) N-O--N 0 146. The atomicity of phosphorus is X and the PPP bond angle
is Y. What are X and Y? [D.C.E. (Engg.) 2008]
o
(d) N-N-O o (a) X =4, Y = 90° 0 (b) X 4, Y =60° 0
137. The hybridization state of the central atom in PCl5 is: (c)X=3,Y 120° IJ (d)X=2,Y=I80° 0
[D.C.E. (Engg.) 2007] 147. The reaction of P4 with X leads selectively to P 406. The X
(a) sp3 d 0 (b) sp3d Z 0 is: [I.I.T.2009]
(c) sp3 0 (d) ~sp3 0 (a) a dry 02 0
138. CI-P-CI bond angles in PCl5 molecule are: (b) a mixture of O 2 and N z 0
[V.L T.E.E.E. 2008] (c) moist O2 0
(a) 120° and 90° 0 (b) 60° and 90° 0 (d) O2 in presence of aqueous NaOH 0
(c) 60° and 120° 0 (d) 120° and 30° 0 [Hin·t : N2 prevents the further reaction of P406 into P40lO.]
139. Bond angles of NH 3, PH3, AsH3 and SbH3 are in the order: 148. Atoms in P 4 molecule of white phosphorus are arranged
[J.E.E. (Orissa) 2008] regularly in the following way: [J.E.E. (W.B.) 2009]
(a) PH3 > AsH3 > SbH3 > NH3 o (a) at the corners of a cube 0
(b) SbH3 > AsH3 > PH3 > NH3 o (b) at the comers of an octahedron
(c) at the comers of a tetrahedron
0
0
(c) SbH3 > AsH3 > NH3 > PH3 o
{d) NH3> PH3 > AsH3 > SbH3 o (d) at the centre and corners of a tetrahedron 0
149. Correct order of bond angles for the following is : (a) 6 o

(b) 4 o
[J.KE. (Orissa) 2009] (c) 2 o
(d) 5 o
(a) NH3 > PCl3 > BCI 3 0 (b) BCl 3 > NH3 > PCl3 0 152. Phosphine can be prepared by the reaction of water with :
(c) BCl3 > PCl3 > NH3 0 (d) PCh > BCl3 > NH3 0 [A.M.U. (Engg.) 2010]
150. The reaction of elemental P4 in aqueous NaOH gives : (a) calcium phosphide o
[J.E.E. (Ol'issa) 2009] (b) calcium hydride o
(a) PH3,NaHzpQz 0 (b) PH3,Na3P04 0 (c) calcium dihydrogen phosphate o
(c) NaH2P04, Na3P04 0 (d) Na3P' Na3P04 0 (d) calcium phosphate o
151. How many bridging oxygen-atoms are present in P401O?
[C.B.S.E. (P.M.T.) 2010]
Set II : The following questions may have J?ore than one correct answers.
153. Nitrogen (I) oxide is produced by: 160. Which of the following fonno:x:ychlorides£l~prec!pitate on .
(8.) thermal deComposition of ammomummtrate hydrolysis?
(b) disproportionation of N z 0 4 D (a) Bi03 0 (b) SbCl3 0
(c) thermal decomposition of anunonium.nitrite 0 (c) CC4 0 ~d) PbClz 0
(d) interaction of hydroxylamine and nitrous acid 0 161. Which of the elements showhllotropy?
154. Ammonia on reaction with hypochlorite anion can. form.: (a}N .D(b) P
[l.I.T. 1999] (c) As 0 (d) Bi 0
(a) NO 0 (b) NH40 0 162. Which of the following reactions can evolve phosphine?
(c) NzHz 0 (d) HNOz 0 (a) White P + Ca(OHh ~
155. Which of the following metals become passive when (b) AlP + H20 ----'i
dropped Into conc. HN0 3? (c) H3P04
(a) Cit 0 (b) Fe 0 (d) P~I + NaOH ~ ~
(c) Cr 0 (d) AI 0
163. A solution of colourless salt H on boiling with excess NaOH
156. White phosphorus has: . [I.I.T.1998]
produces a non-flanunab1e gas.The gas evolution ceases
(a) six P-P single bonds 0
after sometime upon addition of Zn dust to the same
(b) four P-P single bonds 0 solution, the gas evolution restarts. The colourless salt(s)
(c) four lone pairs of electrons 0 H is(are): {I.I.T.2008]
(d) P P P angle of 60° 0
(a) ~03 0 (b) ~Oz 0
157. Which of the following substances are used as fertilizers?
(c) NH40 0 Cd) CNH4hS04 0
(a) Nitrolim i 0
[Hint: NlLtN03 + NaOH ---4 NH3 + NaN03 + H20
(b) Urea 0 [H] Non·flammable
(c) Superphosphate of lime 0 gas
(d) Phosphorite mineral 0 NaN03 + 4Zn + 7NaOH ---4 4Na2Zn02 + NH3 + ZH20
158. Which elements of group 15 are metalloids? NH~02 + NaOH ---4 NH3 + NaN02 + H20
[H]
(a) P 0 (b) As 0
---4 3Na2Zn02 + NH3 + H20 1
3Zn + 5NaOH + NaN02
(c) Sb 0 (d) Bi 0
164. The nitrogen oxide(s) that contain(s) N-N bond(s) is(are):
159. The metals which produce hydrogen only with very dilute
[I.I.T.2009]
nitric acid are:
(a) Zn 0 (b) Sn 0 (a) N20 0 (b) N20 3 0
(c) N20 4 0 (d) N20 5 0
(c) Mg 0 (d) Mn 0
[Hint: N 20 : N=N=O ~ N==N-O
N~l
""'0
1. (a) 2. (c) 3. (c) 4. (d) 5. (d) 6. (b) 7. (d) 8. (a) 9. (b) 10. (c)
11. (a) 12. (d) 13. (b) 14. (b) 15. (a) 16. (d) 17. (c) 18. (a) 19. (c) 20. (c)
21. (a) 22. (c) 23. (b) 24. (d) 25. (b) 26. (b) 27. (b) 28. (a) 29. (b) 30. (a)
31. (d) 32. (b) 33. (c) 34. (c) 35. (a) 36. (c) 37. (d) 38. (d) 39. (c) 40. (a)
41. (a) 42. (d) 43. (a) 44. (c) 45. (b) 46. (d) 47. (b) 48. (c) 49. (d) 50. (b)
51. (d) 52. (b) 53. (c) 54. (d) 55. (b) 56. (a) 57. (c) 58. (a) 59. (b) 60. (c)
61. (d) 62. (b) 63. (c) 64. (d) 65. (a) 66. (d) 67. (b) 68. (c) 69. (a) 70. (b)
71. (c) 72. (b) 73. (d) 74. (a) 75. (d) 76. (c) 77. (d) 78. (d) 79. (b) 80. (b)
81. (a) 82. (a) 83. (a) 84. (d) 85. (d) 86. (d) 87. (d) 88. (c) 89. (d) 90. (d)
91. (b) 92. (a) 93. (a) 94. (a) 95. (c) 96. (b) 97. (d) 98. (d) 99. (c) 106. (c)
101. (dt 102.. Ja). 103. 104. (bL 105. 106. (d) 107. 108. (b)
- ---,--_._,
109. 11il. (a)
'-'----
111. (a) 112. (b) 113. (d) 114. (d) 115. (b) 116. (a) 117. (c) 118. (b) 119. (c) 120. (b)
121. (b) 122. (b) 123. (d) 124. (a) 125~ (a) 126. (a) 127. (d) 128. (d) 129. (a) 130. (b)
131. (d) 132. (c) 133. (c) 134. (a) 135. (d) 136. (d) 137. (a) 138; (a) 139. (d) 140. (b)
141. (b) 142. (a) 143. (c) 144. (c) 145. (b) 146. (b) 147. (b) 148. (c) 149. (b) .150. (a)
15t; (a) - 152. (it) -" 153;' ~it;d) 'f54.(b~c) 155. (b,c,d) 156: (a,c,i.I) 157.-(a;b;C) 158: (b,c) "159;(c,dr-160:-(a,Dr~--;:·-
161. (b,c) 162. (a,b,d) 163. (a,b) 164. (a,b,c)
~ Objective Questions for-liT ASPIRANTS :.~~

1. White phosphorus on reaction with limewater gives calcium (a) (8) is an amphoteric oxide
salt of an acid (A) along with a gas (X). Which of the following (b) (X) is a colourless, diamagnetic gas which combines with
is correct? AI on heating
(a) (A) on heating gives (X) and 02 (c) (X) can be produced by action of (Zn + NaOH) on NaN02
(b) The bond angle in (X) is less than that in case of ammonia (d) none of the above
(c) (A) is a dibasic acid [Hint: NH20RHCI + NaN02~ N20 CuO + N2
(d) (X) is more basic than ammonia (8) (X)
CuO is a basic oxide. N2 is a colourless, diamagnetic
[Hint: 8P+3Ca(OHh +6H20 ~ 3Ca(H 2P02h +2PH3
(X)
gas which combines with AI. 2AI + N2 ~ 2AIN.
Zn + NaOH evolves H2 which reduces NaN02 to form
(A) is H3POZ (Hypophosphorus acid). It is a monobasic
NH3 gas. NaN02 + 6H ~ NaOH + NH3 + H20.]
acid. PH3 is less basic than NH3. The bond angle in (X) is
less than that present in NH3. H3P02 on heating gives 5. If O 2 is removed from the formula of anhydride of HN02,
orthophosphoric acid and phosphine (X).] then the formula of the resulting compound satisfies which
of the following properties ?
2. One mole of H 3P03 on reaction with excess of NaOH gives:
(a) It produces tears in eyes (b) It supports combustion
(a) one mole of Na2HP03
(c) It is paramagnetic
(b) two moles of Na2H2P03
(d) It cannot react with red hot copper
(c) two moles of Na2HP03
[Hint : The anhydride of HN02 is N20 3• If O2 is removed, then
(d) one mole of Na3P0 3
the resulting compound is N20. Nitrous acid does not
[Hint: H3P03 + 2NaOH NaZHP03 + 2H20 ] produce tears in eyes and it is diamagnetic in nature. It
1 mol I mol
supports combustion and reacts with hot copper.]
3. A diatomic gas will be obtained in :
6. Which of the following is correct ?
(a) Cu + dil. HN0 3 ----7
(a) N 20 is a laughing gas and is angular in shape
(b) (NH 4 h Cr20 7 (b) N0 2 is a sweet smelling and is angular in shape
(c) both (c) NO is a colourless gas and acidic in nature
(d) none (d) N0 2 on reaction with NaOH gives a mixture of two salts
[Hint: 3Cu + 8HN03 3Cu(N03h + 2NO + 4H20; [Hint : N20 is a laughing gas and linear in shape. NOz is having
(NH4hCr207 ~ N z + Cr203 + 4H2O] pungent odour and angular in shape. NO is a colourless
and neutral in nature. NO z on reaction with NaOH forms
4. For NH20H·HCI + NaN02 ----7 (A) Cu) (8) + (X)gas' two salts NaNO z and NaN0 3.
which of the following is correct? 2NaOH + 2N0 2 ~ NaN02 + NaN03 + H20]
7. When a mixture of NO and NOzis passed through an aqueous [Hint: H3P309 is a cyclic trimetaphosphoric acid.
solution of ammonium sulphate, we get:
(a) a dibasic acid which has no dehydrating property
(b) a diatomic gas which on reaction with acetylene under
electric spark gives a monobasic acid whose anion is
pseudohalide
(c) a dibasic acid whose dinegative anion has all bonds equal
with bond angle 90°
(d) a dibasic acid whose anhydride in solid state forms a 12. The equivalent mass of phosphoric acid (H3P0 4) in the
cyclic trimer reaction, NaOH + H3P04 -----f NaH2P0 4 + H20, is :
(a) 25 (b) 49
[Hint: NO + N0 2 + (NH4hS04 + H 20 -7 2NH4N02 + H 2S04
(c) 59 (d) 98
t [Hint : Only one hydrogen atom of H3P04 is replaced, so its
2Nz+ 4H20
.equivalentmass. is equal to.its.molecular-mass.l··· ....._ - _ .
N+CH . Electric)2HCN
2 Z Z spark 13. The oxyacid of phosphorus in which phosphorus has the
CW is a pseudohalide.] lowest oxidation state is :
8. Copper metal on treatment with dilute RN03 produces ~ gas (a) hypophosphorus acid (b) orthophosphoric acid
(X). (X) when passed through acidic ~olllti()n qLstannqus (c) pyrophosphoric acid .(d)_Illetapho~Eh()Jj.c acid.
chloride, a nitrogen containing compound (Y) is obtained. [Hint: H3PO Z• O.S. P = +1; H3P04, O.S. P = +5;
(Y) on reaction with nitrous acid produces a gas (Z). Gas (Z) 14P2~. O.S. P = +5; HP03, O.S. P = +5]
is : 14. Which is/are correct statements about P406 and P40 lO ?

(a) NO (a) Both form oxoacids H 3P03 and H3P04 respectively
(c) NOz (b) In P406 each P is joined to three 0 and in P4010 each P
is linked to four 0 atoms
[Hint: Cu + dil. HN0 3 -7 NO SnCl2 /HCI) NH 20H·HCI (c) Both
(X) (Y) HNO
----4 NzO] (d) None
(Z) 15. Blue liquid which is formed at -300c by mixing of two
9. A tetra-atomic molecule (A) on reaction with nitrogen (I) oxide, gases is :
produces two substances (B) and (C). (B) is a dehydrating (a) N20 (b) N20 S
agent while substance (C) is a diatomic gas which shows (c) N20 3 (d) N20 4
almost inert behaviour. The substances (A), (B) and (C) are: [Hint: NO + NO z -30"C) N2 0 3 (Pale blue colour)]
(a) P4,P40 lO,N2 (b) P4,N20s,N2 16. For H 3P03 and H3P04, the correct choice is :
(c) P4,P20 3,Ar (d) P4,P203,02 (a) H3P03 is dibasic and reducing
[Hint: P4 + ION 20 ------7 P40lO + ION z ] (b) H3P03 is dibasic and non-reducing
(A) (B) (C) (c) H3P04 is tribasic and reducing
10. The number of P-O--P and P-O-H bonds present (d) H3P03is tribasic and non-reducing
respectively in pyrophosphoric acid molecule are : 17. The compound molecular in nature in gas phase but ionic in
(a) 1,2 (b) 2,2 solid state is :
(c) 1 , 4 . (d) 1,8 (a) PCl 3 (b) CCl4
[Hint : The structure. of pyrophosphoric acid is· (c) PCIs (d) POCl3
o 0
[Hint: PCl 5 exists as [PCI4t[pCl6 r in solid state.]
II II 18. The decreasing order of the boiling points of the following
HO-P-O-P-OH hydrides is :
I I
OH OH (i)NH3 (ii)PH3 (iii) AsH3 (iv)SbH3 (v)H20
(a) (v) > (iv) > (i» (iii) > (ii)
There are one P-O-P and four P-O-H bonds.]
(b) (v) > (1) > (ii) > (iii) > (iv)
11. Which of the following is a cyclic oxoacid ?
(c) (U) > (iv) > (iii) > (i) > (v)
(a) ~P2~ (b) ~206
(d) (iv) > (iii) > (i) > (ii) > (v)
(c) H SPS0 15 (d) H3P3P9
[Hint; B.pts : NH3 = -33OC; PH3 = -89°C; AsH3 -63;
SbH3 -9; H20 lOO'C]
1. (b) 2. (a) 3. (c) 4. (b) s. (b) 6. (d) 7. (b) 8. (d) 9. (a) 10. (c) 11. (d) 12. (d)
13. Ca) 14. (cJ 15. (c) 16. (a) 17.Cc) 18. (a)

The following questions consist of two statements as 4. (A) Nitrogen is unreactive at room temperature but becomes
. Assertion (A) and Reason (R). While answering these questions reactive at elevated temperatures or in presence of a
choose correctly anyone of the following responses. catalyst.
(a) If both (A) and (R) are true and (R) is the correct (R) In nitrogen molecule, there is extensive delocalization of
explanation of (A). electrons. [A.I.I.M.s. 1996]
(b) If both (A) and (R) are true but (R) is not the correct 5. (A) PH3 is more basic. than NH3. •
explanation of (A). (R) Electronegativity of N is more than phosphorus.
(c) If (A) is true but (R) is false. 6. (A) H3P03 and H 3P0 4 are tribasic acids as they contain three
hydrogen atoms each.
(d) If (A) is false but (R) is true.
(R) Both H3P0 3 and H3P04 are reducing in nature.
(e) If both~tA:)~and~tRyarefalse; 7. (A)F6rruyiiig ammoma· gas, The common .dehydrating-··-
1. (A) RN0 3 is stronger than RN0 2. agents like H2S04 , CaCl2 or P20 j cannot be used.
(R) In RN03 there are two nitrogen to oxygen bonds whereas (R) H2S0 4, CaCl2 or P20 j react with NH3.
in RN0 2 there is only one. [I.I.T. 1998] 8. (A) Phosphorite mineral cannot be used as a fertilizer of
2. (A) P4 is more ieactivethan N2. phosphorus,. ..
(R) P-P siagle bond is rnuch· more weaker as compared to (R) .. Superphosphate·· of Hille is usect as afertiliier·of-
. N N triple bond. phosphorus.
3. (A) Although PFj, PClj and PBrj are known, the penta- 9. (A) H3P03 is a dibasic acid.
halides of nitrogen have not been observed. (R) There are two H-atoms directly attached to P.
(R) Phosphorus has lower electronegativity than nitrogen. [A.I.I.M.S.·2007]
[I.I.T. 1995]
1. (c) 2. (a) 3. (b) 4. (c) 5. (d) 6. (e) 7. (a) 8. (b) 9. (c)
11111111 11111111
(c) calcium ammonium nitrate
(d) urea
Nitrogen, phosphorus and potassium are regarded as essential (e) basic calcium nitrate
plant nutrients. Mter a few years of continuous cultivation, the The important phosphatic fertilizers are :
soil becomes poorer and poorer in materials supplying nitrogen, (a) calcium superphosphate
phosphorus and potassium to plants. If the soil is not (b) nitrophosphate
compensated, it would become less productive and infertile. In (c) triple phosphate
order to maintain soil fertility, it is necessary to add materials (d) phosphatic slag
containing nitrogen, phosphorus and potassium in the form of
The commonly used potassium fertilizers are :
fertilizers. Chemical substances which are added to the soil as to (a) potassium nitrate
make up the deficiency of essential elements are called chemical (b) potassium chloride
fertilizers. Every chemical compound of nitrogen, phosphorus and
(c) potassium sulphate .
potassium cannot be used as a fertilizer. Substances to be used
. Fertilizers containing N, P and K in suitable adjusted propor-
as fertilizers must have the following characteristics :
tions are known as NPK fertilizers.
(a) it must be soluble in water
1. Which one of the following substances is used as a fertilizer?
(b) it should be easily assimilated by plants
(a) K2S04·Al2(S04h·24H20
(c) it should be stable (b)Ca(CNh
(d) it should not disturb the pH of the soil
(c) Ca(H2P04hH20·2(CaS04·2H20)
(e) it should be cheap
(d) CaS04
The important nitrogeneous fertilizers are : 2. Fertilizer having highest percentage of nitrogen is :
(a) ammonium sulphate
(a) urea (b) calcium cyanamide
(b) calcium cyanamide
(c) ammonium nitrate (d) ammonium sulphate
3. Sindhri fertilizer is chemically known as : 1. Which one is monobasic acid?

(a) ammonium nitrate (b) ammonium sulphate (a) H3POz (b) H3P03
(c) urea (d) calcium nitr/l.te (c) H3P04 (d) H3POS
4. Ammonium salts are oxidised in the soil to nitrites by : 2. Which one has +4 oxidation state?
(a) denitrifying bacteria (b) ammonifying bacteria (a) H3P04 (b) H3P03
(c) nitrosifying bacteria (d) nitrifying bacteria (c) RtP2~ (d) .H4P206
5. The actual composition of nitrolim is : 3. The acid which forms two series of salts is :
(a) Ca(CN)2 (b) CaC2 + Ca(CN)2 (a) H3P04 (b) H3P03
(c) CaCN2+C (d) CaR2 (c) HJB~ (d) H3P02
6. Expression like 4-8-2 used for a NPK mixed fertilizer indi- 4. Which of the following is a cyclic oxoacid?
cates that it contains : (a) RtP2~ (b) H4P20 6
(a) 4% N2, 8% P20 S and 2% K 20 (c) H3P3~ (d) HSPS01s
(b) 4% urea, 8% Ca(H2P04h and 2% KCI 5. The number of P-40 or P=O and P---O-H bonds in
(C}4rLL~3,8.%H3P04AI192~K2SQ4 H3P04 are:
(d) 4% ~03' 8% P20 S and 2% KN0 3 (a) 3, I (b) 2,2
(c) 1,2 (d) 1,3
THOUGHT2 _ _ _ _ _ _ _ _ _ __
The pronouncedchangeJromnon"metallic to metallic behaviour
THOUGHT
and also increase in the basicity of oxides from nitrogen to bismuth There are some deposits of nitrates and phosphates in earth's
in group 15 is principally due to increasing size of the atoms. The crust. Nitrates are more soluble in water. Nitrates are difficult to
ionisation potential of nitrogen is very high on account of its small reduce under the laboratory conditions but microbes do it easily.
size. However, ionisation potential decreases regularly on descen- Ammonia forms large number of complexes with transition metal
ding the group. ions. Hybridization easily explains the ease of sigma donation
1. Which one of the following is a strongest base ? capability ofNH3 and PH3' PH3 is a flammable gas and is prepared
(a) AsH3 (b) SbH3 from white phosphorus. '[I.I.T.2008]
(c) PH3 (d) NH3 1. Among the following, the correct statement is:
2. Among the trihalides of nitrogen, which one is least basic? (a) Phosphates have no biological significance in humans
(a) NF3 (b) NCl3 (b) Between nitrates and phosphates, phosphates are less
(c) NBr3 (d) NI3 abundant in earth's crust
3. Which one of the following fluorides does not exist ? (c) Between nitrates and phosphates, nitrates are less
(a) NFs (b) PFs abundant in earth's cr:ust
(c) AsFs (d) SbFs (d) Oxidation of nitrates is possible.in soil
4. Which of the following oxides is most acidic ? 2. Among the following, the correct statement is:
(a) Bi2~ (b) P2~ (a) Between NH3 and PH3, NH3 is a better electron donor
(c) AS203 (d) Sb20 3 because the lone pair of electrons occupies spherical
5. The most unstable hydride is : s-orbital and is less directional.
(a) NH3 (b) PH3 (b) Between NH3 and PH3, PH3 is a better electron donor
(c) BiH3 (d) SbH3 . because the lone pair of electrons occupies' sp3 -orbital
6. In all .the group 15 elements, the number of unpaired and is more directional.
electrons in the valence shell is : (c) Between NH3 and PH3, NH3 is a better electron donor
(a) 4 (b) 3 because the lone pair of electrons occupies sl-orbital
(c) 2 . (d) 5 and is more directional.
7. Which trihalide is most ionic among the following? (d) Between NH3 and PH3, PH3 is a better electron donor
(a) NCl3 (b) PCl3 because the lone pair of electrons occupies spherical
(c) BiF3 (d) SbF3 s-orbital and is less directional.
3. White phosphorus on reaction with NaOH gives PH3 as one
THOUGHT of the products. This is a:
Phosphorus forms a number of oxoadds which differ in their (a) dimerization reaction
structures and oxidation state of phosphorus. All the acids contain (b). disproportionation reaction
phosphorus atom/atoms linked tetrahedrally to four other atoms (c) condensation reaction
or groups. Each of them has at least one 1'>=0 or P-40 unit and (d) precipitation reac~ion
one P--:OH unit The OH group is ionisable but H atom linked o +1 -~
[Hint : P4 + 3NaOH + 3H20~ 3NaH 2 po; + PH 3 ]
directly to P is non-ionisable. Structures of all the acids are
considered to be derived either from phosphorus acid or
phosphoric acid.
Thought 1 1. (c) 2. (a) 3. (b) 4. (d) 5. (c) 6. (a)

Thought 2 1. (d) 2. (a) 3. (a) 4. (b) 5. (c) 6. (b) 7. (c)
Thought 3 1. (a) 2. (b) 3. (b) 4. (c) 5. (d)
Thought 4 1. (c) 2. (c) 3. (b)
BRAIN):8rrORMING PROBLEMS
~~ .
1. Which oxy-anion of nitrogen is present in Angeli's salt? [Hint: Trimethyl amine has pyramidal structureJike NH3 because
[Aos. Na2Nz03·HzO; Nzoh lone pair of electron is present at nitrogen.
2. Write down the two compounds of Vth or 15th group elements •• N·
which are covalent in vapour state but ionic in solid state.
[Am:·· N:z05~pt:lsr .. H3C/~I-~CH3.··
3. Write the formula of: CH3
(i) Scheele's green (iii) Graham salt
(n) Paris green (iv) Pearl white Trisilyl amine has planar structure because lone pair of
nitrogen is donated to vacant d-orbital of silicon.]
[Aos. (i)CuHAs03; (ii) (CH 3COOhCu.3Cu(AsOzh
(iii) (NaP()3)6; (iv) BiOCI] . ...... ····"';SiH3
4. Explain why all P-F bonds in PFs are not equivalent? H3Si---'N~("
[Ans. Phosphorus in PFs lie in sid hybrid state, out of five '<- SiH3
P-F bonds, three are equatorial bonds which have different
11. Explain why NF3 has no donor property of electrons but PF3
length.]
has, and PF3 forms several complexes.
5. Write comment on non-existance of PIs?
12. What is composition of Devarda's alloy? Which gas is
6. Although phosphorus pentabromide exists in the vapour
evolved when this alloy is treated with HN0 3?
phase as PBrs molecules, in the solid phase the substance is
[Ans. AI 45%; Zn 5%; eu 50%; NH3(g)]
ionic and has the structure [PBr4]+ar-. What is the expected
geometry of PBrt? 13. When HN03 is added to conc. H2S04 we get NO! and
[Ans. Tetrahedral] N03 ; explain this fact.
7. With the help of NH 3, 02, Pt and H20, write equations for
preparation of N 20 from these substances.
In polar solvent, N20 5 gives solvated ions NOr and NO).]
[Hint: 4NO(g) + 6H 20(g)
14. Explain why nitride oflithium (Li3N) is more stable than nitride
2NO(g) + 02(g) ~ 2N02(g)
of potassium (K3N)?
3N02(g) + H20(l) 2HN03(aq.) + NO(g) [Hint: Lattice energy of U3N is very high.]
HN0 3(g) + NH3(aq.) ~ NH 4N0 3(aq.)
15. In oxidation of P4 to P406 we cannot use pure 03; we use
N~N03(aq.) ~N03(S) mixture of 0 3 and N2. What is the reason behind it?
[Hint: Pure O2 will oxidise P40 6 to P40 IO.]
NH4 N0 3(s) N20(g) + 2H2O(g)]
16. Arrange the following as indicated:
8. Give the formula of: (a) AS 20 3, P20 3, N20 3 (Decreasing acid strength)
(i) Polyphosphoric acid
(b) P20S, N20S. AS20 3, Bi 20 s , Sb20s
(n) Polymetaphosphoric acid
(iii) Sodium triphosphate (Decreasing acid strength)
(iv) Trimetaphosphate (c) N20. N20 S, N20 4, N203, NO (Increasing acid strength)
[Ans. (i) Hn+2 Pn 03n+l: (ii) (HP03)n ; (d) P20 S, Bi20 S, N20S, Sb20S, AS20 3 (Decreasing stability)
(iii) Na5P301O ; (iv) Na3P309] (e) NBr3, NCI3, NF3 (Decreasing stability)
9. Write down the formula of those compounds of phosphorus (f) Nl3, NBr3, NC13, NF3 (Increasing Lewis base strength)
which are used as: (g) BiCl3• NCI 3, PC13, AsCI 3, SbCl3
(i) detergent additive (n) in soft drink (Decreasing trend of hydrolysis)
(iii) in tooth powder (iv) animal feed additive (h) PF3, PCI3, PBr3, PI3 (Decreasing Lewis acid strength)
[Aos. (i) Na5P301Q; (ii) H3P0 4 ; (i) H3Sb04, H3As04' H3P04, HN03
(iii) CaHP0 4·2H2O; (iv) CaHP04 ·2H 2O] (Decreasing solubility in water)
10. Comment on the structure of trimethyl amine [(CH3hN] and [Ans. (a) N20 3 > P203 > AS203
trisilyl amine [(SiH3hN], (b) N20 5 > P205 > As Z0 5 > Sb20 5 > Bi20 5
Elements of Group VA or 15 (Elements of Nitrogen and Phosphorus Family) 529--~---
(c) N20 < NO < N20 3 < N20 4 < N205 (f) SO~- + NO:;: + H+ ----?
(d) P20 5 > As 20 3 > Sb 20 5 > N2 0 S > Bi20 S [Ans. (a) [Fe(CO)s] + 2NO [Fe(COh(NOh] + 3CO
(e) NF3 > NCl 3 > NBr3
(b) 3KN02 + KNO) + Cr203 2K2Cr04 + 4NO
(0 NF3 < NCl 3 < NBr3 < NI3 "
(c) 3Cr2+ + NO + 3H+ NH 20H + 3Cr3+
(g) NCl 3 > PCl 3 > AsCl 3 > SbCl 3 > BiC]3
(d) S02 + 2NO + H20 NzO + H2S04
(h) PF) > PCl) > PBr) > PI3
(i) RN03 > H3P04 > H3As04 > H3Sb04 .]
(e) 3Mn04 + 5NO + 4H+ ----7 5N0'3 + 3Mnz+ + 2HzO
(f) SO~- + 2N02 + SO~- + 2NO + H20]
17. What are the products formed by hydrolysis of NCl3 and
20. Answer the following questions:
PC13?
(a) What is Swart's reagent?
Cl
10 . 0+ (b) Give chemical formula of Vortex ring.
[Ans. CI-N--------H-O ----7 NHCl2 + Hocl (c) Cold fire and Phossy Jaw are related to ............ ..
I I (d) Which gas of nitrogen is used as anaesthetic in dental
Cl H 1+
2H2o
NH3 2HOCI
surgery?
(e) Give the chemical formula of phosphorus sulphide present
Cl in 'strike anywhere matches'.
I . H' (f) What is 'Ghost light'?
crp~o<' .~ 'P(0H)CI2+HCF (g) What is the chemistry of Holme's signal?
~;,~~,,~k~~~7· .. =4'!§'q~", [Ans. (al
(b)
SbF3 is a fluorinating agent called Swart's reag~nt._ .• =
White smokes of P20 S is called Vortex ring.
H 3P03 + 2HC] 1 (c) White phosphorus.
18. NF3 is stable but NCl3 and NI3, are unstable and explosive. (d) N 20
Explain why? (e) P4 S 3
[Hint: In NF3, there is strong p1t-p1t bonding due to large (f) Bones glow in dark due to oxidation of white phosphorus
electronegativity difference between N(3) and F(4). On the present. The phenomenon is called chemiluminescence.
other hand, there, is weakp1t-p1t bonding in NCl 3 and NI3, (g) Mixture of CaC2 and Ca3P2 filled in container with a
hence these compounds are unstable and explosive.] hole is thrown into sea or river, so that following
19. Complete the following reactions: reactions take place:
(a) [Fe(CO)s] + NO----? CaC 2 + 2H 20 Ca(OHh + CZH2
Ca3P2 + 6H20 3Ca(OH)z + 2PH3 or P2~
(b) KN0 3 + KN02 + Cr203----?
P2H4, catches fire. The acetylene produces a bright
(c) Cr2+ + W + NO----? luminous flame which serves as a signal to approaching
(d) S02 + NO + H+ ----? ship or boat (Holme's signal).]
(e) Mn04' + NO + H+ ----?
The answer to each of the following questions is a single 5. When excess of ammonia and chlorine react, nitrogen and
digit integer, rallging from 0 to 9. ammonium chloride are formed. Write the balanced equation
1. How many nitrogen oxides are known ? and find out how many ammonium chloride molecules are
2. How many lone pairs are present in nitrogen molecule? involved in the balanced equation?
3. In group 15 elements, the number of unpaired electrons in 6. How many a-bonds are present in N20 3?
valence shell is: 7. What is the basicity of pyrophosphoric acid?
4. How many P-O--P bonds are present in P408? 8. In solid PCls molecule, how many P--:CI bonds are present
in the cation?
1. (5) Five oxides are known. These are N 20, NO, N 203, N02 and 5. (6)
N 20 5 ·
2. (2) Nitrogen molecule has a triple bond and each nitrogen atom is
associated with a lone pair of electrons. :N == N:
3. (3) The valence shell in group 15 elements is Ilini i.e., all the 6. (4) The structure of N203 is
three p-orbitals are occupied by single electron each. 7. (4) H4P20 7. It has four OH groups.
r
o /1\0
8. (4) [PC]4t[pCI 6
4. (6) The structure of P40g is : 0 ~ p( 0 0 ~~0

010
----------p/
·11
Group
16 or VIA
8
o
Oxygen
CHAPTER
2s"2p'
16
S
Sulphur
Ss"sp'
34
!
Se
Selenium Elements of Group VIA or 16
4s"4P'
52
(The Oxygen Family, ns2np4)
Te
Thllurium
5s25p4
84
Po
Polonium 11.1:;'
·'.U
POSITION IN PERIODIC TABLE
. 68~p~·.
116 Group 16 or VIA of the extended form of periodic table consists of six elements-
~oxygeil (0), sulphur (S),selenil.1il1TSe),~teIlririum-{Te)~ polomum(Po) ana~
Ul.in
Ununhexium ununhexium (Uuh)*. This family is known as oxygen family. These (except
7s·7p' Contents: polonium and ununhexium) are the ore forming elements and thus called
ll.1 Position in Periodic Table chalcogens. These are p-block elements as the last differentiating electron is
11.2 Abnonnal Behaviour of Oxyge.n
accommodated on np shell. These elements have six electrons in their valency
11.3 Dissimilarities between Oxygen and Sulphur
11.4 Oxygen shell and thus placed in the Vlth group.
11.5 Oxides The elements oxygen and sulphur are common while selenium, tellurium and
11.6 Ozone polonium are comparatively rare. Oxygen is the most abundant element and is
ll.7 Sulphur found both in free as well as in combined state. Oxygen makes up 20.9% by
11.8 Compounds of Sulphur volume and 23% by mass of atmosphere. Most of the oxygen present in the
I~ VA VIA VDA atmosphere is produced by photosynthesis in plants. It also occurs in the form
Period (15) (16) (17) of ozone in the upper atmosphere which protects us from the harmful radiations
0 F of the sun. Oxygen makes up 46.6% by mass of the earth's ernst. Sulphur is the
N
2 (7) (8) (9) sixteenth most abundant element and constitutes 0.034% by mass of the earth's
P S crnst. It occurs maiilly in combined form. The member, polonium is radioactive
3 (15) (16) in nature. The inclusion of these elements in the same subgroup is justified on the
As Se basis of same electronic configuration and similarities as well as gradation in their
4 (33) (34) (35) physical and chemical properties.
Sb Te I
Like other groups, the first element oxygen differs from other elements of the
5 (51) (52) (53) group in several respects.
Bi Po At
6 (83) (84) (85) ~ 1. Electronic Configuration
Uup Uuh - The distribution of electrons in various energy shells of the atoms of these
7 (115) (116) elements is given as below:
Element At. No. Electr~)Dic confIgUration With ~ert gas core
Oxygen 8 2, 6 Ii, 2s2 2p4 2
[He] 28 2p4
Sulphur 16 2,8,6 Ii, 2s2 2l, 3i 3p4 [Ne] 382 3i
Selenium 34 2,8, 18,6 Ii, 2s2 2l, 3i 3l3dlO, 4s2 4p4 [Ar] 3dlO, 4i 4p4
Tellurium 52 2, 8, 18, 18, 6 Ii, 2s2 2p6, 3i 3i 3dlO , 4i 4i 4dlO , 5l [Kr] 4dlO, 5i 5i
Polonium 84 2, 8, 18, 32, 18, 6 Ii, 2i 2p6, 3i 3i 3dlO , 4i 4i 4d1O 4l4, 5i 5i 5d lO , 6i 6p4 [Xe] 4J14, 5dlO , 6i 6l
Ununhexium 116 2, 8, 18, 32, 32, 18, 6 Ii, 2s2 2i, 3i 3p6 3dlO, 4i 4p6 4d1O 4l4, 5i 5p6 5d w 5l 4, 4 lO
[Rn] 5l , 6d , 7i 7l
6i 6p6 6d lO, 7i 7p4
*Recently a new element with atomic number 116 (Ununhexium) has been discovered. It is a synthetic and radioactive element. It is not very
stable elemerit. Not much is known about its properties.
Elements of-Group VIA or 16 (The Oxygen Family) 53'1--
All have six electrons in their outermost shell, i.e., they have and sulphur are distinctly non-metallic. Selenium and tellurium
electronic structure ip4. The penultimate shell contains 2 show both non-metallic and metallic characters but poloQium
electron~ in oxygen, 8 electrons in sulphur and 18 electrons in is definitely a metal.
Se, Te, Po and Uub. This explains why oxygen differs from (c) There is a gradual gradation in physical properties:
sulphur and these two from the remaining elements. (i) Atomic and ionic radii: The atomic radii of the
elements of group 16 are smaller than those of the corresponding
~ 2. Physical Characteristics elements of group 15. The atomic radii of the elements of this
(a) Physical state: Oxygen is a gas while others are group increase gradually on moving down the group.
solids. Oxygen molecule is diatomic while the molecules of Element o S Se Te Po
other elements are more complex. Sulphur, selenium and Atomic radii (pm) 66 104 117 137 146
tellurium exist as staggered 8-atom rings. However, the tendency [covalent radii (single bond)]
to exist in 8-atom rings is maximum with sulphur and decreases The smaller atomic radii of group 16 elements as compared
as w_e godownthe grQ!lP,lrl S8 mQI~cule,every sulphllr lltom withcorrespondingelements-ofgroups·15 are due-to the increased--
is in sp3 hybridized state involving both bonding and non- effective nuclear charge with increase in greater attraction
bonding pairs of electrons. towards nucleus. The attraction brings contraction in size. The
S'...\ /s~
. . . ······S··· .• ~...
..... S/
gradual increase on moving down the group is due to the
increase in the number of electron shells from member...to--
member.
S/S~S In the formation of anions, two electrons are being added
to an atom. Therefore, the effective nuclear charge is reduced
and hence, the electron closed expands. Thus, the negative
2
Fig. 11.1 Staggered ring structure of sulphur molecule, Sa ions (M l are bigger in size than the corresponding atoms.
Like atomic radii, ionic radii also increase gradually on moving
[Oxygen atom has the tendency to form multiple bonds down the group.
(p1t-pn interaction) with other oxygen atom on account of
small size while this tendency is missing in sulphur atom. The Element 0 S. Se Te
bond energy of oxygen-oxygen double bond (0=0) is quite Ionic radii (pm) 140 184 198 221
large (about three times that of oxygen-oxygen single bond, (Ii) Ionisation energy: The ionisation enthalpies are high
0-0 = 34.9 kcal mol-i) while sulphur-sulphur double bond and thus the elements do not lose the electrons to form positive
(S=S) is not so large (less than double of sulphur-sulphur ions easily. The values decrease as the atomic number increases
single bond, S-S = 63.8 kcal mol-i). As a result, from 0 to Po and thus the tendency to fOmI positive ion
-0-0-0- chains are less stable as compared to 0==0 increases gradually, i.e., metallic nature increases.
molecule while -S-S-S- chains are more stable than S=S
molecule. Therefore, at room temperature, while oxygen exists
o S Se Te Po
as a diatomic gas molecule, sulphur exists as S8 solid.] Ionisation energyLl#1 1314 1000 941 869 813
(kJ morl )
The plastic sulphur which is formed by pouring liquid 2251 2045 1790
SXS /
. sulphur into water contains zig-zag long chains of sulphur atoms. )
Decreases gradually
The ionisation energies of ftrst three elements of group 16
l~sjA-sfS s are less than corresponding elements of group 15 inspite of the

fact that nuclear charge increases. The abnormal behaviour is
s tifS 1 due to symmetrical and more stable electronic configuration of

N, P and As as compared to 0, S and Se respectively.
However, the second ionisation values of group 16 elements
are higher than those of group 15.
(iii) Electronegativity: Electronegativity decreases gradu-
ally. Oxygen is second most electronegative element after
At temperatures above the boiling points, sulphur forms a red fluorine.
vapour, which turns to yellow as temperature is increased. In o S Se Te Po
vapour there exist S8, S6 and S2 molecules. Above 1()()()oC, there Electronegativity 3.5 2.44 2.48 2.01 1.76
exist only S2 molecule, which has structure like 02. -------------------7)
Decreases gradually
(b) Metallic and non-metallic character: Metallic
This decrease indicates a change from non-metallic to
character increases with the increase of atomic number. Oxygen
metallic character.
(iv) Melting and boiling points: The melting and boiling Thus, oxygen is never more than divalent while other
points increase gradually with increase in atomic number. members may be divalent, tetravalent and hexavalent. The
o S Se Te compounds having +4 oxidation state show both oxidising and
Melting point ("C) -219 119 217 450 reducing properties while compounds having +6 oxidation states
(Monoclinic) are only oxidising.
Boiling point ("C) -183 445 688 990 (g) Mnltiple bonding: Oxygen atom has the tendency to
(v)Electronaffinity: Group 16 elements have high electron form multiple bonds (p1V--pre interaction) with the other oxygen
affinities. On moving from oxygen to sulphur, the EAl value atom on account ofsmall size andhigh electronegativity. However,
increases and then decreases from S to Po: the rest of the elements do not form pre-pre multiple bonds due to
Element
(kJ mol-i)
°
-141 -200
S ~
-195
Th
-190
~
-183
their large size. Sulphur and higher members of group 16 possess
vacant d-orbitals in their valence shell. They use these orbitals to
The electron density in 2p energy shell in oxygen is high due form drt-pre bonds. However, this tendency is maximum and
to small size atom and thus, there is some resistance to stronger in sulphur and decreases from sulphur onwards.
-----------------------
the incoming electron and thereby the EA 1 of oxygen is com-

III 3. Trends in Chemical Reactivity
paratively low. Sulphur has maximum value and on moving from
S to Po, the EA 1 values decrease due to increased size. Oxygen is the most reactive element of the group despite it
(d) Allotropy: All the elements show allotropy: has high bond dissociation energy of oxygen molecule (493.4
Elenient- ...... AUotroplcforms ..-- .-- kJ mol-l) asnearryaUits reactions are exotheTIriic. OnGe~=
Oxygen Ordinary oxygen and ozone initiated, these reactions continue spontaneously. Oxygen
Sulphur Rhombic, monoclinic, plastic, amorphous directly combines with almost all the metals except noble metals,
Selenium Red form (non-metallic), grey fonn (metallic form) all the non-metals except noble gases and halogens and many
Tellurium Crystalline and amorphous
compounds under suitable conditions. The oxides are generally
Polonium a and ~ forms (Both are metallic forms)
stable compounds. The elements such as W, Pt, Au, halogens
(e) Catenation: Oxygen and sulphur show the property and noble gases which do not directly combine with oxygen,
of catenation. The property is more pronounced in sulphur. form compounds with oxygen indirectly.
H-O---O-H, H-S-S-H, H-S-S-S-H, H-S-S- After oxygen, sulphur is quite reactive element especially at
,c:,--,c:,--rl. the peroxides and polysulphides are fairly stable. high temperatures which help in breaking ofS-S bonds. Sulphur
Note : Catenated compounds of sulphur are the following : burns in air and reacts directly with carbon, phosphorus, arsenic
(i) Polysulphides : S;;-
where n = 2, 3, 4, etc. and many metals. Oxidising acids oxidise it into S02 and
(in SuJpbanes : X-S lI-X, where X = I, CI, CN, etc. alkalies dissolve it to give sulphides and thiosulphates. It reacts
Compounds corresponding to n - 100 have been reported.
with H2 and halogens. The sulphides are stable compounds and
(iii) PolysuJpbonic acids : These have general formula
H03S--S1/-S03H compounds corresponding to n - 22 many metals are found in nature in the form of sulphides.
have been reported. These are also called thionic acids. However, the reactivity of group 16 elements decreases
(f) Oxidation states: As the configuration of outer- from oxygen to polonium.
4
most shell is ni np , these elements try to gain or share two o > S > Se > Te > Po
. electrons in order to attain inert gas configuration. Oxygen being Selenium and tellurium combine with highly electropositive
highly electronegative shows -2 oxidation state in its compounds elements such as alkali and alkaline earth metals. Se and Te combine
except in oxygen fluorides and most of the metal oxides are ionic with oxygen, fluorine and chlorine. In general, the compounds
and contain oxygen as dinegative anion, 0 2-, Since, the of selenium and tellurium are less stable than oxygen and sulphur.
electronegativity decreases, the tendency to exhibit -2 oxidation Some important trends in chemical reactivity of elements of
state decreases as we go down in the group. However, positive group 16 are discussed here.
oxidation states are exhibited by S, Se, Te and Po. In addition to
+2 oxidation state, +4 and +6 oxidation states are observed. This (a) Hydrides
is due to the availability of d-orbltals in these elements. Oxygen All the elements of this group form the hydrides of type
has no d-orbitals and hence cannot show +4 and +6 oxidation H2M where, M = 0, S, Se, Te and Po, i.e.,
states while sulphur can have 2, 4 or 6 unpaired orbitals forming H 20, H2S, H 2Se, H 2Te and H 2Po
2, 4 or 6 covalent bonds.
H20 is obtained by burning hydrogen in the atmosphere of
S-atom oxygen while H 2S, H2Se and H2Te are obtained by the action
(Ground state) +2 of acids on sulphides, selenides and tellurides.
S-atom FeS + H 2S04 ----7 FeS04 + H2S
(Excited state) +4
Na2Se + H 2S04 ----7 Na2S04 + H 2Se
S-atom
(Doubly excited state)
(i) Physical state: Water is colourless, odourless liquid while
+6
other hydrides are colourless, poisonous gases with bad odours.
Elements of Group VIA or 16 (The Oxygen Family)
(ii) Volatility: Water has low volatility (high boiling point) (b) Oxides
as hydrogen bonding brings association. H2S has high volatility
The most important oxides are of the type M02 and M03'
as no hydrogen bonding is present. Volatility decreases from
S02 and Se02 are acidic oxides and are soluble in water. Te0 2
H2S to H2Te due to increase in molecular masses of the hydrides.
and P002 are insoluble in water. These are amphoteric oxides
(iii) Covalent character: As the electronegativity
as they dissolve in both acids and bases.
difference between M and H decreases, the covalent character
of these hydrides increases from H20 to H2Te. Water molecule S02 + H20 -----t H2S03 (Sulphurous acid)
is highly polar. It has high dielectric constant and hence acts
Se02 + H20 -----t H2Se03 (Selenous acid)
as an excellent solvent for inorganic compounds.
(iv) Thermal stability: The thermal stability decreases Te02 + 2NaOH -----t Na2Te03 + H20
Sodium tellurite
as the atomic mass increases. Water dissociates at 2000°C
while tellurium hydride, H2Te, decomposes at room tem- 2Te02 + RN03 -----t 2Te02·RN03 or Te203·(OH)N03
Basic nitrate
peratur{!.!11!~i~_<ll1~~()an increase in M-H bond
(v) Acidic nature.: The hydrides are all weak acids and S02 is a gas, Se02 is a volatile solid and Te02 is a white
dissociate to varying degrees to give H+ ions. The acidic strength non-volatile solid. All the dioxides possess different structures.
increases from H20 to H2Te as it is evident from the values of S02 is an angular molecule with an O-S-O angle of 119.5°,
dissociation constants. The sulphur undergoes sl-hybridization. Both the bonds have'
~~~. ~H;O--:--~ H Se ----- --- H2Te same' b()Ild'leIlgths. ThissuggesfSiesOI1ance~iIlilie' molecule..:~
2
Dissociation 1.0 X 10-14 1.0 x 10-7 1.7 x 10-4 2.3 X 10-3 Se02 has the same structure as S02 in the gaseous state but
constant (2S°C) the solid has a chain like structure which is not planar.
The increasing trend can be explained on the basis of
dissociation energies. The dissociation energies decrease as
the bond length M-H increases from oxygen to tellurium. Oxygen atom in ground state
This facilitates the release of proton. The acidic nature can also
be explained on the basis of charge density on M 2- anion. The Sulphur atom in excited state
charge density on the M 2- ion decreases as the size of M-atom
increases from oxygen to tellurium. The decrease in charge
density is responsible for the decrease in dissociation energies
and thereby increasing the tendency to furnish proton.
(vi) Reducing nature: All hydrides except H20 act as
reducing agents. The reducing nature increases as the atomic O-~-S-~-O - - - O-~-S-~-O
pn-pn pn-dn pn-dn pre-pn
number of the central atom increases. This is due to weakening
of M-H bond as the bond length increases with increase of Fig. 11.2 Formation of S02 molecule
size of M-atom.
(vii) Burning: H2S, H2Se, H2Te and H 2Po burn in
atmosphere of oxygen with blue flame forming dioxides.
_ 2H2S + 302 -----t 2H20 + 2S02
(viii) Shape: All these hydrides are V-shaped. In these
hydrides, the central atom is sp3-hybridized. The bond angles Te02 and Po02 are crystalline ionic solids.
are 104.5°, 92S, 91° and 90° in H20, H 2S, H 2Se and H 2Te,
respectively. ' Trioxides: S03, Se03 and Te03 are acidic in nature.
This can be explained on the basis of decreasing electro- S03 + H20 -----t H2S04 (Sulphuric acid)
negativity of central atom and decreasing tendency of
Se03 + H20 -----t H2Se04 (Selenic acid)
sp3 -hybridization.
Te03 + 3H20 H6Te06 (Telluric acid)
Other hydrides
Oxygen and sulphur have a tendency to form poly oxides The acidic nature decreases on moving down the group.
and poly sulphides which are comparatively less stable. The S03 is a gas and has plane triangular structure. The structure
two common examples are H20 2 (hydrogen peroxide) and of S03 is similar to that of S02 except for the fact that lone
H2S2 (hydrogen disulphide). They decompose on heating. pair of electrons of sulphur atom is donated to third oxygen
2H202 -----t 2H20 + O2 atom. According to another view, the true structure of S03
H2S2 -----t H2S+ S molecule is considered to be resonance hybrid of the following
Hydrogen poly sulphides (H-Sn-H', n may be 2,3,4,5) are structures.
yellow oily liquids which possess a more strong odour than H2S,
o agents. These properties decrease from S to Te. Oxyacids are
~
dibasic in nature.
1.43A,
(d) Haljdes
O/'--/~O
120 0
S, Se and Te form hexafluorides showing the maximum
o o valency of six. They all involve
2
sid
hybridization.
+E---+)
II
S ~E---+)
t 3s 3p
Ill] IiJl j! Ii I I I I I
3d
0/ ~O ~S~ Sulphur atom in ground state

o 0
Sulphur atom in excited state rn ITIIlJ] I 'f Ii I I
In the solid state, S03 exists as a cyclic trimer or a linear ··sp3d 2 hybridization
chain.
Thus, hexafluorides possess
octahedralstructuIe. F
These are colourless gases.
SF6 is extremely inert. -~-+---.""F
SeF6 is slightly reactive while
TeF6 .is hydrolysed by wat~r.
TeF6 + 6H20 ~ 6HF + H6Te06
No other halogen forms the F IC:-_ _ _.--~
hexahalides due to larger size of
Cyclic trimer of 803 Linear chain of 803 CI, Br and I.
Many tetrahalides are known. F
Solid selenium trioxide is a cyc1ictetramer [Se4012l. SF4 is a gas, SeF4 is a liquid
Fig. 11.3
while TeF4 is a solid. S, Se, Te
and Po form tetrachlorides and bromides while Te and Po form
tetraiodides. All tetrahalides possess trigonal bipyrarnid structure
with sid hybridization.
3s 3p
Sulphur atom in ground state [liJ Ii] iii I ,----I -'-----'--'----L----.J
Sulphur atom in excited state [liJlililillil
Four unpaired electrons form bonds with four halogen atoms

(c) Oxyacids Qr oxoacids and one position is occupied by lone pair.
Sulphur forms a number of oxyacids but selenium and x
tellurium form only two series of oxyacids, the -ous and -ic .-
acids. ~---I-~ x
H 2S0 3 H2Se0 3 H 2Te0 3
Sulphurous acid Selenous acid Tellurous acid
Salts : Sulphite Selenites Tellurites
H2SO4 H2Se04 H2Te04 or H6Te06
Sulphuric acid Selenic acid Telluric acid x
Sulphates 'Selenates Tellurates
Fig. 11.4
Oxyacigs with S-S linkages are called thioacids and with
0-0 linkages are termed peroxy acids. Thionic acids have SF4 is very reactive and is readily hydrolysed by water to
two -'-S03H groups linked either directly or through a S-chain give S02 and HF inspite of the fact that average bond energy
(poly thionic acids). in SF4 is greater than SF6. This is due to the presence of empty
With increase oxidation number, the acid strength of oxyacid 3d-orbitals in sulphur atom in SF4. It is used as fluorinating
of an element increases, i.e., sulphuric acid is stronger than agent for many inorganic and organic compounds.
sulphurous acid. In the oxyacids of group 16 elements in same All the elements except selenium form stable dichlorides and
oxidation state, the acidic nature decreases from S to Te. The dibromides. Di-iodides are not formed. Dihalides form tetrahedral
-ous acids act as reducing agents while -ic acids act as oxidising molecules due to si
hybridization. .
Elements of Group VIA or 16 (The Oxygen Family) 535-'·
Points of difference
(i) Oxygen is a gas while others are solids.
(ii) It is diatomic molecule, while the rest are complex
ns· np molecules, e.g., S8, Ses With puckered ring structure.
[ll] Inl i i i I \ (iii) \ Oxygen' is hlghlYllon-metallic due -to high value of
'--v-------'
sp' hybridization x ... electronegativity.
(iv) Oxygen is more ionic in its compounds. The dinegative
x anion 0 2- is quite common. The dinegative anions of other
Fig. 11.5 members are less common.
(v) Oxygen exhibits an oxidation state of only -2 except in
The bond angle is less than 109°28' due to the presence of OF2 and peroxides. It does not show +4 and +6 oxidation
lone pairs. The bond angle is 1030 in SCl2, 101,50 in OF2 and states as shown by other members.
98°--m-TeBr2'-~~--~~~~~ . ~-~ ~ '~(vi1~0x:ygen~molecule~is~hi~y-stable, The-twoatoms~am-
Dimeric monohalides. as S2F2, S2Cl2 and S2Br2 are known. held together by mUltiple bonds. The bonds are fairly strong
Their structure is similar to H2~' and bond energy is quite high (117 kcal per mole). It is only
CI at a high temperature that these bonds are broken and oxygen
S
/ atoms react with other materials. TI1Us,~ordinary~oxygen jsnoL'~~ .
active under ordinary conditions:
(vii) Hydrogen bonding is present in water and many other
,sL
/ - 104
0
compounds due to high electronegativity of oxygen. On account
of this, water boils at higher temperature.
(viii) Oxygen molecule is paramagnetic in nature in gaseous,
CI
liquid and solid states. It is weakly attracted by a magnet. It has
Fig. 11.6 been explained by molecular orbital theory that oxygen molecule
[Note : As fluorine is more electronegative than oxygen, the compounds has two unpaired electrons.
of oxygen and fluorine are called fluorides. For example, OF2 is (ix) Oxygen is the most abundant element in the earth's crust.
named oxygen difluoride. The compounds of oxygen and other (x) Metals like Cu, Ag, Hg, etc., show lesser affinity with
halogens are called oxides as oxygen is more electronegative than O 2 to form oxide than with sulphur to form sulphide. It is due
chlorine, bromine and iodine. For example, CI02 is called chlorine
dioxide and hOs is named iodine pentoxide.]
to polarizing power of Cu2+, Ag+, Hl+ ion, owing to which
they form strong bond with S2-.
(e) Oxyhalides 11~a:~ DISSIMILARITIES BETWEEN OXYGEN
Only S and Se form oxyhalides. They are called thionyl and oj AND SULPHUR
selenyl halides.
Property Oxygen . Sulphur
SOFi
SeOF2 1. Electronic 2 electrons in the penul- 8 electrons in the penul-
These react with water readily. configuration timate orbit timate orbit
2. Physical state Colourless, odourless Pale yellow solid with
SOCl2 + H20 ~ S02 + 2HCl
gas faint odour
In addition, sulplWryl halides are also known. 3. Abundance Most abundant Less abundant
S02 X 2 4. Maximum 2 6
These may be regarded as derivatives of H2S04 where both covalency
the -OH groups have been replaced by two halogens atoms. 5. Action of Not affected Oxidised to H 2SO4
"" ~«
HN03
11 ~2{'i ABNORMAL BEHAVIOUR OF OXYGEN 6. Nature of H 20 is neutral liquid H2S is acidic gas under
Oxygen differs from rest of the members of VIA group . hydride under ordinary condi- ordinary conditions. No
elements. The. abnormal behaviour is attributed due to the tions. Hydrogen bond- hydrogen bonding is
following inherent characteristics: ing is present. present.
(i) Small size 7. Molecule Diatomic, O2 Octatomic, Sg
(ii) High electronegativity 8. Magnetic Paramagnetic molecule Diamagnetic molecule
(iii) Non-availability of d-orbitals in the valency shell. nature
I
1· OXYGEN Laboratory preparation: The usual laboratory method

consists in heating of a mixture of potassium chlorate and
Historical: Priestley and Sch...ele obtained oxygen within
manganese dioxide in ratio of 4 : I. KCI0 3 evolves oxygen at
a few months of each other by heating suitable oxygen
375°C. At this temperature, it melts and converted into potassium
compounds. Scheele called it vital air or tire air. Lavoisier
perchlorate which decomposes at higher temperature to evolve
regarded it as an essential constituent of all acids and named
oxygen. When Mn02 is added, it starts giving oxygen at 250°C.
it oxygen (oxus acid, gennas = maker).
Here Mn02 acts as a catalyst.
Occurrence: Oxygen occurs in the atmosphere to the
4KCI0 3 ---7 3KCI0 4 + KCI
extent of about 21 % by volume (23% by mass). This percentage Potassium Potassium
remains constant by the operation of the highly complex process chlorate perchlorate
termed photosynthesis. It is an essential ingredient in all living KCl0 4 650°C) KCI + 202
matter and is of great importance in respiration and combustion.
It is most abundant element and forms about one half of the Mn02 used for this purpose should be completely free from
eart1!'s crust:ltf~rtll~1! larg€U'art~fJ1eru:lyJ1lUh.~r()s1<L@<l carbol11!~J5.CI03aI1<l c~QQn I1ILxtl.!!~ ls_exIllosive in_l1atun'!""L'_ __
is present to the extent of 89% by weight in water. The mixture should be first heated gently and then strongly
when it is ensured that there is no vigorous reaction.
II Preparation
Oxygen _can _be_obtained iathelaboratory -b.y_following
II Properties
methods: Oxygen is a colourless, odourless and tasteless gas.
(i) From oxides: (a) By thermal decomposition of the little heavier than air and is slightly soluble in water. This small
oxides of metals which are in lower part of electrochemical amount of dissolved oxygen in water support.'> the respiration
series. of fish and other aquatic animals. It is soluble in alkaline
. 450"C .. 350°C pyrogallol. It can be liquefied to a pale blue liquid (b. pt.-183°C)
2HgO ~ 2Hg+0 2; 2Ag20 ) 4Ag+0 2 by compressing the gas at a very low temperature. It is
(b) By the thermal decomposition of higher oxides. transformed into a blue solid on further cooling (freezing point
3Mn02 ~ Mn304 + O 2; 2Pb 30 4 Heat) 6PbO + O 2 = 218.4°C). Although O2 has an even number of electrons,-
two of them are unpaired, making the molecule paramagnetic;
2Ba02Heat ) 2BaO + O 2
since it behaves like a tiny magnet and is attracted to a magnetic
(c) By action of conc. H 2S04 on Mn02. field. It exhibits allotropy. Its allotropic modification is ozone
2Mn02 + 2H2S04 ---7 2MnS04 + 2H20 + O 2 (0 3), There are three isotopes of oxygen with mass numbers
16
(d) By action of water on sodium peroxide (oxone). 16, 17 and 18 (0 , 0 17 and 0 18 ).0 16 is the main one with
2Na202 + 2H20 ---7 4NaOH + O 2 an abundance of nearly 99.8%. The others are 0 17 (0.04%)
(ii) From salts: (a) Alkali nitrates on heating evolve and 0 18 (0.2%).
oxygen. Oxygen is not a combustible gas, but it is a strong supporter
2NaN0 3 ~ 2NaN02 + O2; 2KN0 3 ~ 2KN0 2 + O 2 of combustion. It is very active element. It directly combines
(b) K2Cr207, KMn04 and KCl03 decompose at high with almost all metals (except noble metals) and non-metals
temperatures evolving oxygen. (except zero group elements and halogens) and reacts with
many compounds under suitable conditions. In fact, all the
400°C
4K2Cr207 ) 4K2Cr04 + 2Cr203 + 30 2 chemical reactions of oxygen are oxidation reactions. Except
250°C very few, the reactions with oxygen are exothermic in nature.
2KMn04 ) K2Mn04 + Mn02 + O 2
A flame may also be produced in certain cases.
2KCI03 ~ 2KCI + 30 2
(c) By heating KMn04 or K2Cr207 with concentrated H 2S04, • Reactions with metals
4KMn04 + 6H2S04 ~ 2K2S04 + 4MnS0 4 + 6H20 + 50 2 (a) Active metals react at room temperature forming
2K2Cr207 + 8H2S04 ~ 2K2S04 + 2Cr2(S04h + 8H20 + 302 respective oxides.
(d) By adding H 20 2 to acidified KMn04 solution. 4Na + O 2 ~ 2Na20
2KMn04 + 3H2S04(dil.) ~ K 2S04 + 2MnS04 + 3H20 + 5[0] 2Ca + O 2 ~ 2CaO
[H202 + 0 ~ H 20 + O 2] x 5 However, Na, K, Rb, etc., further combine with oxygen to
form peroxides and superoxides.
2KMn04 + 3H2S04 + 5H20 2 ~K 2S0 4 + 2MnS04
+ 8H20 + 502 M M 20 M 202 ---=--7 °2 M0 2
Normal oxide Peroxide Super oxide
Pure oxygen is obtained by this reaction. (LiP) ( Na20 2) (K0 2 ,Rb0 2 ,CS0 2 )
Elements of Group VIA or 16 (The Oxygen Family) 537--·
(b) Magnesium bums in atmosphere of O2 to form magnesium
.. ..0:
:0
oxide.
This structure although can explain paramagnetic behaviour
2Mg + O2 ~ 2MgO
yet it does not explain high dissociation energy of oxygen
(c) Metals like Fe, AI combine with dioxygen on heating. molecule and does not conform to the octet rule.
4Al + 302 ~ 2Al20 3 Another structure, involving 3-electron bonds, has been
4Fe + 302 ~ 2Fe203 suggested by Pauling. 1\vo oxygen atoms are joined by one
2-electron bond and two 3-electron bonds. The structure
• Reactions with nonmetals accounts for two unpaired electrons and for the high dissociation
energy but is contrary to octet rule.
Most of the nonmetals react with oxygen under high
temperatures and form respec~ oxides. For example, :0: : :0:
A better explanation for the existence of two unpaired
HYdrogen: 2H2 + O 2 - - - -1073K
- ' - - - 7 ) 2H 0
2 electroIlSjp~am~netic l:l~haviQl.!!) and.<l. very high dissociation
oreie€tnc . Wafer
discharge energy of O 2 molecule has been provided by molecular orbital
3273 K theory according to which the structure of O2 molecule is
Nitrogen: N2 + O 2 2NO
Nitric oxide given below:
. --S02 KKcr(2s)2cr*(2s)~cr(2Px)21t(2py)21t(2pi1t*(2,py)i'1t*(2Pz)1
Sulphur: S
Sulphur dioxide Bond order in this case is ~ (8 4) = 2
Carbon: 2C+ O2 Heat) 2CO
(Limited) Carbon monoxide e Uses
C+ O 2 CO 2 (i) Oxygen mixed with helium or carbon dioxide is used for
(Excess) Carbondioxide
artificial respiration.
Phosphorus : P4 +502 Heat
P4 0 10
(ii) Liquid oxygen is an important constituent of fuels .used
in rockets.
Phosphorus pentoxide
(iii) Liquid oxygen mixed with finely divided carbon acts
• Reactions with compounds like a dynamite in coal mining.
Oxygen is an oxidising agent. It oxidises many compounds (iv) Oxygen is used for production of oxy-hydrogen or
under specific conditions. Some examples are given here. oxy-acetylene flames which are employed for cutting and
. welding purposes.
2NO + O2 ~ 2N02
(v) Oxygen is used as an oxidising agent in several reactions.
4HCl+0 2 700K )2H O+Cl (Deacon's process) (vi) Oxygen is used in the manufacture of large number of
CuCl 2 2 2
compounds such as phenol, ethylene oxide, sulphur dioxide,
4NH3 +50 2 1073K )4NO+6H 0 (Ostwald's process) sulphuric acid, nitric acid, chlorine, etc,
Pt 2
723 K
(vii) 18 0 is used as a tracer in the study of tracer
2S0 2 +0 2 20s )2S0 3 (Contact process) mechanisms.
2ZnS + 302 ~ 2ZnO + 2S02
OXIDES
CxHy +( X+~)02~XC02 +~H20 Oxygen combines nearly with all other elements except inert
gases, noble metals and halogens. The binary compounds of
~ Structure oxygen with other elements are called oxides. However,
the compounds of oxygen and fluorine (OF2, 02F2) are not
The diatomic oxygen molecule has an unusual electronic
called as oxides but oxygen fluorides as fluorine is more
structure. It is believed that two oxygen atoms in the molecule
electronegative than oxygen.
are bonded by a covalent double bond.
:0: :0: or
.. ..0:
:0
Oxides may be prepared by the following general
methods:
. 1. By burning of elements such as C, P, S, Na, K, Mg, etc.,
However, the above structure is not supported by its in air or oxygen atmosphere.
paramagnetic nature. It has been suggested that between the
C + O2 ~ CO2 (Carbon bums with flush light)
two oxygen atoms only one covalent bond is established leaving
two unpaired electrons, one in each atom. (Sulphur bums with blue light)
4Na + O2 ~ 2Na20 (Sodium bums with yellow light)
4K + 02 ~ 2K20 (Potassium burns with violet light) Si02 + 2NaOH ---t Na2Si03 + H 20
2Mg + O2 ~ 2MgO (Magnesium burns with white light) Oxide Base Salt Water
2. By strongly heating carbonates, hydroxides or nitrates. B20 3 + 6NaOH ~ 2Na3B03 + 3H20

Cu(OHh ~ CuO + H20 P4010 + 12NaOH ---t 4Na3P04 + 6H 20
CaC03 ~ CaO + CO2 Acidic oxide Ba~e Salt
2Pb(N03h ~ 2PbO + 4N02 + O2 Si02 + CaO ~ CaSi03 \

\
2Al(OHh ~ Al2~ + 3H20 S03 + PbO ~ PbS0 4 \
CUC03 ~ CuO + CO2 (li) Basic oxides: The oxides which either dissolve in
2Ba(N03)z ~ 2BaO + 4N02 + O2 water to form alkalies or combine with acids to form salts and
water or combine with acidic oxides to form salts are called
(The carbonates, hydroxides of alkali metals do' not
basic oxides. These oxides are formed by metals. Oxides may
decompose onheating~andnitratesof alkali metals form nitrites be ionic or covalent in nature:~~
on heating.)
3. The oxides of some of the non-metals and weak metals Na20 + H 20 ~ 2NaOH
can be formed by the oxidation of the element with nitric' acid. Cao + H20 ~ Ca(OH)z
C + 4HN03(conc.) ~ CO2 + 4N02 + 2HzO CuO + H2S04 ~CUS04~+ H20
Si + 4HN03(conc.) ~ Si02 + 4N02 + 2H20 FeO + H2S04 ~ FeS04 + H20
Sn + 4HN03(conc.) ~ Sn02 + 4N02 + 2H20 BaO + 2HCI ~ BaCl2 + H20
PbO + S03 ~ PbS04
111 Classification of Oxides
(iii) Neutral oxides: The oxides which neither combine
(Based on Chemical Behaviour)
with acids nor with bases to form salts.
(i) Acidic oxides: The oxides which dissolve in water to Examples: CO, H20, N20, NO, etc.
form oxyacids are called acidic oxides. These are also called
(iv) Amphoteric (I"ides: The oxides which react with
acid anhydrides of corresponding acids. The oxides combine
with bases to form salts and water and with basic oxides form acids and bases both are termed amphoteric.
salts only. Examples: ZnO, Al 20 3, BeO, Sb20 3, Cr203, PbO, Pb02,
These oxides are generally formed by non-metals. Examples etc.
are: ZnO + 2NaOH ~ Na2Zn02 + H20
C02, B20 3, Si0 2, N20 3, N02, N20 5, P40 6, P40 8, ·P40 lO, ZnO + 2HCl ~ ZnCl2 + H20
S02, Clz07, 120S and by metals in higher oxidation states such
as Sn02, V20S, Cr03, Mn207, etc. Al203 + 2NaOH ~ 2NaAl02 + H 20
CO2 + H20 ~ H2C03 Al 20 3 + 6HCI ~ 2AlCl3 + 3H20
S03 + H20 ~ H2S04 PbO + 2NaOH ~ Na2Pb02 + H20
S02 + H20 ~ H2S03 PbO + H2S04 ~ PbS04 + H20
N20S + H20 ~ 2HN03 Cr203 + 2NaOH ~ Na2Cr204 + H20
N203 + H20 ~ 2HN02 Cr203 + 3H2S04 ~ Cr2(S04h + 3H20
P406 + 6H20 ~ 4H3P03 (v) Compound or mixed oxides: Oxides which behave
P4010 + 6H20 ~ 4H3P04 as mixture of two simple oxides.
Cl20 7 + H20 ~ 2HCl04 Examples:
Sn02 + H20 ~ H2Sn03 Pb30 4(2PbO + Pb02), Fe304(FeO + Fe203),
Mn207 + H20 ~ 2HMn°4 Mn30 4(2MnO + MnOz)
cr03 + H20 ~ H2Cr04 (vi) Peroxides: The oxides when treated with dilute acids
[Some of the oxides form two oxyacids. These are called form hydrogen peroxide. These oxides are considered as
mixed anhydrides. derivatives of H202 and contain peroxo linkage in their
molecules.
2N02 + H20 ~ HN02 + HN03
Examples: Na202, K20 2, Ba02, etc.
P40 8 + 6H20 ~ 2H 3P03 + 2H3P04 ]
Na202 + H2S04(diL) ~ Na2S04 + H20 2
Ba02 + H2S04(dil.) ~ BaS04 + H202 (i) Siemen's ozoniser

Na20z can be written as Na-O-O-Na. The linkage It consists of two concentric metal or glass tubes sealed
-0-0- is called peroxo linkage. together at one end (Fig. 11.7).
(vii) Dioxides: Like peroxides, these also contain excess
of oxygen but do not form H20 2 with dilute acids. They evolve
Tinfoil
chlorine with concentrated HCI and oxygen with concentrated <
H2 S04'
Examples: Pb02, Ml02
Ml02 + 4HCI (conc.) ~ MnCl2 + Cl2 + 2H20
2Ml02 + 2H2S04 (conc.) ~ 2MnS04 + 02 + 2H20
(viii) Suboxides: The oxides which contain less oxygen
Ozonised
oxygen L3!o---fOil --J
Induction coil
than· eXpeGted-fromthe-normal-valeney of-the elements are -Fig. 41.7

termed suboxides. The inner surface of inner tube and outer surface of the
Examples:
\
Carbon suboxide, C30 2; lead suboxide, Pb20; outer tube are coated with tin foil. The inner and outer coatings
nitrous oxide, N20. are connected with the two terminals of an induction coil. A
(ixJSuperoxides: These oxides contain02:ion. The cuiTerit .of dry oxygen at low temperature is passe&In fromc-=~ -
superoxioes -known are KOi, -Rb02 and C802: These react one end. When the current is put on, the oxygen is partially
with water to give hydrogen peroxide and oxygen. converted into ozone. Ozonised oxygen come out from other
\ 2K02 + 2H20 ~ 2KOH + H20 2 + O2 end and is collected. It contains about 10% ozone, the percentage
can be increased upto 15% if temperature is lowered to 5°C.
11~ OZONE
(ii) Brodie's ozoniser
Historical: In 1758, Van Marum observed a rotten smell
when an electric discharge was passed through air. In 1840, It is shown in Fig. 11.8. The annular space is surrounded
Schonbien attributed that the rotten smell was due to formation on both sides by dilute sulphuric acid in which platinum
of a new gas which he named ozone. The name ozone com(ls electrodes are dipped. These electrodes are connected to an
from the Greek word "ozo" meaning "smell". In 1866, Sorret Platinum electrode
established its formula, 0 3, and pointed out that the ozone is
an allotrope of oxygen.
Occurrence: Ozone is present in sufficient amounts in
the atmosphere at higher altitudes, i.e., :2 to 15 miles above
earth's surface. It is formed from oxygen present there, under
the influence of ultraviolet rays from sun. Near earth's surface
it is decomposed by dust particles. In small amounts, it occurs
near the sea side or big lakes where it is formed by slow
evaporation of water.
!B Laboratory Preparation
Ozone is obtained by passing silent electric discharge through
dry oxygen. It is believed that some of the oxygen molecules
dissociate and then atomic oxygen combines with oxygen Fig. 11.8
~olecules to form ozone.
induction coil. Oxygen passing through the annular space is
O2 Energy ) 0 + 0 subjected to silent electric discharge and is partially converted
02+0~03
into ozone.
30z ~ 203 - energy Recovery of Pure Ozone from Ozonised Oxygen
The mixture obtained consists of 5-10% ozone by volume The ozonised oxygen is passed through a spiral cooled by
and the mixture is called ozonised oxygen. The apparatus liquid air. Ozone condenses as its condensation temperature is
used for this purpose is known as ozoniser. The commonly -112.4°C. The liquid ozone thus obtained may contain some
used ozonisers are : dissolved oxygen. This liquid is fractionally distilled to get pure
(i) Siemen's ozoniser and (ii) Brodie's ozoniser ozone.
Some Reactions Forming Ozone (ii) Acidified ferrous sulphate into ferric sulphate.
03~ O2 + 0
(i) Fluorine reacts with water at a very low temperature
when mixture of ozonised oxygen is formed. 2FeS04 + H2S04 + 0 ~ Fez(S04h + H20
2Fz +2H 20 ~ 4HF+02} . 2FeS04 + H2S04 + 03 ~ Fe2(S04h + H20 + 02

3Fz + 3H20 ~ 6HF + 03 Ozomsed oxygen (iii) It liberates iodine from neutral KI solution.
03~ O2 + 0
(ii) By action of ultra-violet rays, oxygen can be converted
2KI + H 20 + 0 ~ 2KOH + 12
into ozone.
2KI + H20 + 0 3 ~ 2KOH + 12 + O2
02~0+0 (iv) Lead sulphide (black) is oxidised to lead sulphate
02+0~ 03 (colourless).
(iii) The electrolysis of acidified water with high current [0 3 ~ O2 + 0] x 4
density and platinumanodeyields-ozone on the anode; Nascent .PbS+AO---)--PbS04-
oxygen discharged at anode combines with molecular oxygen PbS + 40 3 ~ PbS04 + 402
to form ozone. Similarly, CuS, ZnS and CdS are oxidised to CuS04,
ZnS04 and CdS04, respectively.
IIPr()perties (v)Jt oxidises-nitrites iQto-nitrates, sulphites into sulphates.;
Physical properties arsenites to arsenates, manganate to permanganate and ferro-
(a) It is a pale blue gas with a characteristic strong smell. cyanide to ferricyanide.
(b) It can be liquefied to pale blue liquid at -112.4°C. At NaN02 + 0 3 ~
NaN0 3 + O2
-249.7°C, it forms violet black crystals.
Na2S03 + 0 3 ~ Na2S04 + O2
(c) It is heavier than air.
(d) It is slightly soluble in water but more soluble in turpentine Na3As03 + 0 3 ~ Na3As04 + O2
Sodium arsenite Sodium arsenate
oil, glacial acetic acid, or carbon tetrachloride.
(e) When inhaled in small amounts, it causes headache and 2K2Mn04 + H20 + 0 3 ~ 2KMn0 4 + 2KOH + O2
Potassium Potassium .
nausea. manganate permanganate
(f) It is diamagnetic in nature. 2~Fe(CN)6 + H20 + 0 3 ~ 2K3Fe(CN)6 + 2KOH + O2
Chemical properties: Potassium Potassium
ferrocyanide ferricyanide
(a) Decomposition: It is unstable and decomposes
completely into oxygen at 300°C. (vi) Moist iodine is oxidised to iodic acid.
[0 3 ~ O2 + 0] x 5
Heat
20 3 ~ 302 + 68 kcal 12 + H20 + 50 ~ 2HI0 3
Mn0 2, platinum black, silver, lead dioxide, etc., decompose 12 + H 20 + 503 ~ 2HI03 + 502
ozone at ordinary temperature, i.e., they catalyse its decom- lodie acid
position. Similarly; moist sulphur, phosphorus and arsenic are oxidised
(b) Oxidising nature: Due to the ease with which it can to their corresponding oxyacids.
liberate nascent oxygen, it acts as a powerful oxidising agent. S + H 20 + 303 ~ H2S04 + 302
The potential equation is : 2P + 3H20 + 50 3 ~ 2H3P04 + 50 2
03~02+0 2As + 3H20 + 50 3 ~ 2H3As04 + 502
(vii) H2S is oxidised to sulphur.
The oxidation potential in acid medium is +2.07 V.
H2S + 0 3 ~ H20 + S + O 2
0 3 + 2H+ + 2e- ~ O2 + H20 E' = +2.07 V (viii) Alkaline KI is oxidised to potassium iodate and
[There are only three more substances which have oxidation periodate.
potentials higher than +2.07 V These are fluorine, atomic
oxygen and oxygen fluoride, OF2]. Due to high value of Potassium iodate
oxidation potential it acts as a strong oxidising agent. KI+40 3 ~ KI0 4 +40 2
Examples: (i) It oxidises HCI into C12, HBr into Br2 and Pot. periodate
HI into iodine. (ix) Dry iodine is oxidised to yellow pOWder, 409,
03~02 + 0 [0 3 ~ O2 + 0] x 9
2HCI + 0 ~ H20 + Cl2 212 + 90 ~ 409
2HCI + 03 ~ H20 + C12 + O2
o
Elements of Group VIA or 16 (The Oxygen Family) 541-····--
(x) Silver metal is blackened due to alternate oxidation of the synthetic camphor and potassium permanganate (by oxidation
metal and reduction of oxide. of potassium manganate).
2Ag + 0 3 ----7 Ag 20 + O 2 (iv) It is used for detecting the position of double bond in
Ag20 + 0 3 ----7 2Ag + 202 the unsaturated organic compounds.
(xi) Mercury in presence of ozone is oxidised to suboxide (v) In destroying odours that arise from cold storage rooms,
which dissolves in mercury. It starts sticking to glass and loses kitchens of big hotels or slaughter houses.
mobility. Hence, mercury loses its meniscus in contact with
ozone. This is termed as the tailing of mercury. Ii Structure of Ozone
2Hg + 0 3 ----7. Hg 20 + O2 Trambaruls (1953) and Hughes (1956) have pointed out from
(xii) Ozone reacts with KOH and forms potassium the studies of ozone by electron diffraction that ozone molecule
ozonide, K0 3, which is an orange coloured solid and contains is V-shaped with a bond angle of 116.8° and 0-0 bond length
paramagnetic 0 3- ion. 1.278 A. The central oxygen atom in ozone is s/-hybridized.
_. 2KOH~503_~2K03-±_5QL±ll:&
In all above reactions, oxygen is evolved.
There are few reactions in which whole of the oxygen is
used up in the process of oxidation.
1. Oxidises S02 to S03.
-3802 + 0 3 ----7 3S03 Fig>11.9 .
2. Acidified stannous chloride is oxidised to stannic The bond length is intermediate between that for a single
chloride.' bond (1.48 A as in H202) and for a double bond (1.21 A as
3SnClz + 6HCI + 03 ----7 3SnCl4 + 3H20 in O 2), Ozone is, therefore, considered to be a resonance
(c) Bleaching. property: It is a good bleaching agent hybrid of the following two fornls :
The bleaching action is due to its oxidising action on the organic
/~.
~/"
matter.
Coloured substance + 0 ----7 Colourless
It bleaches oil, ivory, flour, starch, waxes, wood pulp, etc.
(d) Formation of ozonides: Ozone reacts with unsaturated
,
.. / 00'
.. .. ..
organic compounds containing double bonds. The products Fig. 11.10
formed are known as ozonides. The ozonides break up when Tests of ozone: (i) It has a strong rotten smell.
treated with water to form carbonyl compounds. The process is (ii) Metallic mercury loses its fluidity in contact with ozone.
called ozonolysis. H 20 2 is evolved in most of the cases. (iii) It turns an alcoholic solution of benzidine brown.
(iv) It turns an alcoholic solution of tetramethyl base violet
<
CHR-O
R-CH CH-R' + 0 3 --70 I (v) It turns starch-iodide paper blue.
CHR'-O Distinction between Ozone and Hydrogen Peroxide
Ozonide
Hydrogen peroxide (HzO~
1. Pale blue gas with a strong Colourless and odourless syrupy
rotten smell. liquid.
2. It does not decolourise acidified It decolourises acidified potassium
potassium permanganate. perrnanganate.
(e) Reaction with peroxide: Reaction of ozone with 3. Mercury loses its meniscus in No action on mercury.
peroxide results in their mutual reduction with the liberation of contact with ozone. It starts
oxygen. sticking to glass.
4. It turns an alcoholic solution of No action.
Ba02 + 0 3 ----7 BaO + 202 benzidine brown.
H 20 2 + 0 3 ----7 H20 + 202 5. It turns an alcoholic solution of No action.
tetramethy1 base violet.
6. It does not tum starch-iodide It turns starch-iodide paper blue in
Uses paper blue in presence of ferrous presence of ferrous sulphate.
(i) As a germicide and disinfectant for sterilizing water and sulphate.
7. No action with titanium Orange colour with titanium
improving the atmosphere of crowded places like tube railways, sulphate solution. sulphate solution is developed.
mines and cinema halls. 8. No action with pcidified Blue colour in ether layer when
(ii) As a bleaching agent for oils, flour, ivory, wax and potassium dichromate in H20 2 is added to mixture
delicate fabrics. presence of ether. containing potassium dichromate
(iii) In the manufacture of artificial silk, synthetic silk, and concentrated H2S04 in
presence of ether.
as a liquid to the surface where it is allowed to solidify. 99.5%

pure sulphur is obtained by this process.
Compressed
air
Hot sulphur
froth "'-'I2iZ:~':i
The name sulphur has been derived from Sanskrit word Sulveri
meaning killer of copper. The elementary nature of sulphur
was established by Lavoisier in 1777.
{)ccurrence; Itiswidelymstributed··in nature both in
free and combined state. The free sulphur is found in the
volcanic regions of Sicily, Iceland, Japan, Mexico and Louisiana
and Texas states of U.S.A. Sulphur in American deposits occurs
at a depth of about 700-1200 feet while Sicily deposits are
associated with 75% clay ana'gypsum. These are the two main
sources of world supply of sulphur. In small quantities, it
occurs in New Zealand, Russia, Baluchistan (Pakistan) and
Kangra (India).
It occurs in abundance in the combined state as:
(i) Sulphide ores, e.g., Zinc blende or sphalerite (ZnS),
galena (PbS), cinnabar (HgS), copper pyrites (CuFeS2) and iron
pyrites (FeS2)' Iron pyrite is called ''fool's gold" because of its
misleading resemblance to gold metal.
Fig. 11.12 The Frasch process for extraction of sulphur
(ii) Sulphnr as a byproduct: (a) From alkali waste of

Leblanc's process: The alkali waste (mainly CaS) is sus-
pended in water and carbon dioxide is circulated. Hydrogen
sulphide is liberated which is burnt in an insufficient supply of
air.
(a) (b) (c) (d) CaS + H20 + C02 ~ CaC03 + H 2S
Fig.11.11 Sulphide ores (from left to right) : (a) Galena, PbS; 2HzS + 02 ~ 2H20 + 2S
(b) Cinnabar, HgS; (c) Pyrite, FeS2; and (d) Sphalerite, ZnS (Air)
(ii) Sulphate ores, e.g., Gypsum (CaS04·2H20), barytes (b) From the spent oxides of the gas works: It contains
(BaS04), Epsom salt (MgS04·7H20) and celesite (SrS04). ferric sulphide (Fe2S3)' It is exposed to air for a few days
(iii) H2S and S02 in volcanic gases. HzS in spring waters, when sulphur is deposited.
coal gas, sewage gas, etc. 2FezS3 + 30z ~ 2Fez03 + 6S
(iv) Organic compounds of plant and animal origin, e.g.,
(c) From iron pyrites: Iron pyrites is a good source of
onion, garlic, mustard, eggs, proteins, hair, wool, etc., contain
sulphur. It is recovered when pyrite is distilled.
organic sulphur compounds.
Distillation
Sulphur is also found as deposits of the native element 3FeSz ---~) Fe3S4 + 2S
(brium-stone), which are formed by bacterial action on H 2S.
Pure sulphur is obtained by boiling impure sulphur at
Extraction: (i) To extract underground sulphur, Frasch
444°C. The vapours of sulphur evolved are condensed on the
process is used. Three concentric pipes are sunk deep into the
cold walls as a light yellow powder.
ground. Super heated water at 170°C is forced down through
the outer pipe into sulphur deposits, which heats the rock ~ Allotropic Forms
above the melting point of sulphur, 119°C. By this way sulphur
gets melted. Compresed air blown through innermost pipe Sulphur exists in several allotropic forms, the important
forcess the molten sulphur to come out through the third pipe, ones are described ahead:
Elements of Group VIA or 16 (The Oxygen Family) 543~-
1. Rhombic or octahedral or a.-sulphur: This is Uses: Sulphur is used :

the common form of sulphur. It is pale yellow in colour. It (i) in the manufacture of S02, H2S04, CS 2, matches, gun
melts at 114SC. Its specific gravity is 2.06. It is insoluble in powder, fire works, etc.
water but readily soluble in carbon disulphide. It dissolves to (ii) as a disinfectant for houses and for destroying bacteria,
some extent in benzene, alcohol and ether. It is a crystalline fungi, insects, etc. (vapouts of sulphur are poisonous for
variety and consists of S8 structural units packed together into bacteria, etc., but not for human beings).
octahedral shape. This is the stable variety at ordinary (iii) for vulcanising rubber and in the manufacture of sulphur
temperature and all other forms gradually change into this dyes.
form. This form gets converted into monoclinic form when (iv) in medicine, for internal as well as external applications.
heated above 96°C.
11 ~8~J COMPOUNDS OF SULPHUR
The main compounds of sulphur are,
1. HYdrog~ll_suJpl1i<l~or s1.lIphun!tt~(Lhydt'o$n_(H2S) ___~ ___
2. Oxides of sulphur
3. Oxyacids of sulphur
II 1. Hydrogen Sulphide or
SulpnurelteaAyarogen - (H28)
Occurrence: It occurs in volcanic gases, sewage gases,
(a) (b) coal gas and in several spring waters. It is found in small
amounts in atmosphere, where it comes from the heating of
Fig. 11.13 Structure of S8 molecule coal and decay of animal and vegetable matter containing sulphur
compounds.
2. Monoclinic or prismatic or p-sulphur: This form Laboratory preparation : Hydrogen sulphide is
is formed by melting sulphur in a dish and cooling till crust is obtained in the laboratory by the action of dilute sulphuric acid
formed. '!\vo holes are made in the crust and liquid is poured on ferrous sulphide.
out. On removing the crust, needle shaped crystals of
FeS + H2S04 ---? FeS04 + H2S
monoclinic sulphur are obtained.
This form of sulphur is stable above 95.6°C. The crystals As the gas is required intermittently in the laboratory, it is
are amber yellow in colour and have specific gravity of 1.96. prepared in the well known Kipp's apparatus (Fig. 11.14).
Crystals melt at 119°C. It is also soluble in carbon disulphide. The gas obtained is always impure as it is contaminated
Below 95.6°C, it changes into rhombic form. Thus, 95.6°C is with hydrogen. Pure hydrogen sulphide can be prepared by the
the transition temperature. action of pure HCI on antimony sulphide.
Sb2S3 + 6HCl---? 2SbCl3 + 3H2S
Rhombic sulphur Monoclinic sulphur
3. Plastic sulphur: This is obtained when boiling
sulphur is poured into cold water. It is soft rubber like mass
which hardens on standing and gradually changes into rhombic
sulphur. It is amber-brown in colour and has specific gravity
of 1.95. It is insoluble in CS2 and has no sharp melting point.
It consists of a completely random arrangement of. chains of
sulphur atoms.
Action of heat on sulphur

Ordinary sulphur melts at 114°C to a pale yellow mobile
liquid. On heating further instead of becoming more mobile, it
grows thicker. The colour changes to reddish brown and then
to almost black. At about 180°C, the viscosity increases so
much that it cannot be poured out by inverting the container.
At about 200°C the viscosity begins to decrease and at its
(a) (b)
boiling point of 444°C, the liquid is again mobile. No definite
. Fig. 11.14
explanation of these observations is known uptil now.
544 GR.B. Inorganic Chemistry"for Competitions
• Properties (viii) Acidified KMn04 is decolourised.

Physical properties: (a) It is a colourless gas with 2KMn04 + 3H2S04 ~ K 2S04 + 2MnS04 + 3H20 + 5[0]
unpleasant odour of rotten eggs. [H2S + 0 ~ H20 + S] x 5
(b) It is slightly heavier than air and moderatory soluble in 2KMn04+3H2S04+5H2S ~ K2S04+2MnS04+8H20+5S
cold water. The solubility decreases in hot water.
(c) It is poisonous in nature. It produces headache when (ix) Acidified K2Cr207 is reduced forming green chromic
inhaled in small quantities but may cause death when inhaled sulphate.
for a long time. K2Cr207 + 4H2S04 --? K2S04 + Cr2(S04h + 4H20 + 3[0]
(d) It can be easily liquefied by pressure. The boiling point [H2S + 0 --? H 20 + S] x 3
is about -60"C. It freezes to a transparent solid at -85.6°C.
K2Cr207+4H2S04+3H2S --? K 2S04+ Cr2(S04h+ 7H20+3S
Chemical properties: (a) Combustibility: The gas
burns with a blue flame in oxygen or air forming sulphur (d) Acidic nature: The aqueous solution of H 2S acts as
dioxide and wateri~ a weak: dibasi~cid. It ionises
2H2S + 302 ~ 2H20 + 2S02 H2S~H++HS
In restricted supply of oxygen, sulphur is formed due to It forms two series of salts, hydro sulphides and sulphides.
incomplete combustion.
NaOH+H 2S ~ NaHS +H 20
~2I-12S:+ ~02 ~ 2H20 + 2S . Sodiumhydro-
(b) Thermal decompoSition: Th~~gas~i~not~o stable as sulphide
water. It decomposes on heating. The decomposition starts at
310°C and completes at 1700~C. Sodium sulphide
H2S~ H2 + S (e) Reaction with metals and metal oxides: H2S
(c) Reducing nature: Hydrogen sulphide acts as a strong reacts with metals and metal oxides to form" corresponding
reducing agent as it decomposes evolving hydrogen. The sulphides.
following are the important examples of its reducing action: 2Na + H2S ~ Na2S + H2
(i) It reduces halogens into corresponding hydracids. Cu + H 2S ~ CuS + H2
H2S + X2 ~ 2HX + S (X2 = F2, C12, Br2 or 12) 2Ag + H2S ~ Ag 2S + H2
(ii) It reduces ferric chloride to ferrous chloride.
Pb + H2S ~ PbS +H2
2FeCl3 + H2S ~ 2FeCl2 + 2HCI + S
Heat
(iii) Sulphur dioxide is reduced to sulphur in presence of CaO + H2S -----7 CaS + H 20
moisture. Heat
ZnO + H2S -----7ZnS + H 20
S02 + 2H2S ~ 3S + 2H20
(f) Action on salts: Hydrogen sulphide reacts with salts
The occurrence of sulphur in volcanic regions is attributed
of vruious metals forming corresponding sulphides. The metal
due to the above reaction as both gases are present in volcanic
sulphides can be divided into three groups.
gases.
(i) Sulphides precipitated in acidic medium: These
(iv) H2~ is reduced to water.
are sulphides. of Hg, Ag, Pb, Cu, Bi, Cd, As, Sb and Sn.
H 20 2 + H 2S ~ 2H2 0 + S
CUS04 + H 2S ~ CuS + H 2S04
(v) 0 3 is reduced to O2,
Pb(CH3COOh + H 2S ~ PbS + 2CH3COOH
HzS + 0 3 ~ H20 + S + O 2
CdS04 + H 2S CdS + H 2S04
(vi) HN03 is reduced to N02.
2HN03 ~ H 20 + 2N02 + 0 HgS, CUS, PbS - Black }
Insoluble in yellow
Bi 2S 3 - Brown
H2S + 0 ~ H20 + S ammonium sulphide
CdS Yellow
2HN03 + H2S ~ 2N02 + S + 2H20
(vii) H2S04 is reduced to S02. SnS2, AS2S3 - Yellow }
Sb 2S3 - Orange Soluble in yellow
H2S04 ~ H 20 + S02 + 0 ammonium sulphide
SnS-Chocolate
H2S + 0 ~ H20 + S
Oi) Sulphides precipitated in alkaline medium: These
H2S04 + H2S ~ 2H20 + S02 + S
are the sulphides of Zn, Co, Ni, Mn and Fe.
[Note : H2S cannot be dried by cone. H2S0 4 because it oxidises HzS to
S. MnCl 2 + H2S ~ MnS + 2HCI
It is therefore dried by passing through CaClz or P401O'] Ni(N0 3h + H 2S ~ NiS + 2HN03
Elements of Group VIA or 16 (The Oxygen Family) 545
ZnS04 + H2S ~ ZnS + H2S04 (i) Sulphur dioxide, S02

CoS, NiS; Black, ZnS; White, MnS; Flesh coloured
Preparation : The following
(iii) Sulphides which are precipitated neither in acidic reactions can be used for the
. . nor in alkaline medinm: These are the sulphides of Cr, AI, preparation of sulphur dioxide.
Mg, Ba, Sr, Ca, Kand Na. (a) By burning sulphur in air or
(g) Fonnation of polysulphides: Poly sulphides of metals oxygen .
. are obtained by passing H2S through their hydroxides.
S + 02~ S02 Fig. 11.15 Structure of the
Ca(OHh + H2S ~ CaS + 2H20
(b) By heating sulphur with S02 molecule
CaS + 4H2S ~ CaS5 + 4H2 concentrated sulphuric acid.
On passing excess of H 2S through ammonium sulphide,
yellow ammonium sulphide is formed. S+2H 2S0 4 Heat) 2H 20+3S0 2
(cLIlyheltti_ng cOpper Qr .silvec witlLc_oncen~ted~sulphuric_..
2NH40H+H2S~~(NH4hS-+~H20·~~-·
acid.
(NH 4 hS+xH 2S ~ (NH 4 h Sx+l+ xH2
Ammonium Cu + 2H2S04 ~ CUS04 + 2H20 + S02
polysulphide
2Ag + 2H2S04 ~ Ag 2S04 + 2H20 + S02
(d) By reacting sOdium sulphite or sodium hydrosulphite~
• Uses with diL HCL
(i) It is an important laboratory reagent for the detection of
Na2S03 + 2HCI ~ 2NaCI + H20 + S02
basiC radicals in qualitative analysis.
(ii) It is used for the preparation of metallic sulphides many NaHS03 + HCl ~ NaCl + H20 + S02
of which find use in paint industry. (e) By roasting of sulphides.
(iii) It is used as a reducing agent. 2ZnS + 30 2 ~ 2ZnO + 2S02
4FeS 2 + 11 O 2 ~ 2Fe203 + 8S02
• Tests of hydrogen sulphide
The reactions (b), (c) and (d) can be used for the preparation
(i) It has unpleasant odour resembling that of rotten eggs.
of S02 in the laboratory while the reactions (a) and (e) are
(ii) It turns lead acetate paper black.
used in industry to obtain S02.
(iii) It gives a violet colouration with a solution of sodium In places where gypsum or anhydrite are found in abundance,
nitroprusside. sulphur dioxide can be obtained on a large scale by heating
gypsum or anhydrite with carbon at about lOOO°C.
• Structure of H2S
2CaS04 + C ~ 2CaO + 2S02 + CO2
The shape of the H2S molecule is similar to that of the water
molecule, i.e., V-shaped structure with bond length (H-S)
• Properties
1.35 A and bond angle (H-S-H) 92.so.
Physical properties: (a) It is a colourless gas with a
pungent, suffocating odour.
or :S~H
• x (b) It is heavier than air.
H (c) It is highly soluble in water.
H H (d) It can be easily liquefied to a colourless liquid at -lOoC
and into a snowlike solid at -76°C.
Chemical properties: (a) It neither burns nor it helps
ill 2. Oxide. of Sulphur in burning. However, burning magnesium and potassium
Sulphur forms a number of oxides. These are : continue to burn in its atmosphere.
(i) Sulphur suboxide, S20 (colourless gas) 3Mg + S02 ~ 2MgO + MgS
(ii) Sulphur monoxide, SO (colourless gas) 4K + 3S02 ~ K2S03 + K2S203
(iii) Sulphur sesquioxide, S203 (green crystalline solid)
(b) Thennal decomposition: It decomposes at 12000C
(iv) Sulphur dioxide, S~ (colourless gas)
producing sulphur trioxide and sulphur.
(v) Sulphur trioxide, S03 (volatile liquid)
(vi) Sulphur heptoxide, S207 (liquid) 3S0 2 ~ 2S0 3 + S
(vii) Sulphur tetroxide, S04 (white solid) (e) Acidic nature: It is an acidic oxide. It dissolves in
Out of these, sulphur dioxide and sulphur trioxide are common water forming sulphurous acid.
and important and described here. S02 + H20 ~ H 2S0 3 (Sulphurous acid)
The gas is, therefore, known as sulphurous anhydride. It K2Cr207 + 4H2S04 ~ K2S04 + Cr2(S04h + 4H20 + 3[0]
combines with basic oxides and forms sulphites. [S02 + 2H20 ~ H 2S04 + 2H] x 3
BaO + S02 ~ BaS03 [2H + 0 ~ H20] x 3
It reacts with alkalies forming two series of salts ...
K2Cr207 -+ 3S02 + H2S04 ~ K2S04 + Cr2(S04h + H20
NaOH + S02 ~ NaHS03 (Green)
Sod. bisulphite
(iv) Ferric sulphate is reduced to ferrous sulphate.
2NaOH + S02 --"7 Na2S03 + H 20
S02 + 2H20 ~ H2S04 + 2H
Sod. sulphite
Fe2(S04)3 + 2H ~ 2FeS04 + H2S04
It also decomposes carbonates and bicarbonates evolving
CO2 gas. Fe2(S04h + S02 + 2H20 ~ 2FeS04 + 2H2S04
2NaHS03 + CO 2 (v) It reduces acidified iodates to iodine.
Like~C02' iLturnslime water milk)'dueto~the formation of [S'o2_ ± 2H2D_~ ... _LH2.s.04_+2HJ:~L5__ ~ __ .._ . . . . . . . . . . . . . . . ._
CaS03' However, if S02 is passed for a long time,milkiness 2KI03 + H 2S04 ~ K2S04 + 2ID0 3
disappears due to formation of soluble calcium bisulphite.
2ID03 + lOH ~ 12 + 6H20
Ca(OHh +S02 ~ CaS03 + H 20
··(Milkiness) ~ -~ 2KI03 + 5S02 + 4H 20 ~ K.2S04 + 4f12S04. + 12
(f) Oxidising nature: It also· acts as an oxidiSIng agenf~·~c ~
CaS03 + H20 + S02 ~ Ca(HS03h
Cal. bisulphite particularly when treated with stronger reducing agents.
(soluble) 0) It oxidises H2S into S.
(d) Addition reactions: (i) It combines directly with 2H2S + S02 ~ 2H20 + 3S
halogens to form sulphuryl halides. (ii) Metals are oxidised by S02.
S02 + Cl2 ~ S02Cl2 (Sulphuryl chloride) 3Mg + S02 ----7 2MgO + MgS
Oi) It combines directly with oxygen in presence of a catalyst 4K + 3S02 ~ K2S03 + K2S20 3
(platinised asbestos). 3Fe + S02 ~ 2FeO + FeS
2S02 + O2 2S03 (iii) CO is oxidised to CO2 by S02.
(iii) It directly combines with lead dioxide to form lead 2CO + S02 ~ 2C02 + S
sulphate.
(iv) At lO00"C, it oxidises hydrogen into water.
Pb02 + S02 ~ PbS04
S02 + 2H2 ~ 2H20 + S
(e) Reducing nature: The aqueous solution of S02 acts
as a reducing agent as sulphurous acid changes into sulphuric (v) Stannous and mercurous salts are oxidised in presence
acid giving nascent hydrogen. of excess of HCl.
H20 + S02 ~ H2S03 2SnCl 2 + S02 + 4HCI ~ 2SnCl4 + 2H20 + S

2Hg2Clz + S02 + 4HCI ~ 4HgCl2 + 2H20 + S
H2S03 + H20 ~ H2S04 + 2H
(g) Bleaching action: S02 in presence of moisture acts
Examples: (i) It reduces halogens to their respective
as a bleaching agent. This is due to the reducing nature of S02'
hydracids.
S02 + 2H20 ~ H 2S04 + 2H
S02 + 2H20 H 2S04 + 2H
Coloured matter + H ~ Colourless matter
2H + Cl2 ~ 2HCI
The bleaching is temporary. The bleached matter when
S02 + 2H20 + Cl2 ~ H2S04 + 2HCI exposed to air regains its colour due to oxidation.
(ii) Acidified KMn04 is reduced, i.e., it is decolourised.
2KMn04 + 3H2S04 ~ K2S04 + 2MnS04 + 3H20 + 5[0] • Uses
[S02 + 2H20 ~ H2S04 + 2H] x 5 (i) It is used in the manufacture of sulphuric acid and paper
from wood pulp (use of bisulphites).
[2H + 0 ~ H 20] x 5
(ii) It is used as a bleaching agent for delicate articles like
2KMn04 + 5S02 + 2H20 ~ K2S04 + 2MnS04 + 2H2S04 wool, silk and straw.
(iii) Acidified K2Cr207 is turned green due to formation (iii) It is used in refining of petroleum and sugar.
of chromic sulphate. (iv) As a disirifectant for killing disease germs, fu,llgi and
certain moulds.
(v) As a refrigerant in the form of liquid S02. 5S0 3 + 2P ~ 5S02 + P20S

(vi) It is used as an antichlor for removing chlorine from a S03 + PCIs ~ POC1 3 +S02 +C1 2
fabric after bleaching. , Phosphoryl
Structure: Already described in section 11.1 (3b). chloride
S03 + 2HBr ~ H20 + Br2 + S02
(ii) Sulphur Trioxide, S03
Preparation: Sulphur trioxide is Uses
obtained: (i) In the manufacture of sulphuric acid and oleum.
(i) by dehydrating sulphuric acid with (li) It is used as a drying agent for gases.
excess of phosphorus pentoxide. Structure: Already discussed in section 11.1 (3b).
6H2S04 + P40 lO ~ 4H3P04 + 6S03
Fig. 11.16 Structure
(ii) by heating ferric sulphate strongly. of the S03 molecule II 3. Oxyacids of Sulphur
Fei(S04h ~-Fei03+3S03- .A largenumberofoxyacids-areknown-in-thecase-ofsulphttr . . . -
(iii) by oxidation of S02 with oxygen in presence of a either in free state or in the form of salts or both. Oxyacids
catalyst (commercial method). with S-S links are called thioacids. Acids having sulphur in
PI' lower oxidation state belong to -ous series while those having
280 2 +02 \ ........ \ 2S03 sulphm in higher oxidation state belong to-ic -series., EOI"-
BothSOz a.lldOz snoUldJ5ecompletelY'dry.The mixtiih~ is example: .... ...
passed over platinised asbestos at 400°C, when S03 is Sulphurous acid (H2S03) O.N. sulphur, +4
formed. Sulphuric acid (H2S04) O.N. sulphur, +6
The following are mainoxyacids of sulphur :
. Properties (1) Sulpburous acid series: Oxidation Number
(i) S03 exists in three allotropic forms : (i) Sulphurous acid, H2S0 3 +4
(a) a~S03: It is chemically active form. If forms long (ii) Thiosulphurous acid, H2S202 . +1
transparent ice like crystals. The melting point of this form is (iii) Hyposulphurous acid, H2~04 +3
17°C. (iv) Pyrosulphurous acid, H2S20 S +4
(b) P·S03: It is dimeric (S206)' It forms needle like (2) SulphuriC acid series:
silky white crystals. It melts at 32.5°C. Above 5O"C, it changes (i) Sulphuric acid, H2S0 4 +6
to a-form. (ii) Thiosulphuric acid, H2S20:>
(c) 1-S03: It is like p-form and obtained by completely (iii) Pyrosulphuric acid, H2S207 +6
drying P-S03' It melts at 62.2°C under 2 atmospheric pressure. (3) Thionic acid series:
(ii) S03 is an acidic oxide. It dissolves in water forming ,(i) Dithionic acid, H2S206 +5
sulphuric acid with evolution of heat. . (ii) Polythionic acid, H 2Sn0 6 (n = 3, 4, 5, 6)
(4) Peroxy acid series :
S03 + H20 ~ H2S04 + heat
(i) Peroxy monosulphuric acid, H2S0S (Cam's acid) +6
It reacts with basic oxides forming sulphates. (ii) .Peroxy disulphuric acid, H2S20 g (Marshall's acid) +6
CaO + S03 ~ CaS04 .. Only two oxyacids (sulphurous acid and sulphuric acid) are
Na20 + S03 ~ Na2S04 described below :
(iii) It dissolves in concentrated sulphuric acid forming oleum
(fuming SUlphuric acid).
(1) Sulphurous Acid, H2S0 3
H2S04 + S03 ~ H2S207 This acid is known only in solution. The solution is obtained
by dissolving sulphur dioxide in water.
(iv) It dissociates on heating at IOOO"C into S02 and O2.
. S02 + H20 -----7 H 2S03
2S0 3 lOOO"C) 2S02 + O2 The solution gives a smell of sulphur dioxide which is evolved
(v) It combines with concentrated hydrochloric acid and completely on heating. It is, thus, believed that the acid is
forms chloro-sulphonic acid, a derivative of 'sulphuric acid. present in eqUilibrium with the free gas.
S03 +HCI ~ S02 . (OH)CI H2S03 ~ H20 + S02
Chloro-sulphonk acid Properties: It is a strong dibasic acid. It ionises iIi two
(vi) S03 acts as an oxidising agent. stages.
Examples: 2S0 3 + S lOO"C ) 3S0 2 H2S03 ~ H+ + HS0 3 ~ 2H+ +S03-
548 G.R.B. Inorganic Chemistry for CompetitiQns
It thus forms two series of salts. The salts are known as

bisulphites (e.g., NaHS03) and sl1lphites (e.g., Na2S03). The
salts are fairly stable.
Like S02, it acts' as' a reducing agent and shows bleaching
properties. These properties have been described under sulphur
dioxide.
The acid also acts as an oxidising agent particul~ly when
treated with strong reducing agents.
Structure: Sulphurous acid is believed to exist in two
forms which are always in equilibrium with each other.
Fig.11.17 Pyramidal structure of SO~- ion
in which one position is occupied by a lone pair. This distorted

tetniliedral'stiUctufe reduces-{()-pyramidal struCture.-- ,--""""""""'"
Symmetrical Unsymmetrical
(2) Sulphuric Acid (oil of vitriol) H2S04
There is more evidence in favour of symmetrical formula.
(i)Tl1epr~parationQf sulpllU(ollsadd by_theactiQllQf Sulphuric acid is considered as the King of chemicals. The
H20 on thioriyl chloride supports symmetrical formula. prosperity of"ilny country is measured by the amount of-~-~-
sulphuric acid it consumes. Sulphuric acid is, thus, a substance
rei-HI OH OH of very great commercial importance as it is used practically
Of-Sr==!J ~ Of-S(' +2HCI in every important industry.
~CI If1
~--~
OH ' OH In ancient days, it was called oil of vitriol as it was prepared
by distilling ferrous sulphate (Green vitriol).
(ii) The molecule of sulphurous acid readily takes up oxygen
or sulphur atom. This can be explained if symmetrical formula 2FeS04 ·7H20 Fe203 + H2S04 +S02 +13H 20
(Green vitriol) (Oil of vitriol)
is accepted.
Native sulphur is the starting material for the preparation of
OH 0 ) <OH sulphuric acid. Sulphur is burnt and easily converted into sulphur
Of-S ~ S dioxide. The conversion of sulphur dioxide into sulphur trioxide
< OH 0 OH is a matter of difficulty. It requires either a catalyst or a strong
oxidising agent. The trioxide dissolves in water to form sulphuric
acid. The whole process may be summarised as :
S ----7 S02 ----7 S03 ----7 HzS04
For the oxidation of sulphur dioxide into sulphur trioxide,
the following reactions may be used:
The unsymmetrical formula explains the reducing character (i) Byatrnospheric oxygen in presence of a catalyst,
due to presence of H-S bond and it also accounts for the V205, at 400"C,
formation of bisulphite HS0 3 ion. V20 S
X-ray analysis of the crystal of Na2S03 has revealed that 2S02 + O2 ) 2S03
400a C
SO~- ion has a pyramidal structure with three oxygen atoms
S03 + H20 ----7 H2S04
in a triangle. This structure can be possible from sp3
hybridization of excited sulphur atom giving a tetrahedral (ii) By Cl2 or Br2 in presence of moisture,
configuration S02 + 2H20 + Cl2 ----7 H2S04 + 2HCI
S02 + 2H20 + Br2 ----7 H2S04 + 2HBr
(iii) By H20 2,
38 3p
S02 + H20 2 ----7 H2S04
t I t It (iv) By ozone (03),
hybridization (three sigma forms 1t-bond 3S02 + 0 3 ----7 3S03•
bonds with three oxygen atoms (d1t-p1t bond) with
S03 + H20 ----7 H2S04
and one position occupied by one of the oxygen
lone pair) atoms. (v) By conc. HN03•
S02 + 2HN03 ----7 H2S04 + 2N02
Elements of Group VIA or 16 (The Oxygen Family) '549
Manufacture The various parts of the plant and their functions are described
below:
Sulphuric acid is manufactured these days by the follOWIng
(a) Pyrites or sulphur burners: These are specially
two processes :
designed brick furnaces where iron pyrite or sulphur is burnt.
(a) Lead chamber process
The supply of air is regulated by sliding doors.
(b) Contact process
4FeS2 + 1102 ----7 2Fe203 + 8S02
• (a) Lead Chamber Process S + O2 ----7 S02
'rinciple: The mixture containing sulphur dioxide, air (b) Dust chamber: The dust chamber is provided with
and~nitricoxide when treated with steam, sulphuric acid is baffle walls where dust particles in the gaseous mixture coming
formed. from the burners separate due to gravity. This can also be done
2S02 + O 2 + 2H 20+ [NO] ----7 2H 2S04 + [NO] by using Cottrell electrostatic dust precipitator. [This part is
(Air) (Steam) Catalyst Sulphuric Catalyst not shown in Fig. 11.18;]
(c) Nitre pots-: Rlliiiergases'arellienpasseOtfiiiiugh-a---
Nitric oxide acts as a catalyst in this reaction. Various nitre oven in which potassium nitrate is heated with sulphuric
mechanisms have been proposed for this reaction. acid. The nitric acid is decomposed by S02.
(i) Berzelius mechanism: Nitric oxide, NO combines
KN0 3 + H2S04 ----7 KHS04 + HN0 3
with oxygen oithe air and is oxidised to nitrogen dioxide
(N0 )· --, ' - 2HN03 +2S02 ----72S0f+ HiO~+ NO -+N02~'~
2
2NO + O 2 ----7 2N02 In modem plants, oxides of nitrogen are produced by the
S02 is oxidised by nitrogen dioxide into sulphur trioxide catalytic oxidation of ammonia.
which reacts with steam forming sulphuric acid. 4NH3 +50 2 Pt. gauze ) 4NO+6H 20
S02 + N0 2 ----7 S03 + NO 2NO + O2 ----7 2N02
S03 + H20 ----7 H 2S04 (d) Glover's tower: The tower is made of steeL It is
NO formed reacts again with oxygen of air and is oxidised lined inside with sheet of lead or acid resisting bricks. It is
to N02. Thus, NO and N02 act as oxygen carriers. packed with flint stone or quartz. There are two tanks at the
(ii) Davy and Longe mechanism: Nitroso-sulphuric acid top. One tank contains the dilute chamber acid and other the
is first formed as an intermediate product which then reacts nitrated acid from the base of the Gay-Lussac tower. Both
with water forming sulphuric acid. these acids are mixed and then allowed to flow down slowly
NO+N0 2 ----7 N 20 3 in Glover's tower. The gases are allowed to enter from the
2S02 + N 203 + O 2 + H 20 ----7 2HS04 ·NO base of the tower. The following four functions occur in this
Nitroso-sulphuric acid tower:
(Intennediate product)
(i) The gases are cooled down from about 400°C to BO°C,
2HS0 4,NO + H 20 ----7 2H2S04 + NO + N02 (ii) Dilute chamber acid is concentrated.
Working and Plant (iii) The nitrated acid from Gay-Lussac tower is denitrated.
2NO·HS04 + H 20 ----7 2H2S04 + NO + N02
The plant used for the manufacture of H 2S04 in lead chamber (iv) Some S02 is converted into H 2S04'
process is shown diagrammatically in Fig, 11.18. The sulphuric acid is collected at the bottom of the tower
Nitrated acid and is about 80%.
Nitrated acid ---- - -- -
- - - --- - -~,
(e) Lead chambers: The gaseous mixture (S02, air,
Chamber acid
oxides of nitrogen) is then allowed to enter three or more large
Waste: chambers made of lead and supported in wooden frames.
gases i· Steam is admitted into these chambers from the top when
dilute sulphuric acid is formed.
S02 + N02 ----7 S03 + NO
Gaylussac: S03 + H 20 ----7 H 2S04
-.---oe" "·~""I· tower :
:......... c.y The acid is collected at the bottom of the chambers in a
Chamber acid
Pyrite Pots T ' common receiver. This is known as chamber acid and contains
.... - 65-70% H 2S04, It is pumped to the top of Glover's tower for
burners
•~ --------" - -~--~-~---- --
1:~~~~ 80% acid

•
--------.~ -~ .- ~----~- ~--- - --~-~--:
the concentration.
(f) Gay-Lussac tower: The residual gases mainly air
Fig. 11.18 and oxides of nitrogen from the lead chambers are allowed to
enter another tower called Gay-Lussac tower. This tower is

Acid vapoLirs
lined with sheet lead packed with coke. A stream of cold and steam
~
concentrated sulphuric acid pumped from the base of Glover's
tower flows down when it absorbs oxides of nitrogen from
residual gases.
2NO·HS04+ H 20
Nitrated acid
This acid is pumped on the top of the Glover's tower.

The waste gases are allowed to escape through a chimney
on the extreme right of the plant.
Removal of impurities: The chief impurities present in
the sulphuric acid manufactured by lead chamber process are:
Ei)-arseniolls-oxide--(from-pyrites);----
(ii) lead sulphate from the action of H2S04 on lead chamber.
Fig. 11.19
(iii) oxides of nitrogen.
These are removed as follows : (b) Gaillard process: The dilute acid is allowed to flow
(a) The acid-is diluted with-water when lead-sulphate is downin the form of a spray in a tower lined withacidresist;fu:g __ -~
precipitated which is filtered off. stone. Hot air enters from the base of the tower. The dilute acid
(b) Hydrogen sulphide is passed through dilute sulphuric comes in contact with hot air and loses water content. By the
acid which combines with arsenious oxide to form arsenious time the acid reaches the bottom, it becomes concentrated to
sulphide. about 95% (Fig. 11.20).
ASz03 + 3H2S ---:1 AS2S3 + 3H20
Arsenious sulphide is filtered off.
(c) The acid is now distilled over-ammonium sulphate when
oxides of nitrogen are reduced to nitrogen.
(NH4)zS04 + NO + N02 ~ 2N2 + 3H20 + H 2S04
Usually, the chamber acid is not purified and is used as such
for most of the purposes. Whenever pure H 2S04 is needed,
Hot
the acid manufactured by the. contact process is used. gases
Concentration of chamber acid: The acid obtained from
Glover's tower contains about 80% H2S04 and is known as
brown oil of vitriol (B.O.V.) due to its colour. It can be further
concentrated and the concentrated acid is called rectified oil of Fig. 11.20
vitriol (R.0.v.). The concentration is done by evaporation of
water present in the acid with the help of hot gases. Two
• (b) Contact Process
methods are used for this purpose :
(a) Cascade process and Principle: This process involves the oxidation of sulphur
(b) Gaillard process. dioxide by air in the presence of a catalyst.
(a) Cascade process: A series of ferrosilicon dishes are
arranged, one below the other, on a slope. The heating is done 2S0 2 + O 2 ,Catalyst, 2S0
3
by means of hot gases playing below the dishes (Fig. 11.19). Sulphur trioxide is dissolved in 98% sulphuric acid when
As the acid flows downwards, it is subjected to stronger heat, oleum is formed. .
so that when it reaches the lowermost dish it has been
H2S04 + S03 ---:1 H2S2~ (Oleum)
concentrated to the maximum. Addition of ammonium sulphate
during concentration helps to remove any dissolved oxides of Sulphuric acid of any desired concentration can be
nitrogen. obtained from oleum by dilution with water.
H2S207 + H20 ---:1 2H2S04
The oxidation of sulphur dioxide is reversible and furnace in which sulphur or iron pyrite is burnt to sulphur
exothermic. dioxide.
2S02 + O2 ~ 2S03 + 46.98 kcal S + 02~ S02
4FeS2 + 11 O2 ~ 2F~03 + 8S02
According to Le-Chatelier principle, the favourable conditions
for the greater yield of sulphur trioxide are: The gases leaving the furnace contain S02, air, dust particles
(a) An excess of air: Best results are obtained when S02 and arsenious oxide.
and oxygen are present in molecular proportion of 2 : 3. . (b) Purification unit: The gases are passed into dust
(b) A low temperature: The optimum temperature is . chamber in which heavy dust particles are removed by
450°C. Even at this temperature, the rate of reaction is slow mechanical precipitation aided by steam or electrically by using
and to accelerate the rate of reaction a catalyst is required. The the Cottrell precipitator. The gases are now passed through
commonly used catalysts are platinum, ferric oxide or vanadium cooling pipes and cooled to 100°C. The gases are led to steam
p-entoxide~JlLoLthese~the--hest-¥ieldc-is--Obtained by--th~use·· s(;I1!~~_~!....~here these are washed with steam or spray of
water. The dust partici~ and imp~riti;- soluble in ~ater- ~
. of platinum. But it is very expensive and is easily poisoned by
impurities. The purification of gases is done carefully when removed. If the catalyst is vanadium pentoxide, the gases
platinum is used as the catalyst. Nowadays, vanadium pentoxide should be made completely free from chlorine by using lime
(V20S) ispreferred.as jt ischeapeLalldnOLpoisonedby water in the scrubber.
impurities.' However,· it cannot be recove:redafter' use: . The gases arid:r1edbypassll1gtlrCOiigiYihe :drying-tower=-
(c) A higher pressure: The optimum pressure for carrying packed with coke or flint stone. A steam of concentrated acid
the oxidation of sulphur dioxide is kept about one atmosphere. flows down in this tower. Finally, the gases are allowed to
arsenic purifier which contains shelves holding ferric hydroxide.
Working and' Plant Ferric hydroxide absorbs arsenious oxide. The dry aild pure
mixture of S02 and air is then sent to the testing box in order
The manufacture of sulphuric acid involves three steps : to test the purity of the gas mixture.
(i) Production of sulphur dioxide (c) Preheater and contact tower: The dry and pure
.(ii) Conversion of S02 into S03 mixture of S02 and air is preheated to about 400°C are allowed
(iii) Absorption of S03 in H 2S04 to enter contact chamber (Fig. 11.22). It consists· of iron
The plant used has been shown diagrammatically in Fig. cylinder containing a· number of vertical pipes packed with
11.21. platinised asbestos heated to about 450°C. S02 is oxidised to
The various parts of the plant and their functions are S03 by O 2 of the air. As this conversion is an exothermic
described below : . reaction, the heat evolved maintains the temperature of the
(a) Pyrite burners or sulphur burners: It is a kind of catalyst.
Preheater Valve
r;=::rm::::=::;"
Cooler Arsenic
purifier
Testing
box
Sulphur Dust Fe(OHh Contact
burners remover tower
Fig. 11.21
(b) It boils at 338°C (constant boiling mixture containing

98.3% H2S04 and 1.7% water). It freezes into colourless
Platinised
asbestos crystals at lO.soC.
(c) It fumes strongly in moist air and is highly corrosive in
1 1 1 1 1 1 nature.
(d) It is a conductor of heat and electricity.
Iron tubes
is
(e) It highly soluble in water. Various hydrates such as
H2S04·H20, H 2S04·2H20, H 2S04·3H20, H2S04-4H20, are
\ 2803
--- known. Heat is evolved when dissolved in water, usually
bllmping--OGGllr-s.-Du€ --to--this--reason-watel'shouldnotbe-- -
added to concentrated sulphuric acid for dilution but
concentrated sulphuric acid should be added slowly to cold
water with constant -stirring. Due to its great affinity for
- - -------h----~s----~----~---~~L-~ water, it is used as a dehydrating substance.

---Chemicar'~propefties :~- --
(a) Dissociation: At 444°C, the vapours of _sulphuric
acid dissociate into steam and sulphur trioxide,
Fig. 11.22 Contact tower H2S04 ~ H20 + S03
(b) Acidic nature: Dilute sulphuric acid is a strong dibasic
(d) Absorption tower: The S03 formed is passed up an
acid. It ionises as :
absorption tower where it meets a descending stream of conc.
H 2S04. The acid absorbs sulphur trioxide forming oleum H2S04 ~ H+ + HS04 ~ 2H+ + SO~
(fuming sulphuric acid). The S03 cannot be absorbed in water (i) It forms two series of salts with bases.
because it produces a dense fog which does not easily condense. NaOH + H 2S04 ~'NaHS04 + H20;
Sodium
COMPARISON BETWEEN THE LEAD CHAMBER bisulphate
AND CONTACT PROCESSES 2NaOH + H 2S04 ~ Na2S04 + 2H 20
Sodium
Lead chamber process Contact process sulphate
1. Catalyst used is a gas--nitric Catalyst used is a solid vanadium

(ii) It decomposes carbonates and bicarbonates into carbon
oxide. pentoxide or platinum asbestos. dioxide.
2. Acid obtained is impure. Acid obtained is pure. Na2C03 + H 2S04 ~ Na2S04 + H20 + C02
3. Acid obtained is 80%. Oleum is obtained. Sulphuric acid NaHC0 3 + H2S04 ~ NaHS04 + H20 + CO 2
of any concentration can be (iii) It reacts with electropositive metals evolving hydrogen.
obtained from oleum.
4. Methods of concentration of the Further concentration is not Zn + H 2S04 ~ ZnS04 + H2
acid are troublesome. necessary. Fe + H 2S04 ~ FeS04 + H2
S. It is not necessary to purify the It is absolutely necessary to purify (iv) It displaces more volatile acids from their metal salts.
gases. the gases as impurities act as
poison to catalyst. 2NaCI + H 2S04 ~ Na2S04 + 2HCI
6. It is a cheaper method. This method is costly. The cost has Ca3(P04h + 3H2S04 ~ 3CaS04 + 2H3P04
been reduced by the use of V205
in place of platinum. CaC204 + H 2S04 ~ CaS04 + H 2C 20 4
Calcium oxalate Oxalic acid
Properties FeS + H2S04 ~ FeS04 + H2S
Physical properties: (a) It is a colourless syrupy liquid. 2CH3COONa'+ H 2S04 ~ Na2S04 + 2CH3COOH
It contains 98.3% sulphuric acid. Its specific gravity is 1.84 2NaN03 + H 2S04 ~ Na2S04 + 2HN0 3
at lS C. It has high viscosity because its molecules are
Q
CaF2 + H 2S04 ~ CaS04 + 2HF

associated. due to hydrogen bonding.
Elements of Group VIA or 16 (The Oxygen Family) 553--
2NaN02 + H2S04 ~ Na2S04 + 2HN02 corrosive action on skin is also due to dehydration of skin. It
J, absorbs water from organic compounds.
NO + N02+ H 20 H 2S0 4
C12H22011 - ) 12C
(c) Oxidising nature: It acts as a strong oXidising agent. Cane sugar (-IlH 2 0)
The potential equation is :
C H 12 0 H 2S04 ) 6C
H2S04 ~ H 20 + S02 + 0 6 6
Glucose (-6H 20)
(Hot cone.)
H2S0 4
or 2H2S04 + 2e- ~ soi- + 2H20 + S02 (COOHh --~) CO + CO 2
Oxalic acid ( - H 20 )
(i) Non-metals such as carbon and sulphur are oxidised to
their oxides. HCOOH 2
_H_ S_O_4~) CO
Formie acid (-H 20)
[H2S04 ~ H20 + S02 + 0] x 2
H 2S04 j
C+20~ CO2
·C + 2H2S04 ~ C02 + 2S02 + 2H20
i~;I~~?JJ - (=HiO) )<:2H~£~>H5
Cloth, wood, starch, paper, etc., are all charred in con-
[H2S04 ~ H20 + S02 + 0] x 2 centrated sulphuric acid.
S +20~ S02 -(e) Miscellaneous reactions:
(i)Stilphoruitioii:AroiriatiGGoiriporinds reaetwIthsulphUri&~~ -
S-+-2H2SD4~3SU2-+~2H20 -
acid forming sulphonic acids.
Phosphorus is oxidised to orthophosphoric acid.
C6H6 + H 2S04 -----7 C6HsS03H + H 20
[H2S04 ~ H20 + S02 + 0] x 5 Benzene Benzene
sulphonic acid
2P+50~ P 20 S
(ii) Action of pels: The molecule of sulphuric acid
P20s + 3H20 ~ 2H3P04
contains two hydroxyl groups. One or both the hydroxyl groups
2P + 5H2S04 ~ 2H3P04 + 5S02 can be replaced by chlorine when treated with PCIs.
(ii) Metals like copper, silver, mercury, etc., are first oxidised
by conc. H2S04 and then the oxides combine with acid to 02S <OH + PCls -----7 02S<CI +·POCI3 + HCI
form corresponding sulphates.
OH OH
H2S04 ~ H 20 + S02 + 0 Chloro-sulphonic
Cu +O~ CuO acid
CuO + H2S04 ~ CUS04 + H20 OH + PCIs <CI-

Cu + 2H2S04 ~ CUS04 + S02 + 2H20 - 02S. -----702S - +2POC1 3 +2HCI
< OH+PCI _ CI
2Ag + 2H2S04 ~ Ag2S04 + S02 + 2H20 s
Sulphuryl
Hg + 2H2S04 ~ HgS04 + S02 + 2H20 chloride
(iii) Iodine is liberated from KI (HI is oxidised to 12) (iii) On heating potassium ferrocyanicte with concentrated
2KI + H 2S04 ~ K2S04 + 2HI sulphuric acid, carbon monoxide is evolved.
H2S04 ---7 H20 + S02 + 0 ~Fe(CN)6 + 6H2S04 + 6H20 ~
2HI + 0 ~ H 20 + 12 2K2S04 + FeS04 + 3(~hS04 + 6CO
2KI + 2H2S04 ~ K2S04 + S02 + 12 + 2H20 (iv) On heating potassium chlorate with concentrated
sulphuric acid, chlorine dioxide is evolved with explosion.
Similarly, bromine is liberated from KBr (HBr is oxidised to
3KCI03 + 3H2S04 ~ 3KHS04 + HCI04 + 2CI02 + H20
Br2)'
(v) Sulphuric acid reacts with barium and lead salts to form
2KBr + 2H2S04 ~ K2S04 + S02 + Br2 + 2H20
insoluble sulphates. These sulphates are even insoluble in conc.
(iv) In presence of Hg as a catalyst, naphthalene is oxidised HCI and conc. HN03.
to phthalic acid.
BaCl 2 + H2S04 ~ BaS04 + 2HCI
CIOHs +9H 2S0 4 ~ CgH604 + IOH 20+9S02 +2C0 2 Pb(N03h + H 2S04 ~ PbS0 4 + 2HN03
Phthalic acid
(vi) H 2S04 absorbs sulphur trioxide forming oleum or fuming
(d) Dehydrating nature: As sulphuric acid has great sulphuric acid.
affinity for water, it acts as a powerful dehydrating agent. Its
554 CiR.B. Inorganic Chemistry for Competitions
~owever, the ion shows· a considerable amount of double

H 2S0 4 + S0 3 ~ H2~207
$Qleum character as the bond lengths are all rather short. Thus, the
(vii) H2S04 when treated with phosphorus pentoxide loses sulphate ion is a resonance hybrid, as represented below:
water and fonus sulphur trioxide.
H2S04 + P20S ~ 2HP03 + S03
Uses
It is used:
The unionised acid is, therefore, resonance hybrid of the
(i) for the manufacture of fertilizers such as ammonium
.?~~::~ :X:-:. _--

following two structures:
sulphate and superphosphate of lime.
(ii) in the manufacture of other acids such as hydrochloric
acid;~orthophosphoric~·acid,nitric-acid,etc;··
(iii) in the manufacture of explosives such as, nitroglycerine,
gun cotton, TNT (trinitro-toluene), picric acid, etc.
(iv) in the manufacture of important chemicals such as In crystals, SO~- ion has a tetrahedral stnIcture. This can
. .... .~~Il!ll carb.c:~ate'.:~ums, me!a1sulp~~!e~, ether~.d)~~sl'~orus, be explained on the basis of sp3 hybridization.
------ -_.
etc.
(v) in the refining of petroleum. S-atom in excited state
(vi) in the manufacture of coal-tar dyes and a I).umbei of 3d
drugs and disinfectants.
(vii) in the textile, paper and dyeing industries.
It It I I
~
fonn n-bonds
(viii) in the leather industry for tanning. with two
(ix) for cleansing metals before electroplating, enameling, oxygen atoms
galvanising, etc., (Pickling). 8P~ hybridization
(x) in storage batteries. tetrahedral geometry
(xi) in manufacturing paints and pigments.
(xii) as an important laboratory reagent. In organic chemistry
it is used for synthesis of various organic compounds and
sulphonation reactions. It is also used as an oxidising and a
dehydrating agent.
St~cture: Sulphuric acid has two OH groups whk.u, are
directly attached to sulphur. The molecule has been assigited
the following structure:
o
.. .. ..
:0:
i
Fig.ll.23 Tetrahedral geometry of SO~- ion
H:O: S :O:H HO-S-OH

.. J,
Tests for H2S04 :
..
:0: o (1) When heated with copper, it evolves S02.which has a
characteristic smell. The gas reacts with acidified K2Cr207
The sulphate ion, SO~-, is therefore, represented as
solution which is turned green.
}2- (2) It forms white precipitate with barium chloride solution
{ o-t-o0
which is insoluble in conc. HCI and conc. HN03.
(3) When heated with NaCI, it evol~es Hel which forms
white fumes with NH40H.
Elements of Group VIA or 16 (The Oxygen Family) 555---
Example 1. A is a binary compound of univalent metal. Reaction with KOH

1.422 g of A reacts completely with 0,321 g of sulphur in an 2KOH + 50 3 ---72K0 3 + 50 2 + H 20
(A) (B) (C)
evacuated and sealed tube to give 1.743 g ofa white crystalline (Deep red coloured)
solid,-B, that forms a hydrated double salt, C, with Alz(S04h-
Identify A, B and C. [LI.T.19941 Example 3. How you will obtain the following from
Solution: sulphuric acid ?
As the solid B forms a hydrated double salt with Al2(S04h, (i) S02 (ii) S03 (iii) SOZCl2 (iv) H 2S (v) S.
it should be a sulphate of a univalent metal, M 2S04 . Solution:
One molecule of sulphate contains one sulphur atom, i.e., ill.SQ2j~t obtillned~by_heating.c.Qpp_erwi~conc·...H2S04 _____ _
the-massoTthnulphare which contains~rg sulphur sooUTd.
Cu + 2Hz804 ---; CUS04 + S02 + 2H20
be its molecular mass.
0,321 g'sulphur is present in (1.422 + 0.321 1.743 g) of B. It can also be obtained by boiling sulphur with conc. H2S04,
S + 2HzS04 ---; 3S0z + 2H20
32.1 gof sulphur is ~res~l1t in =5~i;_X_32.l =174.3 (ii)H2S0~ when treated with-Pz05Josescwaterand fo~-=-~ ____ .
Let the atomic mass of univalent metal be x. S03'

.. M ZS04 =2x + 32.1 + 64.0 = 174.3 HZS04 + P205 ---; 2HP03 + S03
or 2x = 78.2 (iii) S02C12 is formed when conc. H2S04 is treated with
x= 39.1 excess of Pe15.
Atomic mass 39.1 corresponds to potassium. H2S04 + 2PCIs ---; SOzCl2 + 2POCl3 + 2HCl
Thus, the compound B is K2S04 and the compound C is (iv) and (v) HzS and S are obtained from conc. H ZS04 by
K2S04·AI2(S04h·24HzO. the following reactions.
Since, B is formed with interaction of A and sulphur, A must 4C HCI Oxid.
. bean oxide of potassium (most probably KOz). - BaCl z + H 2S0 4 ~ BaS04 ---7 BaS ---7 H 2S ---7 S
2KOz + S ---7 K 2S04 Example 4. Explain the following;
2 x 71.1 3Z.1 174.3
(i) An acidified KZCrZ07 paper turns green when exposed
32.1 g of S reacts with A = 2 x 71.1 g to S02.
(ii) HzS acts only as reducing agent while S02 can act both
0.321 g of S reacts with A =2 ~i:.1 x 0.321= 1.422 g as a reducing agent and an oxidising agent.
Thus, A is supported by the given data. (iii) SOz acts as a bleaching agent.
A is, therefore, potassium superoxide, KOz. (tv) Sugar turns black on addition of cone. H2S04'
(v) Ozone destroys mercury meniscus.
Example 2. When gas A is passed through dry KOH at
(vi) SF6 is known but SH6 is not known.
low temperature, a deep red coloured compound, B and a gas
Solution:
C are obtained The gas A, on reaction with but-2-ene, followed
(i) Acidified KZCr2~ acts as an oxidising agent in presence
by treatment with ZnlH20 yields acetaldehyde. IdentifY A, B
of SOz and converted into chromium compound which is
and C. [LI.T.I9941
green in colour.
Solution:
The reaction of gas A with but-2-ene followed by treatment K2Cr207 + 4HzS04 ---; KZS04 + Cr2(S04h + 4HzO + 30
with ZnlHzO suggests that A is 03' 3S02 + 30 + 3H20 ---; 3H2S04
K2Cr20 7 + HZS04 + 3S0z ---; K2S04 + Cr2(S04h + HzO
Green
(ii) On the basis -of electronic configuration (3i3p4), the

But-2-ene Ozonide maximum and minimum oxidation states of S are +6 and -2.
In H2S, the oxidation state of S is -2. It can increase only (e) 2NaHS0 3 ~ Na2S03 + H20 + S02
oxidation state and cannot decrease. Thus, H2S can act only S02 + 2H2S ~ 2H20 + 3S
as a reducing agent. In S02, the oxidation state is +4, i.e., it
can be increased as well as decreased. Thus, S02 can act both 2NaHS0 3 + 2H2S ~ Na2S03 + 3S + 3H20
as a reducing agent and an oxidising agent.
Example 6. Sulphur melts to form a clear mobile liquid
(iii) S02 in presence of moisture is oxidised to H 2S04
at 119°C but on further heating to 180°C, it becomes viscous.
liberating nascent hydrogen. Th& nascent hydrogen bleaches
Why?
the coloured substance.
Solution:
S02 + 2H20 ~ H2S04 + 2[H] Upto 119°C, sulphur exists as S8 molecules which can roll
Coloured substance + 2[H] ~ Colourless over one another to form a mobile liquid. However, when this
(iv) Conc. H 2S04 has great affinity for water molecules, liquid is further heated to 180°C, the cleavage of ring structure
i.e., it acts as a dehydrating agent. When in contact with sugar, occurs and zig-zag open chains are formed which get
all water moleculesart}4ak~nup-and-Garbon- is-left behind. interwoun~and_tangled together and hence sulIilillr becomes
more viscous.
Cone. H 2S0 4
C 12 H 22 0 11 ) 12C + I1H 20 Example 7. SOCl2 can act as a weak Lewis acid as well
as a weak Lewis base. Explain.
(v) Ozone ac~ asa strong oxidising agent. It oxidises mercury
Solution:
... -intomerCUrollnlxi<:le' whicb-starts-stickingto--glass~
Like nitrogen in ammonia, sulphur has a lone
loses its mobility, i.e., mercury meniscus is destroyed.
pair of electrons which it can donate, hence it acts as a weak base.
2Hg + 03 ~ Hg20 + 02 SOCl2 has also empty d-orbitals which can accommodate
(vi) In the highest oxidation state, SUlphur can combine only electron pairs from bases and hence acts as a weak acid.
with highly electronegative element like fluorine and not Example 8. (a) Which form of sulphur does show
hydrogen. Hence, sulphur forms SF6 but not SH6. paramagnetic nature? Explain.
Example 5. State with balanced equation what happens (b) Compounds offluorine and oxygen are called fluorides
when? and not oxides. Explain.
(a) Potassium ferrocyanide is heated with conc. H 2S04 , (c) Sulphur disappears when boiled with an aqueous solution
(b) A mixture of potassium chlorate, oxalic acid and of sodium sulphite. Why?
sulphuric acid is heated. Solution:
(c) Sodium chlorate reacts with sulphur dioxide. (a) In vapour state, sulphur partly exists as S2 molecules
(d) Chlorine gas is passed into water saturated with hydrogen and S2 molecule like Oz molecule has two unpaired electrons
sulphide. [M.L.N.R.1991] in the antibonding n-orbitals and exhibits paramagnetic nature.
(e) Hydrogen sulphide is passed through sodium bisulphite . (b) This is because of higher electronegativity of fluorine than
solution. [UT.I991] oxygen. In naming a compound, the electropositive or less
Solution: electronegative element is taken first, thus, the compounds of
(a) CO is evolved. fluorine and oxygen are called oxygen fluorides and fluorine
~Fe(CN)6 + 6H2S04 + 6H20 ~
oxides.
2K 2S04 + FeS04 + 3(NH4hS04 + 6CO (c) Sulphur combines with sodium sulphite and forms sodium
thiosulphate which·is soluble in water and hence S disappears.
(b) Potassium chlorate is reduced while oxalic acid is
oxidised. Example 9. Knowing the electron gain enthalpy valuesfor
KCI03 + H2S04 ~ KHS04 + HCI + 30 .
o 0- and 0 02- as-141 kJmor l and 702 kJmoZ- 1
respectively, how can you account for the fonnation of a large
3HzC204 + 30 ~ 6C02 + 3H20 number ofoxides having 0 2- species and not O-?
KCI03 + 3H2C204 + H2S04 ~ KHS04+ HCI + (jC0 2+ 3H20 Solution:
Although the formation of 0 2- anion requires more energy
(c) NaCI0 3 is reduced to NaC!. in comparison to the formation of 0- anion iictually energy is
[S02 + 2H20 ~ H2S04 + 2H] x 3 released), yet in large number of oxides, oxygen is divalent in
NaCI0 3 + 6H ~ NaCI + 3H20 nature. This is due to the fact that lattice energies of the oxides
2
having 0 - anions are very high on account of greater magnitude
NaCI03 + 3S0 2 + 3H20 ~ 3H2S04 + NaC! of electrostatic forces of attraction.
(d) Cl2 + H2S ~ 2HC! + S
Example 10. Give at least one example to explain the H 2S04 + 2NaOH ~ Na2S04 + 2H20
following properties: Sodium sulphate
(Normal salt)
(x) Sulphuric acid is a dibasic acid.
(ii) Sulphuric acid is a dehydrating agent. (ii) H 2S04 has great affinity for water molecules and hence,
(iii) Sulphuric acid is an oxidising agent. acts as a dehydrating agent ..
Solution: HCOOH Cone. H 2S0 4 )H 0+CO
(i) H 2S04 forms two series of salts, i.e., both the hydrogen 2
atoms are replaceable. (iii)H2S04 oxidises metals, nonmetals and other compounds.
H 2S0 4 ............ H+ + HS04~2H+ +SO~- Cu + 2H2S04(conc.) ~ CUS04 + S02 + 2H20
H2S04 + NaOH ~ NaHS04 + H 20 S + 2H2S04 ~ 3S02 + 2H20

Sodium hydrogen 2Hl + H 2S04 ~ 12 + S02 + 2H20
.. . _ .. _Sulp~af:()~cids..alt1
t) SUMMARY AND IMPORTANT POINTS TO REMEMBER

_... 1._Dtollp16or~VIA6fthe:peri0dictableeonsistso:f.six:efements
a
····(b)Atomic-raUii,--ato:tfi1cYolUmeaniroensity-iilc reas e=~
--oxygen, sulphur, selenium, tellurium, polonium and unun- gradually from 0 to Po.
hexium. These elements are called cllaIcogens, i. e., ore forming (c) Electronegativity decreases gradually. Oxygen is second
elements .. These are p-block elements as the last differen- most electronegative element.
~ting electron is accommodated on np shel~. All have six (d) The melting and boiling points increase gradually from
electrons in their outermost shell, i.e., nsZnp4 configuration. o to Po.
2. The. elements oxygen and sulphur are common while (e) The ionisation potential values are high and decrease
selenium, tellurium and polonium are comparatively rare. gradually. The elements do not lose the electrons to form
Oxygen is the most abundant element. It makes up 46.6% by positive ions easily.
mass of the earth's crust. It is found both in free and (f) All the members show allotropy.
combined state. Sulphur is the sixteenth most abundant Oxygen: Ordinary oxygen and ozone are allotropic forms.
element. It occurs mainly in the combined form. The last Sulphur : Rhombic, monoclinic, plastic and amorphous
member is radioactive in nature. are allotropic forms.
3. Oxygen is a gas while other members of group 16 are solids. Selenium: Red form and grey form are allotropic forms.
Oxygen is a diatomic molecule while the molecules of other (g) Oxygen and sulphur show the property of catenation but
. members are complex. Sulphur, selenium and tellurium exist this property is more pronounced in sulphur.
as S::'atom staggered rings. In S8 molecule, each S-atom is sp3 5. All these elements have six electrons in their valency shelL
hybridized involving both bonding and non-bonding electron They complete the octet either (a) by forming bivalent anion
pairs. gaining two electrons .such as :.
Oxygen atom is capable to form multiple bonds (pre-pre OZ-, S2-, Se2- and Te2- showing electrovalency (di).
interaction) with other oxygen atom on account of sman size. or (b) by forming two covalent .bonds, i.e., sharing two
However, this tendency is missing in sulphur atom. The bond electrons.
energy of oxygen-oxygen double bond is quite high as Po does not form P02- anion. However, it forms P02+ ions.
compared to oxygen-oxygen single bond. In sulphur, the
Oxygen shows -2 oxidation state in its compounds except in
sulphur-sulphur double bond energy is not so large in
oxygen fluorides. The tendency to show -2 oxidation state
comparison to single bond energy. As a result-O-O--O--
decreases as we go down in the group. However, positive
chains are less stable as compared to 0=0 molecule while
oxidation states are exhibited by S, Se, Te and Po. In addition
-S-S-S- chains are more stable than S=S molecule.
to +2 oxidation state +4 and +6 oxidation states are observed.
Thus, oxygen exists as a diatomic gas molecule, sulphur
This is due to availability of d-orbitals in these elements.
exists as Ss s o l i d . · :
The diatomic molecule 0=0 accounts for high dissociation The compounds having +4 oxidation state show both oxi-
energy but does not explain paramagnetic nature. Pauling dising and reducing properties while compounds having +6
oxidation state are only oxidising.
proposed 3-electron bond structure : 0: : : 0: to explain
6. All the elements of group 16 form hydrides of the type H2M.
paramagnetic behaviour. .
4. (a) Metallic character increases with increase in atomic H20, HzS, HzSe, H2Te and H 2Po.
number. (a) H20 is a liquid while other hydrides are colourless
o S Se Te Po poisonous gases with bad odours. HzO (water) has low
'-----v------'
Metal volatility (high boiling point) as hydrogen bonding is
Non-metals Metalloids
558 GR.B. Inorganic Chemistry for C6mpetiti6ns
present. H2S has high volatility as no hydrogen bonding 10. Only S and Se f6rm qxyhalides. They are called thi6nyland
is present. Volatility decreases from H 2S to H2Te due to selenyl halides.
increase in molecular masses. SOF2 SOCl2 SOBr2
(b) As the electronegativity difference between M and H SeOF2 SeOQ2 SeOBr2
decreases, the covalent character increases from H20 to They react with water readily.
H 2Te/Water is highly polar. It has high dielectric In additi6n, sulphuryl halides are also kn6wn, S02X2'
constant. These may be regarded as derivatives 6f H2S04 where'b6th
(c) Thermal stability decreases. This is due to an mcrease in the OH groups have been replaced by halogen at6ms.
M-H bond length. Water dissociates at 2000"C while 11. Lavoisier regarded oxygen as an essential constituent of all
H2Te decomposes at room temperature. acids named it so (oxus acid and gennas =maker). It occurs
(d) Acidic nature increases from H 20 to H2Te. in the atmosphere to the extent of 21 % by volume and 23%
by mass. This percentage remains constant by the process
(e) Except H 20, other hydrides are reducing agents.
of photosynthesis. It is an essential ingredient in all living
(f) ·Hydrides~6H;,Be;-Te~andP()~bum~in·oxyg~n.with~blue
matter . and ts· ·of· ·grelIt· impurtancem-respiration--and---·
flame forming dioxides. combustion.
(g) All these hydrides ~ V-shaped. The central atom is sp3 It is a colourless, odourless and tasteless gas. It is little
hybridized. The bond angles are l04,SO, 92.5°, 91° and 90° heavier than air and slightly soluble in water. It is para-
in HzO, H 2S,.H2Se and H 2Te. magnetic in nature. There are three isotopes ofoxygen with.
.. ·'.··S:'Se, Teand Po-fom} oxideS onbutiilligli{arr61futrtype- '-mass· IiumbersT6;~17 arid 18: Oxygen isnofCori:ioustioHfbur~~ .....
M0 2 , e.g., SOz, Se02, Te02 and POO2. it helps in c01I.lbustion. It is very active element. It directly
The acidic and stability 6f these oxides decrease down the combines with almost all metals (except noble metals) and
group. S02 and Se02 are acidic while Te02 and Po02 are non-metals (except zero group elements and halogens) and
amph6teric. S02 is a gas, Se02 is a volatile solid while Te02 reacts with large number of compounds. The reactions are
and P002 are crystalline solids. S02 is an angular molecule usually exothermic.
with bond angle 119S. S is in sp2 hybridized state. The bond 12. Oxygen combines nearly with all the elements except inert
length is 143 A. gases, noble metals and halogens. The binary compounds
cr+ •• cr+
of oxygen with other elements are called oxides. However,
pn d1t bond ~ pre - pre bond the compounds of oxygen and fluorine are termed fluorides
° .119.5°. ° as fluorine is more electronegative than oxygen. The oxides
can be classified, on the basis of chemical behaviour, into :
S, Se and Te also f6rm tri6xides. The trioxides are acidic in (a) Acidic oxides: The oxides which dissolve in water to
nature. The acidic nature decreases from S03 to Te03. form oxoacids are called acidic oxides or acid anhydrides.
8. Sulphur, selenium and tellurium form similar oxyacids. These react with bases and form salts. They also
combine with basic oxides. These oxides are generally
H2T~31 !
H2S03 H2Se03
Sulphurous acid Selenous acid
formed by non-metals. Examples are : CO2, B203, Si02,
ThlI=.,e "id
Salts : Sulphites Selenites Tellurites. ~ N02, P20 S, N20 s, SOz, Clz07, etc. Some metals in higher
H2SO4 HZSe04 H2Te04 ~ oxidation states also form acidic oxides such as V205,
Sulphuric acid Selenic acid Telluric acid ~ cr0 3, Mn207, etc. Some of the oxides form two oxyacids.
Salts : Sulphates Selenates Tellurates t5 These are called mixed oxides such as N02, P40s, etc.
)
(b) Basic oxides: The oxides which either dissolve in
Strength increases
water to form alkalies or combine with acids to form salts
9. S, Se and Te form hexafluorides of type MF6. They all involve or combine with acidic oxides are called basic.oxides. The
sld 2 hybridization, i.e., possess octahedral structure. These examples are Na20, CaD, CuO, PbO, FeD, etc.
are colourless gases. SF6 is extremely inert. SeF6 is slightly (c) Neutraloxides: The oxides which neither combine wi th
reactive while TeF6 is hydrolysed by water into ~Te06. acids nor combine with bases to form salts.
Many tetrahalides are known. SF4 is a gas, SeF4 is a liquid Examples are : CO, N20, H20, NO, etc.
while TeF4 is a solid. S, Se, Te and Po form tetrachlorides (d) Amphoteric oxides: The oxides which react with acids
and bmmides while Te and Po form tetraiodides. All and bases both are termed amphoteric.
tetrahalides posses trigonal bipyramid structure with sp3d
Examples are : Zno, PbO, SnO, Sn02, Pb02, Ah03, BeO,
hybridization. One p6sition is occupied by lone pair and four
Cr203,etC.
by halogen atoms.
Oxides are also classified on the basis of oxygen content.
All elements except Se form stable dichlorides and dibm-
(a) Normal oxides: These contain oxygen just as much as
mides. Dihalides form tetrahedral molecules due to sp3
permitted by usual valence rules.
hybtidization. Dimeric monohalides as S2F2, S2Cl2 and S2Br2
(b) Polyoxides: These contain more oxygen than permitted
are known. Their structures are similar t6 H202'
by usual valence rules.
Elements of Group VIA or 16 (The Oxygen Family) 559-
(i) Peroxides: These on treatment evolve H 20 2 with '17. Sulphur exists in several allotropic forms: The most common .
dilute acids such as Na202, Ba02, etc. form is the rhombic or octahedral or a-form. It is pale yellow
(ii) Superoxides: Such as Mn02, Mn207, K02, Rb02, in colour. Its specific gravity is 2.06. It melts at 114SC. It is
etc. insoluble in water and readily soluble in CS2. It consists S&
(c) Suboxides: These contain less oxygen pennitted by structural units packed together into octahedral shape. This
usual valency rules such as N 20, CO, etc. is the stable variety at ordinary temperature. All other forms
(d) Mixed oxides: These are made up of two similar oxides such as monoclinic, plastic sulphur, etc., are unstable and
such as Pb30 4 (2PbO + PbOz), Fe304 (Fe203 + FeO), convert themselves into rhombic form. .
Mn 30 4 (2MnO + Mn02). 18. Hydrogen sulphide or sulphureted hydrogen (H2S) occurs
13. In 1840, Schonbien observed that rotten smell during passing in volcanic gases, sewage gases, coal gas and in several
. of electric discharge through air was due to formation oLa spring waters. It is found in small amounts in atmosphere. It
new gas which he named ozone (ozo = I smell). Sorret is obtained in the laboratory by the action of dilute H2S04
established its formula, 0 3 and attributed that ozone is an on FeS in kipp's apparatus. Pure H 2S can be prepared by the
_a110tro~ of()~ygen,- __ _ <i.ft!.ol1Q.{pur!<.HCl onantimonysulpbide-(Sb!lS3)'-
Ozone is present in sufficient amounts in the atmosphere at It cannot be dried by conc. H 2S04 because it is oxidised to
higher altitudes, i.e., 12 to 15 miles above earth's surface. It sulphur.
is formed there by action of ultraviolet rays of the sun. Near H2S + H2S04 ---? 2H2D+ S + S02
earth's surface ozone is decomposed by dust particles. It is, therefore, dried by passing through CaCl2 or P20S.
. -It~is·obt:3.iited-by-passing-sileni·~electric-dischargethrough- . --leis -a..coloudess-gas-wiili~unpleasant-odour~IHs-slightly ... ~.
dry oxygen. The apparatus used for this purpose is called heavier than air and slightly soluble in water. It is poisonous
ozoniser. The commonly used ozonisers are (i) Siemen's in nature. It bums with blue flame in oxygen or air fonning
ozoniser and (ii) Brodie's ozoniser. The mixture obtained from S02 and H20. It acts as a strong reducing agent. It reacts
ozoniser consists of 5-1 0% ozone by volume and the mixture with metals and metal oxides to form corresponding sulphides.
is called ozonised oxygen. The ozonised oxygen is cooled by H 2S reacts with salts of various metals fonning corresponding
liquid air when liquid oxygen is obtained. sulphides. The metal sulphides can be divided into three
groups:
Fluorine reacts with water at low temperature when mixture
of ozonised oxygen is formed. (a) Sulphides precipitated in acidic medium-Examples :
Sulphides of Hg, Bi, Pb, Cu, Ag, Cd, As, Sband Sn.
14. Ozone is a pale blue gas with a characteristic strong smell. It
(b) Sulphides precipitated in alkaline medium-Examples :
can be liquefied to pale blue liquid at -112.4°C. It is heavier
Sulphides of Zn"Ni, Co, Mn and Fe.
than air. It is slightly soluble in water but more soluble in .
(c) Sulphides which are precipitated neither in acidic nor in
turpentine oil, glacial acetic acid or carbon tetrachloride. It
alkaline medium-Examples: Sulphides of Cr, AI, Mg, Ba,
causes headache and nausea.
Sr, Ca, K and Na.
It is unstable and decomposes completely into oxygen at
The shape of H 2S molecule is similar to that of water, i.e.,
3000C. It acts as a powerful oxidising agent. The potential
V-shaped. The bond length is 1.35A and bond angle 92.so.
equation is: 0 3 ---? O 2 + 0. The oxidation potential is
19. Sulphur forms a number of oxides such as S20, SO, S203,
+ 2.07 V. It is a good bleaching agent. The bleaching action
S02, S03, S207 and S04. Out of these S02 and S03 are
is due to its oxidising nature. It bleaches oil, ivory, flour,
important and common:
starch, waxes, pulp, etc.
S02 is a colourless gas with pungent and suffocating odour.
.It reacts with unsaturated organic compounds containing
It is heavier than air. It is soluble in water. It neither burus
double bonds fonning ozonides. The ozonides break: with
nor helps in burning. However, burning Mg or K continue to
water to form carbonyl compounds. The process is known
bum in its atmosphere.
as ozonolysis. Mercury is oxidised by ozone to suboxide
(Hg20) which dissolve in mercury. It starts sticking to glass 3Mg + S02 ---? 2MgO + MgS;
and loses mobility. The mercury loses its meniscus. This is 4K + 3S02 - - ? K2S03 + K2S20 3
termed as the tailing of mercury. Ozone molecule is V-shayed It is an acidic oxide. It dissolves in water fonning sulphurous
with a bond angle 116.81' and 0-0 bond length 1.278 A. acid (H2S03). It combines directly with chlorine to form
15. The name sulphur has been derived from sanskrit word sulphuryl chloride. It combines with oxygen in presence of a
sulveri meaning killer of copper. It is widely distributed in catalyst (platinised asbestos or V 20S or NO) when S03 is
nature both in free and combined state. The free sulphur is formed.
found in volcanic regions of the world. The underground It acts as a reducing as well as an oxidising agent. In presence
sulphur is extracted by Frasch process. of moisture, it acts as a bleaching agent. The bleaching action
16. Organic compounds of plant and animal origin, e.g., onion, is due to reduction. The bleaching· is temporary.
garlic, mustard, eggs, proteins, hair, wool, etc., contain sulphur 20. A }argenumber of oxyacids are known in the case of sulphur
compounds. either in free state or in the form of salts or both. Oxyacids
with S-S links are called thioacids. Acids having sulphur in H2S04·4H20 are known. Heat is evolved when
lower oxidation state belong to -ous series while those dissolved in water. Water should not be added to
having sulphur in higher oxidation state belong to -ic series. conc. H2S04 for dilution but conc. H2S04 should be
(a) Sulphurous acid (H2S03): This acid is known only in added slowly to cold water with constant stirring.
solution. It is formed by passing S02 through water. It is Due to its great affinity for water, it is used as
a strong dibasic acid and forms two series of salts dehydrating agent. Its corrosive action on skin is
(i) bisulphites (e.g., NaHS03) and (ii) sulphites (e.g., due to dehydration. It boils at 338°C. It is a
Na2S03)' The salts are fairly stable. The sulphurous acid, conductor of heat and electricity.
bisulphites and sulphites act as reducing agents. H 2S04 is a strong dibasic acid. It forms two
X-ray analysis of the crystal of Na2S03 has revealed that" series of salts (0 bisulphates (e.g., NaHS04) and
SO~- ion has a pyramidal structure. The S-atom is in sp3 (ii). sulphates (e.g., Na2S04). It acts as a strong
hybridized form, i.e., tetrahedral configuration in which oxidising agent. The potential equation is : H2S04
one position is occupied by a lone pair of electrons.
..
°
- - t H20 + S02 + or 2H 2S04 + 2e - - t SO~- +
2H20+SO:i: IrhastwoOH-gronp'!>whichare-directIy-
-oYcrf~o
0-
attached to sulphur. The acid is a resonance hybrid
of the following two structures.
Sulphurous acid Sulphite ion 0 , . /OH O~· /OH

.-lIlolecule-----.----~--·-···----····-·-~~~ -~-~~,~- "~ O~_S_~O~~-(J~.§.~-u'TTH-·=
(b) Sulphuric acid (H2S04): It is considered as king of
SO,r ion has tetrahedral structure, i.e., S is in sp3
chemicals. The prosperity of any country is measured by
hybridization.
-the amount of sulphuric acid it consumes. It was called
in ancient days oil of vitriol as it was obtained by
distilling ferrous sulphate (green vitriol). Native sulphur ttllcr°
is the starting material for its preparation. It is burnt and 1t,fcrS~o_
is easily converted into S02' The conversion of S02 into
S03 is bit difficult. It requires a catalyst. The trioxide
° 0-
dissolves in water to form H 2S04, (c) Thiosulphuric acid (H2S203): It is a dibasic acid. It
does not exist in free state. Salts are quite stable.
S - - t S02 - - t S03 - - t H 2S04 Thiosulphates are reducing agents.
1\vo processes are used for the manufacture of H2S04. (d) PeroxymoHe:.ulphuric ~cid or Caro's acid (H2805) : It
(i) Lead chamber process: In this process, the is a dibasic stable and crystalline solid. It has a
mixture containing S02, air and NO when treated
peroxolinkage (O>_O_O_H). It is a strong
with steam, sulphuric acid is formed. NO is a
catalyst. The acid obtained contains about 80% oxidising agent. ° "'OH .
H2S04 and is known as brown oil of vitriol (B.O.V.) (e) Peroxydisulphuric acid or Marshall's acid (H2S208) :
due to its colour. It can be further concentrated and It is a dibasic acid. It has a peroxolinkage. It is a strong
the concentrated acid is called rectified oil of vitriol oxidising agent.
(R.O.V.). Usually chamber acid is not purified and
used as such for most. of the purposes. .
A.,
""'S~
#0
_/S""'
(ll) Contact process: The process involves the
0/' O-U ,'0
OH OH
conversion of S02 into S03 by air in presence of a
catalyst (platinum or V 205)' Best results are obtained (f) DUhionic acid (H2S206): It is a dibasic acid. It does
when S02 and O 2 are present in molecular proportion not exist in free state but its salts are quite stable.
of 2 : 3. The optimum temperature is 450°C. The
purification of gases is very necessary in this
process. The S03 formed is absorbed in conc. H 2S04
°°
\I
O/~-~~O
"
when oleum is formed. S03 cannot be absorbed in OH OH

water because it produces a dense fog. The acid
obtained is pure. 21. The IUPAC name of H2S is sulphane.
H 2S04 is a colourless syrupy liquid. It contains 22. (a) SF6 is used in high voltage transformers because of its
98.3% H2S04' Its specific gravity is 1.84 at 15°C. It insulating property.
fumes strongly in moist air and highly corrosive in (b) Liquid oxygen mixed with finely divided carbon is used
nature. It is highly soluble in water. Various hydrates in place of dynamite in coal mining.
such as H2S04·H20, H2S04·2H20, H2S04·3H20, (c) A mixture of ozone and cyanogen is used as a rocket fuel.
(d) Gun powder is a mixture of sulphur. charcoal and KN0 3 .
(e) S2Cl2 is used in the vu1canisation of rubber. of ozone shield of the atmosphere. This is called 'ozone hole'.
(f) Electrical conductivity of Se is negligible in dark but It is feared that this will allow an excessive amount of UV
increases on exposure to light. Due to this property, Se light to reach the earth which will cause melanoma (skin
is used in photo electric cells. cancer) in humans.
23. The chemical reactions of ozone with oxides of nitrogen and
with chlorofluoro-alkanes are responsible for the depletion
• Subjective Type Questions (vi) H2S + HN0 3 ---? ...... + H 20 + S (Colloidal)

(vii) Fe2+ + SO~- + H+ ---? Fe3+ + H20 + S
1. Name the elements of group 16 which have:
-<viii) _..Mn 2+ + S 0 2- + H O---? MnO- + H+ + S02-
_(Q higl1estl'llec~~g~tivity_ .___ ._. . _ ___ . _...'2.. __ ..8_:!2'_ __..... _~ __... A __ ~_~_A_ - - . - - - - -
(:ti) maximum ionisation enthalpy (1X)~ Mn04 + H 2S ---? S + Mn2+ + H 20 (Acidic medium)
(iii) highest catenation property 7. From the reactions given below, identify (A), (B), (C) and (D)
(iv) highest electropositive nature. and their formulae.
2. Among the hydrides of group 16 elements, which have:
_(A)-I-cli!.!I]S9.1~!2~!207==:!1.l1LQ1:e~n colou~ _ . . _.__ _
--....c---{i),-Jo;wesU)()iling-.pQint-~~- ·-cc~cc.,'--'-·'··'·~··
(A) + dil. H2S04 + (C) ~·Mn.S04 - . . . . .-,,---.-
(ii) highest bond angle
. (iii) maximum acidic nature (A)+02~(D)
(iv) neutral in nature.
(D) + BaCl2 ---? White ppt.
3. List the elements 0, S, Se and Te in the order of decreasing:
(i) boiling point (li) electronegativity (iii) ionisation energy. 8. Arrange the following:
4•. Sulphuric acid acts as an acid, an oxidising agent and as a (a) H 2S, H 20, H2Se, H2Te in order of increasing acidity.
dehydrating agent. In which way does it behave when it acts (b) H20, H 2S, H2Se,H2Te in order of increasing stability.
on: (c) H 20, CO2, S03, N20S, Si02 in order of decreasing
(a) Glucose, (b) Sulphur, (c) Calcium carbonate, (d) Copper, acidity.
(e) Formic acid, (f) Hydrogen iodide, (g) Sodium hydroxide, (d) Po, Se, Te, S, 0 in order of increasing metallic
(h) Carbon. properties.
S. What happens when? (e) Po, Se, Te, S, 0 in order of decreasing ionisation
(i) Hydrogen sulphide is bubbled through an aqueous potential.
solution of sulphur dioxide. 9. Give at least one example to explain the following proper-
(ii) Hydrogen sulphide is passed through acidified ferric ties:
chloride solution. . (i) Sulphuric acid is a dibasic acid.
(iii) Sulphur is boiled with caustic soda solution. (li) Sulphuric acid is a dehydrating agent.
(iv) Ozone reacts with potassium ferrocyanide solution. (iii) Conc. H2S04 acts as an oxidising agent.
(v) Ozone is treated with ethylene. [M.L.N.R. 1990J
(iv) H2S acts as a reducing agent.
(vi) Sulphur dioxide is bubbled through aqueous solution
(v) . S02 acts as a reducing agent.
of copper sulphate in presence of potassium thio- (vi) S03 is an acid anhydride of H2S04'
cyanate. 10. A mixture of three gases A, B and C is passed first through
(vii) Sulphur dioxide gas, water vapour and air ar~ passed acidified K2Cr207 solution when A is absorbed turning
over heated sodium chloride. K2Cr207 solution green. Remainder is passed through excess
(vjii) Sulphuric acid is treated with PCls. of lime water which turns milky resulting in absorption of B.
(jx) Ozpne is passed through acidified stannous chloride The residual gas C is absorbed in alkaline pyrogallol sOlution.
solution. The mixture of A; B and C does not turn lead acetate paper
(x) Potassium iodide is heated with conc. H 2S04, black. Identify A, B and C.
6. Complete the following equations: 11. Answer the following:
(i) Write the general electronic configuration of VIA or
(i) (NH4hS20S + H 20 + MnS04 ~
..... . + ....... + ..... . 16th group .
(li) Name two chalcogens.
. H [1.1.1'. 1993]
ril) S + H 2S04 (conc.) ----7
eat ...... +H20 (iii) Which element of VIA group has maximum catenation
\'
property?
(iii) 12 + S02 + H 20---? SO~- + ....... + H+
(iv) Name the hydride of VIA group elements which is
(iv) 12 + 0 3 + H 20 ---? HI03 + ........ . liquid at room temperature.
(v) Cr209- + H+ + S02 ---? SO~- + H20 + ....... . (v) Which allotropic form of sulphur is more stable at room
temperature?
(vi) Which gas is formed in the upper layers of atmosphere orbitals can be unpaired by shifting electrons to
by action of UV radiations? d-orbitals.
(vii) The common oxidation states of VIA group elements ns np nd
are ...... . Ground state Illliitl iii I LI --L--'--...l..-..L..- +2 oxidation state
(viii) What is the other name of peroxy disulphuric acid?
1st excited state IITII iii Ii I LIi'-.JIL......J.---L---'--_ +4 oxidation state
(ix) Name theacid used in storage batteries.
(x) What is the reason for the syrupy nature of conc. 2nd excited state [1J Iiii Ii I LIi~l,-,-i--LI---,-----,------, +6 oxidation state
H2S04? The elements of oxygen family except oxygen,
(xi) Among the hydrides, H 20, H 2S, H 2Se, which has the therefore, show +2, +4 and +6 oxidation states
highest bond anglr? besides -2.]
(xii) Write the formula of oleum.
(v) The tendency to show -2 oxidation state diminishes
(xiii) Which catalyst is used in the manufacture of H 2S0 4
from sulphur to polonium.
by contact process? [M.L.N.R.1997]
[Ans. On moving down the group, the size of the atom
(xiv) What are the most favourable conditions of tempera- _ increases and_the_electronegativity_decreases.-.lTh-'1J.Lills>,-,_ __
ture-andpressure for the conversion-orS021ntoSO~? the tendency to accept two more electrons as to
(xv) The other name of sulphuric acid is ..... . attain octet in outermost shell decreases, i.e., the
12. Write the hybridization state of the central atom, shape and tendency to show -2 oxidation state decreases.]
electronic structure of the following molecules or ions. (vi) Sulphur dioxide is more powerful reducing agent in
__(iLSulphurJriQxide,___(iyLS_ulphatdQn _________ _ ---- n---an-alkaline-mediumthan-1n-aeidie-medium~fI.I.T.lmh]==~
(ii) Sulphuric acid, (v) Ozone [Ans. The reducing property is represented as,
(iii) Sulphur dioxide, (vi) Hydrogen sulphide S02 + 20H- ----t SO ~- + 2H+ + 2e-
13. Explain the following:
Addition of acid favours reverse reaction whereas
(i) Oxygen is a gas while sulphur is a solid. presence of OH- favours the forward reaction.]
.[Ans. The oxygen molecule is diatomic involving a double
bond. Its small size produces weak intermolecular (vii) Dry S02 does not bleach dry flowers.
forces amongst its molecules and is, thus, a gas at [Ans. Only in presence of moisture, the nascent hydrogen
room temperature. Sulphur is incapable of forming responsible for bleaching (reduction) is produced.
1t-bonds. Its molecule has a puckered ring structure S02 + 2H2 0 ----t H2S04 + 2H
of eight sulphur atoms joined by single covalent Coloured flower + H ---,---t Colourless flower]
bonds. The intermolecular forces acting between S8
(viii) H 2S is stronger acid than H 20.
molecules are stronger and hence, sulphur is a solid.]
[Ans. The H-S bond is weaker than H-O bond and the
(ii) Water is liquid while H 2S is a gas. proton is more easily released when H2S reacts with
[Ans. Oxygen is more electronegative than sulphur. Thus, water.]
oxygen can form hydrogen bonds. Water is an
(Jx) Hydrogen sulphide cannot be dried by passing
associated liquid due to hydrogen bonding. The
hydrogen bonding is absent in H2S, hence the through conc. H2S04'.
molecules are unassociated. It, therefore, exists in [Ans. Conc. H2S04 is an oxidising agent while H2S is a
gaseous state.] reducing agent. Both react to form free sulphur.]
(iii) Sulphuric acid has high boiling point and viscosity. (x) Nitric acid cannot be used to prepare H 2S.
[Ans. The high boiling point and viscous nature of conc. [Ans. Nitric acid is an oxidising agent. It will oxidise H2S.
H2S0 4 is.due to hydrogen bonding due to which a 3H2S + 2HN0 3 ----7 2NO + 3S + 4H20
number of sulphuric acid molecules are associated (xi) In the manufacture of sulphuric acid by the contact
to form a cluster. process, sulphur trioxide is not directly dissolved in
HO)S(O----H-O)S(O---j water.
[Ans. S03 reacts with water to form H2S04 which is not
HO O---H-O 0--- easily condensed and escapes in the atmosphere. It
is, therefore, absorbed in conc. H2S0 4 to form
(iv) Oxygen almost invariably exhibits an oxidation state oleum which may be diluted to form H2S04 ,
of -2 but the other members of the family exhibit H2S04 + S03 ----7 H2S20 7
negative as well as positive oxidation states of
H2S20 7 + H20 ----7 2H 2S04]
+2, + 4 and + 6.
[Ans. All the elements of oxygen family have a (xii) For the dilution of H2S04, water should not be added
configuration of· ni n/ of the outermost orbit. to conc. H 2S04.
They all tend to attain 8 electrons by accepting two [Ans. Conc. H2S04 has great affinity for water molecules.
more electrons, i.e., all show -2 oxidation state. During addition of water, large amount of heat energy
Oxygen has no d-orbitals while, others have is released. The temperature rises suddenly and
d-orbitals in their valency shells. Thus, the paired bumping takes place. To avoid any accident, acid
should be added to water with constant stirring [Hint : Substance (A) is· sulphur.
rather than water to acid.] S +6HN0 3 ~ H2S04 +2H 20+6N02
(A) (B)
(xiii) Conc. HZS04 cannot be used for drying Hz.
[Ans. Hydrogen, sometimes, ignites with the large amount S + Na2S03 ~ Na2S203
(A) (e)
of heat released when water is absorbed by acid.]
Na2S203+H2S04 ~ Na2S04+S0Z +S+HzO
(xiv) The bond angle in HzS is lower than in HzO. (C) (D) Turbidity
[Ans. Sis less electronegative than oxygen. The bonded 2NazS203 + Iz ~ NaZS406 + 2Nal]
(C) Colourless solution
electrons in H2S move further away from S-atom
than O-atom in H 20. This decreases repulsion 16. An inorganic halide (A) reacts with water to form two acids
between bonded electrons and thus, there is (B) and (C). (A) also reacts with NaOH to form two salts (D)
contraction in bond angle.] and (E) which remain in solution. The solution gives white
(xv) KMn0 4 should not be dissolved in co.nc. HzS04 . precipitates with both AgN03 and BaClz solutions
[Ans. Mn207 is formed which is unstable and explosive respectively. (A) is a useful organic reagent
mnattire. [Hint:A:::S02C12_
2KMn04 + 2H2S04 ~ K2S04 + (Mn03hS04 + 2H20
S02Clz+2HzO~ H ZS04 + 2HCl
(Mn03hS04 + H20 ~ Mn2~ + H2S04] (A) (B) (C)
(xvi) Ozone layer in the upper regions of atmosphere SOzClz +4KOH ~ KZS04 + 2KCI +2H zO
protects earth from the harmful radiations of sun.
~[Ans. .. Hamifill UV~riidiiifions-are . ertiitted~bysun.TIiec
ozone layer is capable of absorbing these radiations
and thus protects the earth from these radiations.]
.- (A) .
--~--~-Fl'--~--
(D) (E)
14. An aqueous solution of a g<is (X) gives the following BaS04 AgCl
Whiteppt. Whiteppt.
'reactions:
(i) It decolourizes an acidified KZCrZ07 solution. 17. In the contact process for industrial manufacture of sulphuric
(ii) On boiling with HZ0 2, cooling it and then adding an acid some amount of sulphuric acid is used as a starting
aqueous solution of BaClz, a precipitate insoluble in material. Explain briefly. What is the catalyst used in the
dil. HCI is obtained. oxidation of SOz7 [I.I.T.1999}
(iii) On passing HzS in the solution, white turbidity is
obtained. Identify (X) and give equations for steps (i), • Matching Type Questions
(ii) and (iii). [Roorkee 1993)
Match the following:
[Hint: Step (iii) suggests that (X) is SOz.
[A] (a) OleUm (i) NO·HS04
SOz + 2HzS ~ 3S + 2HzO (b) Peroxy disulphuric acid (ii) HZS05
Turbidity
(i) K2CrZ07 + H2S04 +3802 ~ K 2S04 +Cr2(S04h +H20 (c) Peroxy monosulphuric acid (iii) HzS~
Colourless solution (d) Chamber crystals (iv) H2Sz~
(ii), H202 +S02 ~ IhS04 (e) Sulphurous acid (v) HzSz0 8
HZS04 + BaCl2 ~ BaS04 +2HCl]
White ppt.
[B] (i) Sulphur dioxide (a) Laboratory reagent
15. A pale yellow substance (A) when heated with conc. HN03 for mixture analySis
evolves a brown coloured gas (B). The substance (A) also (ri) Oxygen (b) Olewn
dissolves in sodium sulphite solution on· heating. A clear (iii) Ozone (c) Vulcanizing rubber
solution (C) is formed which on acidification gives a turbid (iv) Hydrogen sulphide (d) Petroleum refining
solution and a pungent smelled gas (D) which is formed by (v) Sulphur (e) Paramagnetic
the substance (A) in air. The solution (C) decolourises iodide (vi) Sulphuric acid (f) Marshall's acid
solution. Identify (A) to (D). (vii) Fuming sulphuric acid (g) Antichlor
(viii) . Peroxy disulphuric acid (h) Detection of double
bond in organic
compoun.ds.
Answers : Subjective Type Questions 2NaOH + H 2S0 4 ------7 Na2S04 + 2H 20

1. (i) oxygen (ii) oxygen (iii) sulphur (iv) polonium or ununhexium Sodium sulphate
2. (i) H2S (ii) H 20 (iii) H2Te or H2Po (iv) H20 (normal salt)
3. (i) Te > Se > S > 0 (ii) H2S04 has great affinity for water molecules, and hence it
(ii) 0 > S > Se > Te acts as a dehydrating agent.
(iii) 0 > S > Se > Te H 2S04
C12H22011 --~) 12C +lIH 20
4. (a) dehydrating agent, (b) oxidising agent, (c) an acid, (d) oxidising Sugar Carbon
agent, (e) dehydrating agent, (f) oxidising agent, (g) 'an acid,
H 2S0 4
(h) oxidising agent. HCOOH --~) CO + H20
5. (i) (Moist) S02 + 2H2S ------7 3S + 2H20 Formic acid
(ii) 2FeCl3 + H2S ------7 2FeCl2 + 2HCI + S (iii) H2S04 oxidises metals, non-metals and other compounds.
Sulphur in H2S04 is in +6 oxidation state, thus it can change
(iii) 4S + 6NaOH ------7 Na2S203 +2Na2S + 3H20
----- - - - --into-Iower-oxidation-states,- i.e.,-+4,~2,-etc.-----------
Excess sulphur) Na2SS Cu + 2H2S04 (conc.) ------7 CUS04 + S02 + 2H20
(iv) 2K~e(CN)6+03 + H20 2K3Fe(CN)6 + 2KOH + O2
------7 2P + 5H2S04 ------7 2H3P04 + 2H20 + 5S02
_ . . 0 2HBr + H2S04 ------7 S02 + Br2 + 2H20
/ ~ (iv) Sulphur in H2S is in -2 oxidation state, thus it can increase
(-v) nCH2-=-CB2±D3-----):-TH2---~H2- -- - - - - - ----------:--'=th-eoXfilatron state-orily aillrlience-rt acts as--a teduci-;;;-ng~ag"'e-';nCFr.====-=---=-~
0--0 H2S + Cl2 ------7 2HCI + S
(vi) 2CUS04 + S02 + 2KCNS + 2H20 ------7 H2S + 2HN03 ------7 2N02 + 2H20 + S
2CuCNS + K2S04 + 2H2S04 (v) As it can be oxidised to sulphuric acid, it acts as a reducing
(vii) 2S02 + 02 + 2H20 ------7 2H2S0 4;, agent.
2NaCI + H2S04 ------7 Na2S04 + 2HCI S02
H2S04 ------7
O.N. +6 +4
(viii) H2S04 + 2PCIs ------7 S02Cl2 + 2POCI3 + 2HCI Cl2 + 2H20 + S02 ------7 H2S04 + 2HCI
(ix) 3SnCI 2 +' 6HCI + 0 3 ------7 3SnCl4 + 3H20 2FeCl3 + 2H 20 + S02 ------7 H2S04 + 2FeCl 2 + H2S04
(x) 2Kl + H2S0 4 ------7 K2S04 + 2ID (vi) S03 combines with water to form H2S04, hence it is an
2ID + H2S04 ------7 12 + S02 + 2H20 acid anhydride of H2S0 4,
6. (i) (Nl4hS20g + H20 ------7 (NH4hS04 + H2S04 + 0 S03 + H20 ------7 H2S04
MnS04 + H20 + 0 ------7 Mn02 + H2S04 10. A is S02 as it turns acidified K2Cr207 solution green. (It is not
H2S as it does not turn lead .acetate paper black.) B is CO2 as it
(NH4hS20g + MnS04 + 2H20 ------7 (NH4hS04 + Mn02 + 2H2S04 turns lime water milky and C is oxygen which is absorbed in alkaline
pyrogallol.
(ii) S + 2H2S04 ------7 3S02 + 2H20
(iii) 12 + S02 + 2H20 ------7 SO~+ + 2r + 4H+
11. (i) ni n/, (ii) Oxygen and sulphur, (iii) Sulphur, (iv) Water, H20,
(v) Rhombic, (vi) Ozone, (vii) -2, +2, +4, +6, (viii) Marshall acid,
(iv) 12 + 503 + H20 ------7 2ID03 + 502 (ix) H2S04, (x) Intermolecular hydrogen bonding, (xi) H20,
(v) Cr20~- + 2H+ + 3S02 ------7 3S0~- + H20 + 2Cr3+ (xii) H2S20 7, (xiii) Platinised asbestos or vanadium pentoxide,
(xiv) Low temperature (optimum temperature 450°C) and high
. (vi) H2S + 2HN0 3 ------7 2N0 2 + 2H20 + S (colloidal)
pressure (optimum pressure 2 to 3 atmospheres), (xv) Oil of vitriol.
(vii) 2
4Fe + + SO~- + 6H+ ------7 4Fe3+ + S -+ 3H20
12. (i) S03, si hybridization, planar triangular
(viii) 2Mn2+ + 5S20~- + 8H 20 ------7 2Mn04 + 16H+ + lOS0~
o
(ix) 2Mn0 4 + 6W + 6H2S ------7 2Mn2+ + 5S + 8H20 II
S
7. (A) = Na2S03; (B) = Cr2(S04h; (C) = KMn04; (D) = Na2S04 ~20~
8. (a) H20 < H2S < H2Se < H2Te o 0
(b) H2Te < H2Se < H2S< H20 The equivalence of all s-o bonds suggest that S03 is a resonance
(c) S03 >-N 20s > CO 2 > Si0 2 > H20 hybrid of the following structures :
(d) 0 < S < Se < Te < Po o 0
(e) 0 > S > Se > Te > Po II t
S~ S~
9-. (i) One molecule of H2S04 consists two replaceable hydrogen
/ f------? / f------?
atoms and forms two series of salts.
o 0 0 0
Sodium hydrogen
sulphate (acidic salt)
(ii) H2S04, sp3 hybridization, tetrahedral (iv) 0 3, s/ hybridization, angular (V-shaped)
/0,
..
:0: :0:
(v) H2S: sp3 hybridization,V~shaped
:8:
~+ .~
(iii) S02, sp2 hybridization, V-shaped

... Answers : ~a.tc_~ing I~Q.u.e_sti~ns
[A] (a-iv); (b--v); (c-ii); (d-i); (e-iii)
[B] (i-g); (ii--e); (iii-h); (iv-a); (v--<:); (vi-d); (vii-b);
:0: :0: (viii-f)
'UUS1~1'ONS OF OBJECTIVE QUESTIONS

1. Concentrated H2S04 can be used to dry the gas : 2NaHS03 + Na2C03---:> 2Na2S03+ H20 + CO2
(B)
(a) H~ (b) ~
(c) NH3 (d) all Na2S03 + S---* Na2S203 ]
(e)
Ans. (b)
5. Acidified KMn04 is dropped over sodium peroxide taken in
[Hint: HzS and NH3 react with H2S04 while C02 is not affected.
a flask at room temperature, vigorous reaction takes place to
H2S + H2S04 ---:> S + 2H20 + S02
produce:
2NH3 + H2S04 ---:> (NH4hS04 ]
(a) hydrogen peroxide
2. Sulphur on reaction with concentrated HN03 gives (A) which (b) a mixture'of hydrogen and oxygen
reacts with NaOH gives (B). (A) and (B) are : (c) a colourless gas hydrogen
(a) H2S03•Na2S203 (b) N0 2, Na2S (d) a colourless gas dioxygen
(c) H2S04• Na2S04 (d) H2S20 3, Na2S2~ Ans. (d)
Ans. (c)
[Hint : [Na202 + H2S04 ---:> Na2S04 + H20 Z] x 5
[Hint: 6HN03+S---:> H2S04+6N02 +2H 20;
(Al 2KMn04 + 3H2S04 ---* K2S04 + 2MnS04 + 3HzO + 50
H2S04 +2NaOH---:> Na2S04+2H20] [H 20 2 + 0 ---:> H20 + O2] x 5
• (B)
3. The structures of 0 3 and N3 are : 2KMn04 + 8H 2S04 + 5Naz02---:> 5Na2S04 + K2S04 + 2MnS04
(a) linear and bent respectively + 8H20 + 502]
(b) both linear 6. Among the oxides given below which are acidic?
(c) both bent Cr03, Mn20?, CuO, CO, S02
(d) bent and linear respectively (a) Only S02 (b) cr0 3• Mn20? and S02
Ans. (d) (c) Mn20? and S02 (d) CO and S02
4. When an inorganic compound reacts with S02 in aqueous Ans. (b)
medium produces (A), (A) on reaction with Na2C03 gives the [Hint : cr03 + H20 ---* H2Cr04;
compound (B) which with sulphur gives a substance (C) used Mn207 + H20 ---:> 2HMn04;
in photography. The compound (C) is : S02 + H20 ---:> H2S03
(a) Na2S2~ (b) Na2S04 (c) Na2S (d) Na2S20? CuO is a basic oxide while CO is a neutral oxide.]
Ans. (a) 7. In which of the following reactions O2 is not formed as one
[Hint: Na2C03 + 2S02 + H2 0---* 2NaHS03 + CO2 of the product?
(A)
(a) KCIO Mn02 )
3 Heat
(b) SnCl2 + HCI + Or-~ 12. The number of unpaired electrons in a paramagnetic diatomic
(c) FeS04 + H 2S04 + 0 3 ~ molecule of an element with atomic number 16 is:
(a) 4 (b) 1
(d) PbS +03~
(c) 2 (d) 3
ADS. (b)
ADS. (c)
[Hint : 3SnCl2 + 6HCI + 0 3 ~ 3SnCl4 + 3H20]
[Hint : S2 molecule is paramagnetic like O2 having 2 unpaired
8. The formation of which of the substance is known as tailing electrons.] . . '
'of mercury?
13. The molecular formula of dithionic acid is: \
(a) Hg20 (b) HgO
: [C.R.,. (J&K) 2006]
(c) Hg(N~)z (d) HgS
ADS. (a) .: (a) H2S20 4 (b) H2S20 6 I
9. Which of the following elements forms p1t-d1t bonding in its (c) H2~OS (d) H2S20s
oxide? ADS. (b)
{a)-bitbium- -----{b)-Boron 14•. Whichamong.thefollowing.statements.are.correct2
(c) Sulphur (d) Nitrogen [PAT. (Kerala) 2007]
ADS. (c) (i) Carbon monoxide is neutral whereas S03 is acidic
[Hint : Among the given elements, sulphur fonns d1t-p1t bonding (Ii) Potassium oxide is basic whereas nitrous oxide is acidic
in its oxides such as S~ and S03'] (iii) Aluminium and zinc oxides are amphoteric
,---- --io-:- .
fil willchOfiliefoi1owingspecies~-atom assumes sp3-iiybrid --..- -·(iv}·Sulphur~-trioxide-:-is---acidie--wher-eas--phosphorus:=-==~
state? ' pentoxide is basic
I(S03); II (SOz); ill (H S); IV (S8) (v) Carbon dioxide is neutral whereas sulphur dioxide is .
2
(a) 1, n (b) n ill amphoteric
(c) II,IV (d) rn,IV . (a) (ii)and(iii) (b) (i) and (iv)
ADS: (d) (c) (i)and(iii) (d) (ii) and (iv)
(e) (iii) and (v)
11. Which of the following chemical reactions depicts the ADS. (c)
oxidising behaviour of H2S04? [AJ.E.E.E. .2006]
15. Ozone is used for purifying water because: [C.P.M.T. 2007]
(a) 2Hl + H2S04 ~ 12 + S02 + 2H20
(a) it dissociates and release oxygen
(b) Ca(0H)2 + H2S04 ~ CaS04 + 2H 20
(b) it does not leave any foul smell like chlorine
(c) NaCI + H2S04 ~ NaHS04 + HCI
(c) it kills bacteria, cyst, fungi and acts as a biocide
(d) 2PCIs + H2S04 ~ 2POCl3 + 2HCI + S02Cl2
(d) all of the above
ADS. (a)
Ans. (d)
[Hint: In reaction (a), the O.N. of S reduces from +6 to -t4.]
I , OBJECTIVE QUESTIONS 0
- ... -
Set I: This set contains questions with one con'ect answer.
1. The formula of sulphur molecule is: 14. The number of unpaired electrons in the p-subshell of VIA
(a) Sz 0 (b) S4 0 or 16th group of the periodic table is:
(c) S6 0 (d) S8 0 (a) 1 0 (b) 2 0
2 The most stable allotropic form of sulphur is: (c) 3 . 0 (d) 4 0
(a) rhombic 0 (b) monoclinic 0 15. Which shows maximum catenation property?
(c) plastic 0 Cd) milk of sulphur 0 (a) Te 0 (b) Se 0
3. Ozone is: . (c) S 0 (d) 0 0
(~t.comPQl.IDQ.oLO;li.ygill:\ o 16. Ozone readily dissolves in:
(b) allotrope of oxygen o (a) -HzO . o
(c) isotope of oxygen o (c) turpentine oil 0 (d) ammonia o
(d) mixture of atomic and molecular oxygen o 17. The maximum bond angle is in:
4. The percentage of ozone in ozonised oxygen is about: (a) H20 . 0 (b) H2S 0
--·--(a}-40----- .......... (c.)..HzSe.. _.~-~-~-7~Q~(qU1iA~~_. ~D=~
(c) 10 0 (d) 100 o 18. Which one of the metal sticks to glass piateontreat~ent
5. The product A in the following equation : with ozone?
2KMn04 ~ A + MnOz + Oz, is : (a) Silver 0 (b) Mercury o
(a) KzMnZ0 7 0 (b) KzMn04 0 (c) Copper 0 (d) Lead o
(c) KzO 0 (d) KzOz 0 19. Moist iodine reacts with ozone to form:
6. When MnOz is added to KCI03 in the preparation of oxygen
(a) HI 0 (b) I20 5 o
the decomposition temperature of KCI0 3 is reduced from (c) HI03 0 (d) HI04 o
3500Cto ...... . 20. In the laboratory HzS is prepared by the action of:
(a) dilute H2S04 on FeS 0 (b) dilute H 2S04 on FeS03 D
(a) 3000C 0 (b) 150°C o (c) hydrogen on sulphur 0 (d) hydrogen on SbZS3 0
(c) 250°C 0 (d) room temperature o 21. When HzS is passed through acidified KZCrZ07 solution, the
7. The oxide which on strong heating evolves oxygen is:
solution turns:
(a) NazO 0 (b) Alz0 3 o (a) yellow 0 (b) blue o
(c) Cao 0 (d) Ba02 o (c) white 0 (d) green o
8. Non-metals combine with oxygen to form usually:
22. Which one of the followi~g is purely reducing agent?
(a) basic oxides 0 (b) neutral oxides o (a) Hydrogen sulphide 0 (b) Hydrogen peroxide 0
(c) acidic oxides 0 (d) amphoteric oxides o (c) Sulphur dioxide 0 (d) Ozone 0
9. Which one of the following is an amphoteric oxide? 23, Sulphur dioxide is obtained by the action of dilute HZS04
(a) Mn02 0 (b) Zno o on:
(c) CaO 0 (d) COz o (a) copper turning o
(b) sodium sulphate o
10. In ~e upper layers of atmosphere, ozone is formed:
(a) by action of electric discharge on oxygen molecules 0
(c) sodium sulphite o
(d) sodium sulphide o
24. The formula of oleum is:
(b) by action of ultraviolet rays on oxygen molecules 0
(c) by action of infrared rays on oxygen molecules 0 (a) HZS05 0 (b) HzSz~ o
(d) due to sudden drop of pressure 0 (c) HZSZ0 3 0 (d) HzSzOg o
11. On heating ozone, its volume: 25. Low volatile nature of HZS04 is due to :
(a) increases to 1~ times 0 (b) decreases to half o (a) strong bonds 0 (b) hydrogen bonding 0
(c) remains unchanged 0 (d) becomes double o (c) van der Waals' forces 0 (d) none of these 0
12. Which requires catalyst? 26. The ratio of the gases obtained on dehydration of HCOOH
(a) S+02~SOZ 0 (b) 2S02+02~2S03 0 and HZCZ04 by conc. HZS04 is :
(c) C + O2 ~ CO2 0 (d) All of these 0 (a) 2: 1 . 0 (b) 1 : 2 o
13. In the reaction, (c) 3 : 1 0 (d) 1 : 3 o
H 2S04
2Kl + H20 + 0 3 ~ 2KOH + O2 + A, [ Hint ~ HCOOH )CO+H 20;
H 2S04
the compound A is: H 2C20 4 )CO+C0 2 +H 20
(a) KI03 o The ratio is 1 : 2.]
(c) HI03 o
n. Whi?.h one of the following on heating will give mixture of o 0

S02 and S03? . . II II
[Hint: HO-S-S-OHJ
(a) ZnS03 0 (b) CuS0 4 0 +5 +3
II
(c) Na2S04 0 (d) FeS04 0 o
28. Which of the following oxides is amphoteric in character? 39. Which is the most basic of the following oxides?
[A.I.E.E.E. 2005] (a) Na20 0 (b) B20 3 0
(a) Cao o (b) C~ o (c) ZnO 0 (d) P203 0
(c) Si02 o (d) Sn02 o 40. Which of the following is the most acidic?
29. Ozone molecule is: (a) Al203 0 (b) Na~ 0
(a) linear 0 (b) triangular 0 (c) MgO 0 (d) Cao 0
«c) tetrahedral 0 (d) none of these 0 41. Which is not the characteristic of cone. H2S04?
30., Which of the following hydrides of the oxygen family shows (a) Oxidising agent
< 0 (b) Efflorescent 0
. th~ 10W~JlLbl()iliIlgJ)oiIl!? . (c:)l!ygr()~f()picOi(j)~u!pjl()l!atingag~I)t --=~-~.......
(a) H20 I 0 (b) H2S 0 42. H2S is passed through potassium permanganate solution, we
(c) H2Se lP (d) H2Te 0 get:
31. A considerable part of the ~armful ultraviolet radiation of the (a) potassium sulphide 0 (b) sulphur 0
sunpoes not reach the surface of earth. This is because in (c) potassium sulphite 0 (d) manganese sulphide 0
.. thdlpper~atmosphere,-there-is~a-Iayer--of:-·--- .. ~-43.~The.gas03cannotcoxidise-~ .. ---~-. ···~---~-~~7--~~~~~~
(a) ~ b (b) C~ 0 (a) KMn04 0 (b) FeS04 0
(c) NH3 0 (d) H2 0 (c) KI 0 (d) K2Mn0 4 0
32. SF6 is unreactive towards water because: 44. Which statement about H2S is false?
(a) It is a covalent compound 0
(a) sulphur has very small1size 0 (b) It is a gas with bad smell 0
(b) fluorine is most electronegative element 0
(c) It is a weak base in water 0
(c) sulphur shows +6 oxidation state 0 (d) It is a stronger reducing agent 0
(d) due to steric hindranc.e water moltkule cannot attack 45. Sulphur does not exist as S2 molecule because:
S-atom 0 (a) It is less electronegative 0
33. In sulphate ion the oxidation state of sulphur is +6 and (b) It'has ability to exhibit catenation 0
hybridization state of sulphur is: (c) It is not able to constitute p1t-p1t bond 0
(a) sp2 Q (b) sp3 d 2 0 (d) It has the tendency to show variable oxidation statesO
(c) dsi 0 (d) sp3 0 46: The gases respectively absorbed by alkaline pyrogallol and
34. The catalyst used in the manufacture of sulphuric acid by oil of cinnamon is:
lead chamber process is: (a) 03, CH4 0 (b) S02, ~ 0
(a) Pt 0 (b) Ni 0 (c) 02,03 . 0 (d) N20,03 0
(c) NO 0 (d) N203 0 47. Ordinary oxygen contains:
35. From the following information (a) a mixture of 0 16,0 17 and 0 18 0
X + H2S04 - 7 Y (a colo~rless and irritating gas) (b) a mixture of 0 and 0
16 17
0
Y + K2Cr207 + H2S04- 7 green coloured solution (c) only 0 16 0
8
Identify the pair X and Y. (d) only 01 0
(a) CeHCI 0 (b) SO~-,S02 0 48. Anhydride of sulphuric acid is:
(c) S2-, H2S 0 (d) CO~-, C02 0 (a) S02 0 (b) S03 0
36. The catalyst used in the manufacture of H2S04 by contact (c) H S
22 30 0 (d) H S0
2 3 0
process is: 49. Sulphuric acid is a dibasic acid in nature, hence it forms:
(a) platinised asbestos o (b) Ni o (a) acidic salt 0 (b) acidic and basic salt 0
(c) Fe o (d) NO o (c) acidic and normal salt 0 (d) double salt 0
37. Oleum is: SO. When S02 is passed through a solution of H2S in water:
(a) a mixture of conc. H2S04 and oil 0 (a) sulphuric acid is formed 0
(b) sulphuric acid saturated with S03 0 (b) a clear solution is formed 0
(c) a mixture of H2S04 and HN03 0 (c) sulphur is precipitated 0
(d) a mixture of H2S04 and HCI 0 (d) no change is observed 0
38. In disulphurous acid or pyrosulphurous acid, the oxidation 51. Conc. H2S04 displaces hydrogen chloride from chlorides
states of sulphur can be : because:
(a) +6 and -2 0 (b) +6 and 0 0 (a) it is stronger than hydrochloric acid 0
(c) +5 and +3 0 (d) +5 and -2 0 (b) HCI is a gas while H S0
2 4 is a liquid 0
Elements of Group VIA or 16.(The Oxygen Family) 569
(c) sulphates are more soluble than chlorides 0 66. Caro's acid is:
(d) sulphates are less soluble than chlorides 0 (a) H2SOS o (b) H2S03 o
52. The valency of sulphur in SO~- is: (c) H3S20S o (d) H2S20g o
(a) 2 0 (b) I 0 67. Marshall's acid is:
(c) 4 0 (d) 6 0 Ca) H2S20S 0 (b) H2S20S o
53. S02 + H2S ~ Product. The fina! product is; (c) H2SOS 0 (d) H2SO4 []
[J.E.E. (Orissa) 2005] 68. Ozone turns benzidine paper:
(a) H2SO4 0 (b) H2S03 0 (a) violet 0 (b). brown o
(e) H2S20 3 . 0 (d) H20 + S 0 (c) blue o (d) red o
54. An element forms a gaseous oxide which on dissolving in 69. S02is:
water gives an acidic solution. The element is: (a) acidic 0 (b) alkaline 0
(a) hydrogen 0 (b) sodium o (cl neutral 0 (d) amphoteric 0
(<:lsulphw: . o
. (d)..ll1agnesium p . 70._Whlch~one-oLthefollowing--Statements-is~wrong?----~--···
55. Fuming sulphuric acid is; (a) H2S is a dibasic acid 0
(a) H2S04 + S02 0 (b) H2S04 o (b) H2S acts only as a reducing agent 0
(c) H2S04 + S04 0 (d) H2S04 + S03 o (c) The bond angle in H2S is 109"28' . 0
56. Which of the following turns lead acetate paper black? (d) H2S has rotten sinell .0
....~ .... ~(a)~~~~ ~~,-cc-~-rlcl,~(b)~~-...~ .. ~-.~~~... ..{J- 11;.-Whieh~one-ohhe..followirrgstatements ·is~wtong<r·cc--c~~=~···~
(c) H2SO4 0 (d) H2S 0 (a) S02 dissolves in water and forms §ulphurous acid 0
57. What is same in various hydrides of chalcogens? (b) S02 acts as a bleaching agent 0
(a) Molecular shape o - . (c) S02 has pungent odour 0
(b) Reducing nature o (d) S02 acts only as oxidising agent 0
(c) Central bond angle o 72. About H2S04, which of the following statements is incorrect?
(d) Magnitude of interparticle forces o (a)' It acts as a reducing agent 0
58. Which of the following elements occurs in native state? (b) It acts as an oxidising agent 0
(a) I 0 (b) S 0 (c) It acts as dehydrating agent 0
(c) Si 0 (d) P 0 (d) It is highly viscous D·
59. When concentrated H2S04 ,is added to dry KN0 3, brown 73. Which one of the following is wrong?
fumes evolve. These fumes are of: (a) Oxygen and sulphur belong to the same group of periodic
(a) S02 0 (b) S03 0 . table 0
(c) NOz 0 (d) NO 0 (b) Oxygen is a gas while sulphur is solid 0
00. Mark the wrong statement. When Na2S is added to sodium (c) Both show +2, +4 and +6 oxidation states 0
nitroprusside solution: (d) H2S has no hydrogen bonding 0
(a) beautiful violet colour is produced 0 74. Which one of the,following is not true peroxide?
(b) a complex [Fe(CN)sNOS]4-- is formed 0 (a) Pb02 0 (b) Ba9z 0
(c) acomplex[Fe(CN)sNOSP-isformed 0 (c) Na202 0 (d) H2Dz 0
(d) thecomplexN~[Fe(CN)sNOS] is formed 0 75. Which of the following oxides exists as trigonal planar
6l. When H2S is passed through nitric acid solution, the product molecule in gaseous state and a cyclic "trimer in the' solid
formed is: state?
(a) H2S04 0 (b) colloidal sulphur 0 (a) S02 0 (b) Se02 o
(c) S02 0 (d) plastic sulphur 0 (c) Se03 0 (d) S03 o
62. Mark the compound which gives carbon with cone. H2S04: 76. Which of the following acts as pickling agent?
(a) formic acid 0 (b) succinic acid 0 [C.P.M.T.2006]
(c) oxalic acid 0 (d) sugar 0 (a) HN03 0 (b) H2SO4 o
63. Oxygen can be obtained from bleaching powder by: (c) HCl 0 (d) HN02 o
(a) adding dilute acid o 77. H2S is far more volatile than water because:
(b) passing carbon dioxide o (a) sulphur atom is more electronegative than oxygen atom
(c) heating with a cobalt salt o o
(d) adding alkalies .. o (b) oxygen atom is more electronegative than sulphur atom
64. Ozone reacts with ~Fe(CN)6 to form: o
(a) Fe203 0 (b) Fe(OHh ,p (c) H20 has bond angle of nearly 105° 0
(c) Fe(OH)2 0 (d) K#e(CN)6 o (d) hydrogen atom is loosely bonded with sulphur 0
65. Bleaching action of S02 is due to: '.
78. Which compound acts as an oxidising as well as a reducing
(a) reduction 0 (b) oxidation o agent?
(c) its acidic nature 0 (d) hydrolysis o (a) S02 o (b)Mn02 o
(c) Al20 3 o (d) 0:03 o
79. When S02 is passed through cupric chloride solution: (a) three 0 (b) two 0
(a) the solution becomes colourless and a white ppt. of (c) one 0 (d) zero 0
CU2Cl2 is obtained 0 92. In OF2 molecule, the total number of bond pairs and lone
(b) a white ppt. is obtained 0 pairs of electrons present respectively are: [D.P.M.T. 2002]
(c) the solution becomes colourless 0 (a) 2,6 0 (b) 2,8 0
(d) no visible change takes place 0 (c) 2,10 0 (d) 2,9 0
80. The acid used in lead storage cells is: 93. Which of the following has p1t-drt bonding?
(a) phosphoric acid 0 (b) nitric acid 0 [C.B.S.E. 2002]
(c) hydrochloric acid 0 (d) sulphuric acid 0 (a) N0 0 (b) SO~- 0
3
81. Hydrolysis of one mole of peroxydisulphuric acid produces: (c) BOt 0 Cd) CO~- 0
(a) two mOlles off sulphuric acid I h " d DO' 94. In the species O 2, 01. O 2 and O~-, the correct decre,asing
(b) two mo es 0 peroxymonosu p unc aCl
order of bond strength is: [A.I.E.E.E.2002]
(c) one.moILoLs_uln~uri.J: acid, an~~QllJLmQl~ of ,per()xy~, ,.,
monosulphuric acid
l'
0
(a:)-02-:>-01-::>(')t?or- --a--
(d) one mole of sulphuric acid, one mole of peroxymono- (b) oi > O2 > O 2> or 0
sulphuric acid and one mole of hydrogen peroxide 0 (c) O~- > O 2> 01 > O 2 0
82. Which of the following bonds has the highest energy? (d) O 2> O~- > O 2 > 01 0
---------(-a)~Se-S~---.-,~,_:~~(b}~Te-,..'fe--.---,''" ~~--I:J----95;--The-angular-shape-of--ozon(7moleeule(03)-eon~ists-OE==~
(c) S-S 0 (d) 0-0 0 [C.B.S.E. 2008]
83. Which of the following molecule does not possess a (a) I sigma and I pi bond 0
permanent dipole moment? (b) 2 sigma and 1 pi bond 0
(a) HzS 0 (b) SOz 0 (c) 1 sigma and 2 pi bonds 0
(c) S03 0 Cd) CSz 0 (d) 2 sigma and 2 pi bonds []
84. Which of the following is the most powerful oxidising agent? 96. Excess of PCIs reacts with conc. H 2S04 giving:
Ca) H2S04 0 (b) H3B~ 0 [C.E.T. (Karnataka) 2008]
(c) ~ 0 (d) H~4 0 (a) sulphuryl chloride 0 (b) sulphurous acid 0
85. In which ofthefollowing species, S-atom assumes sp3-hybrid (c) chlorosulphonic acid 0 (d) thionyl chloride 0
state? 97. The element evolving two different gases on reaction with
(i) S03 (ii) H2S (iii) CS2 (iv) S8 conc. H2S04 is: [p.E.T. (Kerrua) 2008]
Ca) (i) and (ii) 0 (b) (ii) and (iii) 0 (a) P 0 (b) C 0
(c) (ii) and (iv) 0 (d) (iii) and (iv) 0 (c) Hg 0 (d) S 0
86. All the elements of the oxygen family are: (e) Sn 0
(a) non-metals 0 (b) metalloids 0 98. Select the incorrect statement about the following:
(c) radioactive 0 (d) polymorphic 0 [J.E.E. (W.B.) 2008]
87. The geometry of H 2S and its dipole moment are: (a) 03 is used as germicide for purification of air 0
(a) angular and non-zero 0 (b) angular and zero 0 (b) In 0 3, 0-0 bond length is identical with that of
(c) linear and zero 0 (d) linear and non-zero 0 molecular oxygen ' 0
(c) 03 molecule is angular in shape 0
88. The oxidation number of sulphur in S8, S2F2, H2S respec-
(d) 03 is an oxidising agent 0
t(iv)e~, are: d 2 0 (b) +2, + I and ~2 0 99. The correct order ofa-o bond length in O2, H 20 2 and 03
a , +1 an - is: [P.E.T. (Rajasthan) 2006]
(c) 0, +1 and +2 0 (d) -2, +1 and -2 0 (a) 03> H 0 > O 0 (b) Oz > H 0 > 0 0
2 2 2 2 2 3
89. Which of the following does not have S-S linkage? (c) O > 0 > H 0 0 (d) H 0 > 03> O 0
2 3 2 2 2 2 2
[Roorkee (S) 2000] 100. In which of the following ions, there is no S-S bond?
Ca) S20~- 0 (b) S20~- 0 [PM.T. (Kerala) 2008]
(c) S20~- 0 Cd) S20~- 0 (a) s20l- 0 (b) S20~- 0
90. Amongst H 20, H 2S, H 2Se and H 2Te, the one with highest (c) S20~- 0 (d) S20~- 0
boiling point is: [I.I.T.(S) 2000] (e) S20~- 0
(a) H20 because of hydrogen bonding 0 101. Which of the following is not correct? [A.F.M.C. 2008]
(b) H2Te because of higher molecular weight 0
silent electric
(c) H2S because of hydrogen bonding 0 Ca) 30 2 ' ' 20 3 ; AH == -284.5 kJ. o
(d) H 2Se because of lower molecular weight. 0 discharge
91. The number of S-S bonds in sulphur trioxide trimer S309 (b) ozone undergoes addition reaction with unsaturated
is: [I.I.T. (S)2001] carbon compounds 0
Elements of Group VIA or16 (The Oxygen Family) 571
(c) sodium. thiosulphate reacts with 12 to form sodium 103. The function of Fe(0H)3 in the contact process is:
tetrathionate and sodium iodide 0 [C.E.T. (Karnataka) 2006J
(d) ozone oxidises lead sulphide to lead sulphate 0 (a) to detect colloidal impurity 0
102. The number of sigma and pi bonds in peroxydisulphuric acid (b) to remove moisture 0
are, respectively: [E.A.M.C.E.T. (Engg.) 2008] (c) to remove dust particles 0
(a) 9 and 4 0 (b) 11 and 4 0 (d) to remove arsenic impurity 0
(c) 4 and 8 0 (d) 4 and 9 0
tHint : Structure peroxydisulphuric acid
o 0
qii qli
lt lt
H~O~S~O~O~S~O.JLH] .
qli qli
lt lt
o 0
SefI.t:-This set contains questions with two or more correct answers.
104. Which among the following are peroxo acid of sulphur? 100. Select the correct statements about Na2S203·5H20:
(a) H2S03 0 (b) H2SOS 0 (a) It is also called as hypo 0
(c) H2S20s 0 (d) H2SO4 0 (b) It is used in photography to form comple~\Vitl1_~gBr£::L_c~_
-l05;--Select-theccorrectcstatem~ntsa.bouroxygeh-mOleCille: --------(c) IfCaiibe used as antichlO;:-------- - 0-'
(a) It is paramagnetic 0 (d) It is used to remove stains of 12 0
(b) Its bond order is two 0 110. Which of the following are amphoteric?
(c) In liquld state it is blue coloured 0 (a) BeO 0 (b) A120 3 0
(d) It has two unpaired electrons 0 (c) Zno 0 (d) ~ 0
1<Xi. S02 acts a s : ' 111. Which reagent does not give oxygen as one of the product
(a) bleaching agent 0 (b) oxidising agent 0 during oxidation with ozone?
(c) reducing agent 0 (d) disinfectant 0 (a) S02 0 (b) SnC12IHCI 0
107. Sulphuric acid can be used as: (c) H2S 0 (d) PbS 0
(a) hygroscopic agent 0 (b) oxidising agent 0 112. In which of the following S-S link is present?
(c) sulphonating agent 0 (d) efflorescent 0 (a) Caro's acid 0 (b) Dithionic acid 0
108. H2S can be used as: (c) Thiosulphuric acid 0 (d) Chlorosulphonic acid 0
(a) acid 0 (b) base 0 113. Peroxo acids of sulphur are:
(c) oxidising agent 0 (d) reducing agent D Ca) H2S04 D (b) H2S~ 0
(c) H2SOS 0 (d) H2S20s 0
1. (d) 2. (a) 3. (b) 4. (c) 5. (b) 6. (c) 7. (d) 8. (c) 9. (b) 10. (b)
11. (a) 12. (b) 13. (d) 14. (b) 15. (c) 16. (c) 17. (a) 18. (b) 19. (c) 20. (a)
21. (d) 22. (a) 23. (c) 24. (b) 25. (b) 26. (b) 27. (d) 28. (d) 29. (b) 30. (b)
31. (a) 32. (d) 33. (d) 34. (c) 35. (b) 36. (a) 37. (b) 38. (c) 39. (a) 40. (a)
41. (b) 42. (b) 43. (a) 44. (c) 45. (c) 46. (c) 47. (a) 48. (b) 49. (c) 50. (c)
51. (b) 52. (d) 53. (d) 54. (c) " 55. (d) 56. (d) 57. (a) 58. (b) 59. (c) 60. (c)
I
61. (b) 62. (d) 63. (c) 64. (d) 6S. (a) 66. (a) 67. (b) 68. (b) 69. (a) 70. (c)
71. (d) 72. (a) 73. (c) 74. (a) 75. (d) 76. (b) 77. (b) 78. (a) 79. (a) 80. (d)
81. (c) 82. (c) 83. (d) 84. (a) 85. (c) 86. (d) 87. (a) 88. (a) 89. (a) 90. (a)
91. (d) 92. (b) 93. (b) 94. (b) 95. (b) 96. (a) 97. (b) 98. (b) 99. (d) 100. (e)
101. (a) 102. (b) 103. (d) 104. (b, c) 105. (a,b,e,d) 106. (a,b,e,d) 107. (a,b,c) 108. (a,d) 109. (a,h,e,d) 110. (a,b,e)
111. (a,b) 112. (b,e) 113. (e,d)
Obj~ctive Que~tions for liT ASPIRANTS ~

1. When sulphur is boiled with Na2S03, a compound (A) is (a) 8,8 (b) 16,8
produced. (A) with excess of AgN0 3 solution gives a (c) 8,16 (d) 8,4
compound (B) which is water soluble and produces a black [Hint : S8 molecule is shown here. Every sulphur atom is in sl-
coloured SUlphide (C). Compounds (A), (B) and (C) will be hybridized state.
respectively : :8: .. .. :S:
(a) Na2S203, Ag2S203, Ag2S
I ~.S.-~.--- I
:S: •• .. :S:
(b) Na2S04, Ag2S04, Ag2S ~S-S./'
(c) Na2S207, Ag2S04, Ag2S
(d) Na2S0S, Ag2S0S, Ag2S04
[Hint: Na ZS03 Na2SZ03 ;
(AI Thus, there are 8 S-S bonds and 16 lone pairs.]
Na2S203 + 2AgN03-----t 2NaN0 3 + Ag2S20 3;
(B) 6. Tailing of mercury test can be used for which of the following
Ag2S203 + H20 -----t Ag2S + H2S04 ] gas?
. . -(ah-Dioxygen~-.~.~. ..~~~=.Jb),.O,jh¥4rogea.,.~~~:;::::_ ~=~
2. An organic acid CA) reacts with concentrated H2S04 to give (c) Dinitrogen (d) Ozone
a neutral oxide (B), acidic oxide (C) and a diatomic oxide (D). 7. Which of the following solutions does not.change its~ colour
When (D) reacts with chlorine gas, a poisonous gas (E) is on passing ozone through it ?
evolved. This gas with ammonia gives an organic compound (a) Starch iodide solution
(F). The compounds (A) and (F) are : (b) Alcoholic solution of benzidine
(a) (A) =H 2C 20 4 and (F) =NH 2CONH 2 (c) Acidic solution of K2Cr207
=
(b) (A) CH3COOH and (F) NH 2CONH2 = (d) Acidified solution of FeS04
(c) (A) =CHCl3 and (F) =H 2C 20 4 [Hint : Ozone does not react with acidified solution of
=
(d) (A) ::: CCl4 and (F) CH3CHO K 2 Cr20 7']
[Hint: (COOH)z Cone.H 2S04 ) H20 + C02 + CO 8. A green coloured solution of a salt changes its colour to light
(A) (B) (el (D) pink on passing ozone through it. Which of the following
Neutral Acidic Diatomic species represent pink and green colour respectively ?
oxide
NH3 (a) Mn2+ and Mn02 (b) Mn0 4 and MnO~-
CO+Ch -----t COCl2 -----tNH2CONH2 ]
(EI (F) (c) C02+ and C03+ (d) MnOr and Mn04
Poisonous
[Hint : MnO~- is green while MnO;; is pink. Ozone oxidises
3. Compounds A and B are treated with dilute HCl separately. MnO~- to MnO:;.]
The gases liberated are Yand Z respectively. Yturns acidified
9.· An oxide of a non-metal has the following properties :
K2Cr207 paper green while Z turns lead aCetate paper black.
(i) acts both as a proton donor as well as proron acceptor
The compounds A and B are respectively :
(ii) it reacts readily with basic and acidic oxides
(a) Na2S and Na2S03 (b) Na2S03 and Na2S
(iii) it oxidises Fe at its boiling point.
(c) NaCI and Na2C03 (d) Na2S03 and Na2S04
The oxide is :
[Hint : S02 turns acidified K2Cr207 paper green.
(a) P20S (b) Si02
Na2S03 + H2S04 -----t Na2S04 +S02+ H20
(YI (c) H20 (d) COz
K2CrZ07 + H2S04 + 3S02-----t Cr2 (S04h+ K2S04 + H20 10. Oxygen is more electronegative than sulphur, yet H 2S is acidic
Green
in nature while H 20 is neutral because:
H2S turns lead acetate paper black.
Na2S + H2S04 -----t Na2S04 + H 2S (a) water molecules are associated due to intermolecular
(Z) hydrogen bonding
HzS + Pb(CH3COOh -----t PbS + 2CH3COOH] (b) water has higher boiling point than H2S
4. A yellow coloured crystalline substance gave a colourless (c) H-S is weaker than O-H bond
gas X on reaction with fluorine, which is thermally stable and (d) H2S is a gas at ordinary temperature while H20 is a liquid
has octahedral geometry. X can be : 11. Which of the following are isoelectronic and isostructural?
(a) SF4 (b) S2F2 (a) N0 3, COr (b) S03, N0 3
(c) SF6 (d) S2F6 (c) 003, coj- (d) CO~-, S03
5. The number of lone pairs and the number of S-S bonds in
Sg molecules are respectively:
[Hint : NO)" and COr both have same number of electrons (32 [Hint: The structure of Caro's acid is
electrons) and central atom in each being sp2 hybridized.
o
II
o o HO-S-O-O-H. The hybrid state is sl and its
II II II
S03 40 electrons
/C""- /N~ o
-0 0- -0 0 CI03' == 42 electrons)
StruCture of Structure of O.N. is +6.)
CO~- NO:; 17. Identify the correct sequence of increasing number of
7t-bonds in structures of the following molecules.
12. 03 cannot oxidise :
(i) H 2SZ0 6 (ii) HZS0 3 (iii) H2S20S
(a) KI (b) FeS04
(a) I,IT,m (b) IT,m, I
(c) KMn04 (d) K2Mn04
(c) IT,I,m (d) I,m, IT
13. Which of the following is/are correct ?
(a) 03 + moist iodine~ ID03 o 0
II II
(b) FeCl3 + H 2S ~ colloidal sulphur [Hint. :H2S206,-H-0-S-£~OH- -4rc-bond~----~--·
(c)Oi-+-Ag ~blacksrfver- II II
(d) All o 0
14. A black sulphide when treated with ozone becomes white. o
The white compound is : II
HO-S-OH -one
(c) BaS04 (d) CaS04 o

II
[Hint: PbS PbS04 ) HO-S S OH -3rc-bonds.]
Black White II II
15. . Which of the following is correct structure of SzCl2 ? o o
18. Sulphur reacts with chlorine in I : 2 ratio and forms (X). (X)
(a) S=S
< CI
CI
(b) CI-S-S-Cl on hydrolysis gives a sulphur compound (Y). What is the
hybridized state of central atom in the anion of (Y) ?
(a) sp. (b) sl
(c) (d) Cl=S=S=CI (c) si (d) sl d
[Hint: S + 2Cl 2 ----7 SCI4;
(X)
16. What is the hybrid state and oxidation state of sulphur in
Caro's acid? SCl4 +4H 20----7 S(OH)4 +4HCl
(a) spz, +10 (b) sl,+l0 t
(d) sp3, +6 H ZS0 3+H 20
(c) si, +6 (Y)
The hybridized state of S in (Y) is .lp3.)
1. (a) 2. (a) 3. (b) 4. (c) 5. (b) 6~ (d) 7. (c) 8. (d) 9. (c) . 10. (c) 11. (a) 12. (c)
13. (d) 14. (b) 15. (c) 16. (d) 17. (b) 18. (b)

The following questions consist of two statements as Assertion 1. (A) Tailing of mercury occurs on passing 03 through it.
(A) and Reason (R). Examine the statements and answer the (R) This is due to oxidation of mercury. [A.I.I.M.S. 1999)
questions according to following instnictions: 2 (A) H20 is the only hydride of the chalcogens which is
Mark (a) if both (A) and (R) are correct and (R) is the correct liquid.
explanation of (A) •. (R) In ice, each 0 atom is surrounded by 4H atoms.
Mark (b) if both (A) and (R) are correct but (R) is not the correct 3. (A) Ozone is a powerful oxidising agent in· comparison to
explanation of (A). Oz·
Mark (c) if (A) is correct but (R) is wrong. (R) Ozone is diamagnetic while 02 is paramagnetic.
Mark (d) if (A) is wrong but (R) is correct. [A.I.I.M.S. 2005)
Mark (e) if both (A) and (R) are wrong. 4. (A) SeCl4 does not have a tetrahedral structure.
(R) Se in SeC4 has two lone pairs. . [A.I.I.M.S. 2005)
5. (A) H2S04 forms only one series of salts. 6. (A) S03 acts as an oxidising as well as a reducing agent.
(R) The molecule of H2S04 consistS of only one OH group. (R) S02 acts as an oxidising as well as a reducing agent.
1. (a) 2. (b) 3. (b) 4. (c) 5. (e) 6. (d)
11111111 THOUGFt,. TYPE ·QUESTIONS 11111111

THOUGHT 2
SJ.liphuric_ acid js. consiclered_~ .. th.e1<!Ilg_Qfc.h~.micals. The The binary compounds of oxygen with other elements are called
prosperity of any country is measured by the amount of sulphuric oxides.-They·are-classifle<feither depending upon their acid-base
acid it consumes. Sulphuric acid is, thus, a substance of very great characteristics or on the basis of oxygen content.
commercial importance as it is used practically in every important (a) Normal oxides: These oxides which contain oxygen
industry. This is due to the following properties of sulphuric acid: atoms as permitted by the normal oxidation number, i.e.,
... "--(a)-acidic-nature----- ...... __ -=2. No.rmal...oxideJllay_hfLaddic,_b.aslc. amphoteric or_ _.. _
(b) oxidising nature neutral.· . ' -~--~-
(c) dehydrating nature (b) Polyoxides: The oxides which contain oxygen atoms
(d) sulphonation different than those permitted by the normal oxidation
1. Sulphuric acid has very corrosive action on skin because: number of -2.
(a) it reacts with proteins (i) Peroxides: 1\vo oxygen atoms are linked to each
(b) it acts as an oxidising agent other and each oxygen has -1 oxidation number.
(c) it acts as a dehydrating agent They contain (0-0)2- unit.
(d) it acts as a dehydrating agent and absorption of water is (li) Superoxides: These oxides contain (O-Ofl unit, .
highly exothermic. i.e., each O-atom has oxidation number -1/2.
2. Which of the following reactions depict the. oxidising (e) SUboxides: These contain low content of oxygen than
behaviour of H 2S04? expected.
(a) 2Hl + H2S04 ~ I2 + S02 + 2H20 (d) Mixed oxides: These oxides are made of two simpler
(b) NaCI+H2S04~NaHS04+HCI oxides.
1. Which pair of species is referred to as suboxides ?
(c) 2NaOH + H2S04 ~ Na2S04 + 2H20
(a) CO,NO (b) S02, CaO
(d) 2PCIs + H2S04~ 2POCl3 + 2HCl + S02Cl2 (c) N20, CO (d) N20, C30:z
3. Sulphuric acid is used: 2. Which of the following pairs contains neutral oxides ?
(a) in lead storage batteries (b) in making fertilizers (a) S02,S03 (b) N2~,N20S
(c) in making explosives (d) in all of these (c) CO,NO (d) Na20,CaO
4. The formation of nitroglycerine is done by the use of 3. Which of the following pairs contains mixed oxides?
concentrated nitric acid and concentrated sulphuric acid. The (a) Pb30 4, Fe304 (b) Mn02, Ba02
process of conversion of glycerine into nitroglycerine is (c) K02,Na202 (d) Mn 30 4, N20 S
termed as: 4. Which of the following pairs contains amphoteric oxides?
(a) sulphonation (b) oxidation (a) BeO,BaO (b) BeO,Al203
(c) nitration (d) dehydration (c) Al20 3,P20 S (d) FeO,CuO
5. Only carbon is obtained when concentrated H2S04 is added 5. Which of the following oxides is paramagnetic in nature ? .
to: (a) K02 (b) Ba02
(a) formic acid (b) cane sugar (c) H20 (d) CO:z
(c) oxalic acid (d) ethyl alcohol
6. Concentrated H2S04 cannot be used to prepare RBr or HI THOUGHT 3
from KBr or KI because it:
(a) reacts too slowly with KBr or KI Sulphur and rest of the elements of group 16 are less electro-
(b) reduces RBr or Hl negative than oxygen. Therefore, their atoms cannot take up
(c) oxidises RBr orHI electrons easily. They can acquire ninl configuration by sharing
(d) oxidises KBr to KBr03 or KI to KI0 3 two electrons with the atoms of other elements and thus, exhibit
+2 oxidation state in their compounds. In addition to this, their
atoms have vacant d-orbitals in their valence shell to which (c) act as oxidising as well as reducing agents
electrons can be promoted from the p and s-orbitals of the same (d) cannot be predicted
shell. As a result, they can show +4 and +6 oxidation states. 4. Like sulphur, oxygen does not show +4 and +6 oxidation
1. The oxidation state of sulphur in S8, S03 and H 2S respectively states. The reason is:
are: . (a) that oxygen is a gas while sulphur is a solid
(a) 0, +6 and -2 (b) +2, +6,-2 (b) that oxygen has high ionisation enthalpies in comparison
(c) 0, +4 and +2 (d) -2, +6, +2 to sulphur
2. The oxidation state of sulphur in Na2S406 is: (c) that oxygen has high electron affinity in comparison to
(a) 2/3 (b) 3/2 sulphur
(c) 3/5 (d) 512 (d) that oxygen has no d-orbitals in its valence shell •
3. The nature of the compounds of sulphur having +4 oxidation 5. Oxygen exhibits +2 oxidation state in:
state is: (a) H20 (b)OF2
(a) act as oxidising agents (c) qp (d) H202
_{b)acL~. reduc.ing.agents
--Thought4'--I~(d)---:-2;-(a)-·-- --.3;-(o)~---4:-(C)- ---S:-(bj--6. (cT

Thought 2 1. (d) 2. (c) 3. (a) 4. (b) 5. (a)
Thought 3 1. (a) 2. (d) 3. (c) 4. (d) 5. (b)
The answer to each oj the jollowing questions is a single 4. How many 1t-bonds are present in Marshall's acid?
digit integer, ranging from 0 to 9. 5. Ozone reacts with dry iodine to form an oxide having .....
1. The number of unpaired electrons in the valence shell of the oxygen atoms in its molecule.
members of oxygen family is : 6. How many lone pairs are present in OF2 molecule?
2. What is oxidation state of sulphur in Caro's acid?
3. How many orbitals are involved in the hybridisation of
sulphur in SCI2?
1. (2) Valence shell has six electrons. Out of which two are unpaired.
ns np o 0
111 113
[llJIUltltl 4. (4) HO- S-O-O- S-OH
112 114
o o 0
II 5. (9) 903 + 2h.~ 1409 + 902
2. (6) H O~S+{j~O~O-H
...
II
o
3. (4) sl-hybridisation .
6. (8)
..
:F /
0:
"'....
F:
Group
17 or VilA
1
H
Hydrogen
IS'
12
9
F
~~:. CHAPTER
17
CI
Chlorine
3s'3,1'
35
Br
: Bromine
_45'4,1'
53
I
Iodine I
Elements ofGroupVIIA-or-l'·-
.~~.c
[MJ
lAt-
... _ .. ~_tll\lF·.~······~·····-·-· . _ ..... _._...._ ... _ ..._ ................- ...
(Halogens)
6s's,l'
117
.?
LJ 12.1 POSITION IN PERIODIC TABLE
~ Zero !!
Contents 17th or VIIA group of the periodic VIA .... V1IA
12.1 Position in Periodic Table table (extended form) consists of five . Period . 16 17 18
12.2 Anomalous Behaviour of Fluorine elements; fluorine (F), chlorine (el), - H* He
1 (1) (2)
12.3 Fluorine bromine (Br), iodine (I) and a.statine
(At). This group of five elements 0 F Ne
12.4 Chlorine . 2
forms a family known as halogen (8) (9) (10)
12.5 Bromine S a Ar
12.6 Iodine family as theIr salts are found in sea 3 (16) ( 17) (18)
12.7 Halogen Acids or Hydracids water. Halogen is a Greek word Se Br Kr
meaning a sea salt. Halogens are 4 (34) (35) (36)
12.8 Oxides of Chlorine
p-block elements as the last differen- Te .I Xe
12.9 Oxy-Acids of Chlorine 5
tiating electron is accommodated on (52) (53) (54)
12.10 Interhalogen Compounds
np subshell. These elements have Po At Rn
12.11 Polyhalides 6 I
(84) (85) (86) I
12.12 Basic Properties of Iodine seven electrons in their valency shell
and thus placed in VII group of the ouh Uuo
12.13 Pseudohalides and Pseudohalogens 7
I (116) ( i8) I
periodic table.
Except astatine, the members are found in combined state in considerable quantities in nature. Astatine is unstable element of
radioactive origin. Astatine is radioactive artificially prepared element. These elements possess same electronic configuration and
show similarities as well as gradual gradation in their physical and chemical properties. Thus, the inclusion of these elements
in the same subgroup is justified. However, like other groups, the first element fluorine differs from other elements of the group
in some respects.
~ 1. Electronic Configuration
The electronic configurations of halogens are given as:
Element At. No. Electronic configuration With inert gas core
•
Fluorine 9 2, 7 Ii, 2s 2/ 2
[He) 2i2/
2
Chlorine 17 2,8,7 Ii, 2i 2p6, 3i 3i [Ne] 3s 3/
Bromine 35 2,8, 18,7 Il2i 2l, 3s2 3p6 3dlO , 4i 4/ [Ar] 3d lD , 4i4i
Iodine 53 2, 8, 18, 18, 7 Ii, 2i 2l, 3i 3p6 3dlO, 4s 2 4p6 4d1O, 5i 5/ lO
[Kr] 4d , 5s 5i
2
Astatine 85 2, 8, 18, 32, 18, 7 Ii, 2; 2l, 3i 3p6 3dlO , 4i 4p6 4dlO4f14, 5i 5p6SdlO, 6i 6i [Xe) 4/
4
, 5d iO , 6i6i
I
NQte : The last member of group 17 or VIlA with atomic number 117 (ununseptium) is yet to be discovered.
"Sometimes hydrogen, the lightest element, is also included in group VIlA or 17.
Elements of Group VIIAor 17 (Halogens) 577
All' the halogens have seven electrons (ninp 5) in their Actually, the bond dissociation energy should have decreased
outermost shell. The electrons in np-orbitals are distributed as from fluorine to iodine but it starts decreasing from chlorine
np;, np;, np~. The penultimate shell in F has 2 electrons, in to iodine.
CI 8 electrons and in Br, I and At 18 electrons. This shows why I-I
X-X bond F-F Cl-Cl Br-Br
fluorine differs from chlorine and these two differ from the 267
Bond length (pm) 142 199 228
remaining elements. 151.1
Bond dissociation 158.8 242.6 192.8
Since the halogens have only one electron less than the energy (kJ/mol)
number present in the adjacent noble gas, they have a tendency
to take up one electron to acquire the stable noble gas confi- It has been suggested by Coulson that the lower value of
guration. Hence, the halogens are very reactive elements. bond dissociation energy of fluorine is due to the high inter-
. electronic repulsions between non-bonding electrons in the
II 2. Physical Characteristics 2p-orbitals of fluorine. As a result, F-F bond is weaker in .
comparison to CI~1 and Br-Br bonds. Thus, the bond
. (at])hysicru._state_:~ThLtendenc.y_to_form condensed dissoCiatloii energyIoIlows-fl1e sequence: ----
molecules increases with increase in atomic number. Fluorine
and chlorine are gases at ordinary temperature, bromine is a Cl2 > Br2 > F2 > 12
highly fuming liquid while iodine is a volatile soli~. (e) Ionisation enthalpy: The ionisation enthalpies of
F . .CI . . . .. Br . ... .. I.. . halogensarevery high. This indicates_tha! the !talogenshave . .~_
·~--Giis ···~··~Gas --c to r
Furriln:i liquid-~vcl;tik soHd----- a-little tendency torose electron form cation. However; ---
the ionisation enthalpies decrease from F to I, i.e., the tendency
Halogens exist as diatomic covalent molecules. These to form cation increases from F to I as the size of halogen
molecules are held together by weak van der Waals' forces. increases.
On account of weak intermolecular forces, the halogens
are volatile in nature. With the increase in size, these forces Element F Cl Br I
increase from fluorine to iodine and hence change in physical First ionisation ·1680 1256 1142 1008
)
enthalpy (kJ marl)
state occurs from gas (F2 and Clz) to solid (12), Decreases gradually
(b) Atomic and ionic radii: The halogens have the lowest Iodine. having the lowest value of ionisation potential has
values of atomic radii in their respective periods. This is due some tendency to form 1+ ion as it forms compounds like ICI,
to maximum effective nuclear charge of the halogen in its ICN, etc., which in molten state conduct electricity showing
respective period. However, the atomic radii and ionic. radii the existence of 1+ cation.
(X- ion) increase gradually from fluorine to iodine.
(f) Electron affInity: Electron affinity values are high
Element F Cl Br I in the case of halogens as they have one electron less than the
Atomic radii (pm) 64 99 114 133 nearest noble gas configuration, and have a strong tendency to
Ionic radii (pm) (X) 133 184 196 220
. )
accept an additional electron.
Increase gradually .
Element F Cl Br I
As we move from fluorine to astatine, an extra shell of Electron affmity (eV) -3.6 -3.8 -3.5 -3.2
electrons is added to each element. The addition of an extra The low value of electron aff~ty of fluorine is probably due
shell increases the atomic and ionic radii from fluorine to to small size of fluorine atom, i.e., electron density is high
astatine. The radius of the halide ion is always greater than the which hinders the addition of an extra electron. As we move
corresponding halogen atom. down from chlorine onwar:ds, the electron affinity values
(c) Atomic volume and density: These increase stea- become less and less negative as the size of the halogen
dily from fluorine to iodine. increases. Thus, electron affinity follows the sequence:
Element. F Cl Br
Cl (-349 kJ mor l ) > F (-333 kJ marl) > Br (-325 kJ mor l )
At. volume (roL) 17.1 18.7 23.5 25.7
> I (-296 kJ mor l )
Density (in liquid state) 1.5 1.66 3.19 4.94 (solid)"·
.(g cm-3) at 85 K at 203 K at 273 K at 293 K (g) Electronegativity: The halogens have high values
)
Increase gradually of electronegativities. Fluorine has the maximum electronega-
tivity. The electronegativity decreases from fluorine to iodine.
(d) Energy and stability of X-X bond: With the
. Element F CI Br I
increase of size, the bond length increases from fluorine to
Electronegativity 4.0 3.0 2.8 2.5
iodine. Since the bond length of fluorine is minimum, its bond
dissociation energy should be highest. However, the bond As· a result of the decrease of electronegativity, the non-
dissociation energy of fluorine is less than CI~1 and Br-Br. metallic character decreases from fluorine to iodine. Metallic
cha;aeter is observed in iodine as it forms in a few cases a F atom has no d-orbitals in the valency shell, thus it
positive ion and has a metallic lustre. cannot have any excited state and consequently cannot
(h) Colour: All the halogens are coloured. The colour show any of the higher oxidation states. In the case of
deepens with the rise of atomic number from fluorine to iodine. bromine, the penultimate shell (i.e., 3i3p6 3dlO) is weakly
F CI Br I screening and hence the energy required to promote an electron
Light yellow Yellow green Reddish brown Deep violet from 4s-orbital is higher than in chlorine and thus. bromine
The colour is due to does not show +7 oxidation state.
the absorption of energy Besides +3, +5 and +7 oxidation states, +4 and +6 oxidation
from visible light by states are also shown by these elements in oxides and oxyacids.
their molecules for exci- Examples:
tation of outer electrons
to higher energy levels. Oxidation
Fluorine Chlorine Bromine Iodine
Fluorine absorbs violet state
portion oLtheJightand -1 NaP,OF2L NaCl,.,MgCI2, NaBr, CaBr2,L Nal, AgI,
thus appears yellow ClF 3,IFs AgCl, HCI AgBr, HBr HI, CaI2
while iodine absorbs +1 x HCIO, CI20 HBrO, Br20 HIO,ICI
yellow and green +3 x ClF3, HCl0 2 BrF3 ICI 3
portions of the light and +4 x CI0 2 Br02 120 4
r---tnus appears vlolet~-·-~--.-.€olour-of-Halogens-c--·-.·-·--- - - - , , " 5 - - - : : -:--x----c- -Het03 - - -HBr0:r,-BrFs -HI0~,--_ ....
Change in colour on (a) Colour of Chlorine (CI2}-Yello~ green . +6 x CI 20 6 Br03 x

. . (b) Colour of Bromme (Br2}-Reddlsh brown
movmg down thIS (c) Iodine (I2)-Deep violet +7 x HCI0 4 x HI0 4, IF7
group is called blue shift Fig. 12.1 (j) Reduction potentials and oxidising nature: Stan-
or bathochromic shift.
dard reduction potentials of halogens are positive and decrease
(i) Oxidation states: Since these elements have seven
from fluorine to iodine. Thus, halogens act as strong oxidising
electrons in their'valency shell, each element tries to attain 8 agents and their oxidising power decreases from fluorine to
electrons either by accepting an electron from an element iodine.
which is less electronegative than it or by sharing its unpaired
electron in p-orbital with another element. When the halogen Element F CI Br I
Reduction potential
atom combines with an element of lesser electronegativity,
it shows -1 oxidation state. On the other hand, when it (E' volt) +2.87 + 1.36 +1.09. +0.54
combines with an element having higher electronegativity, Decreases gradually
it exhibits +1 oxidation state. Fluorine, being the most Oxidising nature also decreases
electronegative, always shows -1 oxidation state only.
Chlorine, bromine and iodine show positive oxidation states The strength of an oxidising agent depends on several energy
as the electrons in the valency shell can be promoted to vacant terms as shown below:
d-orbitals. These elements (i.e., CI, Br and I) can show +3, +5 1 ~heatof 1 ~heatof
and +7 oxidation states depending on the number of singly -2 X2 (solid) ------='---~) 2 X2 (liq. ) ------='---~
. fusion evaporation
occupied orbitals, i.e., oxidation states lie between -1 to +7.
ns np nd
1 ~heatof
-2 X2(gas) ) X (gas)
Halogen atom
(except F atom) in
[TIll i ,LIt11 i I<--I-'--'----'---'-----'
"-v----------' oxid.
dissociation
Electronl
the ground state. potential affinity
1 unpaired electron; -1 or + 1 l
(ns 2np s) oxidation state
ns np nd X-(h d.) (Heat~f X-(gas)
y hydratIOn
Halogen atom in the [ITllnlll ill I I I
'I'
first excited state.
(ninp4nd l )
E = 2:1 H f + 2:1 Hev + 2:1 Hd - electron affinity - H hyd .
3 unpaired electrons; +3 oxidation state
ns np nd The E values decreases from fluorine to iodine.
Halogen atom in the
second excited state.
[Ill Ii 11' Ii I,--,i.-IL:.1i-,---I
--'----L-----'
Fluorine is the strongest oxidising agent. It will oxidise other
halide ions to halogens in solution or when dry.
(ns2np3nd2) 5 unpaired electrons; +5 oxidation state
ns I1p I1d
F2 + 2X- -----7 2F + X2
(X- = CC Br- or 1-)
Halogen atom' in the [[Ilililillililil Similarly, chlorine will oxidise Br- and 1- solution to Br2 and
third excited state.
(nslnp3nd3) 7 unpaired electrons; +7 oxidation state 12, respectively and Br2 will oxidise 1- to 12, In general, a
Elements O'f Group VIIA O'r 17 (Halogens)
halogen of low atomic number will oxidise the halide ion slowly. BrO'mine and iodine dO' not react with nO'ble metals like
of higher atomic number. Au, Pt and even with less active metals.
The halide ions act as reducing agents. F- iO'n does not Halogens also combine with a number of non-metals like S,
show any reducing nature but CC Br-and 1- iO'n act as P, As, etc. The reactivity decreases frO'm fluO'rine to' chlorine.
reducing agents and their reducing nature is in increl;lsing order. FO'r example, sulphur fO'rms hexafluO'ride with fluO'rine (SF6),
cr Br- r tetrachloride with chlO'rine (SCI4) and dibromide with bromine
Reducing nature increases (SBr2) and there is no reaction between sulphur and iO'dine.
(iii) Reaction with hydroearbons : FluO'rine brings
(k) Solubility: Halogens, being nO'n-polar mO'lecules, do decompositiO'n of the hydrocarbon and alsO' forms fluorinated
nO't dissO'lve to a cO'nsiderable extent in a PO'lar sO'lvent like
products readily.
water. However, fluO'rine reacts with water readily forming a CH + 2F2 - - 7 . C + 4HF
4
mixture O'f O'xygen and ozone. Chlorine and bromine give substitutiO'n reactiO'ns. The rates
2F2 + 2H20 - - 7 4HF + 02 Qf t.eac~tionswithbromine areslow.~-Iodine~as-practically-no-.~
3F2 +~~3H20--~~) 6HF +O::f H
actiO'n O'n hydrO'carbO'ns.

C1 2, Br2 and 12 are mO're sO'luble in organic sO'lvents such as
Cl Cl2
CC4, CHCI3, paraffins and prO'duce coloured solutions. Chlorine, C~ + Cl 2 - - 7 CH3Cl CH2Cl2 - -27 CHCl3~ CC4
brO'mine and iO'dine give yellO'w, brO'wn and viO'let CO'IO'ur'(b) Hydrides of the baiogeQS(llydrogea halides):
respectively, in chlO'roform or carbon tetr~(;hlO'ride. It iSl:>~li~yed ~--Al1-th~alogenneacrwitlrnyOrogent6roffiCvolat1IecO'vi.iIeilF'=c:c-
.. -Tliafin nO'n-polarsolvents halO'gens exist as free molecules.
hydrides O'f fO'rn:lUla HX. These hydrides are called hydracids.
In nucleO'philic sO'lvents like alcO'hols, ketO'nes, liquid sulphur The activity O'f halO'gens tO'wards hydrO'gen decreases from
diO'xide, halO'gens produce brO'wn solutiO'ns. It is due to cO'mplex fluorine to iO'dine. .
formation (solvent ~ haIO'gen).
Hydrogen combines explosively with fluO'rine even in dark-It
II 3. Chemical Characteristics combines with chlorine in presence O'f sunlight and with bromine
(a) Reactivity: Halogens are mO'st reactive nO'n-metallic O'n heating. Hydrogen cO'mbines with iO'dine O'n heating and in
elements, high reactivity is due to' low diSsO'ciatiO'n energies O'f presence O'f a catalyst. The reactiO'n with iodine is rev.ersible
the halO'gen mO'lecules and high electron affinities. and incO'mplete. Detailed discussiO'n is given in sectiO'n 12.7.
(c) Oxides: The compounds O'f O'xygen and fluO'rine are
Molecule N2 O2 H2 X2 (halogen)
Dissociation energy 225 118.3 103.2 35.5 to 57.2 not called as oxides but O'xygen fluO'rides as fluorine is more
(kcalJmo1) electrO'negative than oxygen. The cO'mpO'unds of O'xygen and
In halO'gens, fluO'rine is mO'st reactive and iodine is least rest of the halO'gens are termed O'xides. Halogens and O'xygen dO'
reactive. nO't cO'mbine directly with each O'ther. HO'wever, these compounds
This is due to following factors: have been O'btained indirectly. The knO'wn cO'mpO'unds are:
(i) As the size increases, the attraction fO'r an additional OP2 . el20 Br20 'lids
electrO'n by the nucleus becO'mes less. Thus, reactivity decreases. 02Fi Cl02 BrOz' ...
(ii) Due to decrease in electrO'negativity from F to I, the Cl20 6 . Br03
bond between halogen and other elements becO'mes weaker Cl20 7 :
and weaker. Fluorides are mO'st stable while iO'dides are least. In these O'xides, bO'nds are mainly cO'valent due to' small
(iii) DissO'ciation energies of X-X bO'nds are lO'w. difference in the electrO'negativity O'f oxygen and the halO'gens.
The fO'llowing reactiO'ns illustrate the relative reactivity O'f Oxygen fluorides dO' nO't fO'rm O'xyacids. Oxides O'f chlO'rine are
halogens. acidic and the acidic nature increases as % O'f O'xygen increases.
(i) Reaction towards water: Fluorine decO'mpO'ses water Thus, Cl20 is least acidic while Cl 20 7 is most acidic oxide.
very readily even at IO'W temperature and in dark fO'rming Cl20 + H20;;::=:: 2HClO
mixture O'f O2 and 03, Cl2 decompO'ses water in presence O'f 2CI02 + H20 - - 7 HCI02 + HCI03
sunlight while bromine decompO'ses water very slowly in
Cl206 + H20 - - 7 HCI03 + HCI0 4
presence O'f sunlight. Iodine dO'es nO't decO'mpose water.
Cl20 7 + H20 - - 7 2HCI04
X +H 0 Sunlight) HX + HXO The O'xides O'f brO'mine and iO'dine are alsO' acidic in nature.
2 2
(C12 or Br2) All the three mO'noxides, viz., OF2, Cl20 and Br20 have
3F2 + 3H20 - - 7 6HF + 0 3 tetrahedral structure invO'lving sp3 hybridization O'f O'xygen;
2F2 + 2H20 - - 7 4HF + O2 bO'nd angle increases with increase in size of halO'gen atO'm.
12 + H20 - - 7 NO' reaction •• •• ••
(li) Reaction with metals and non·metals: Nearly all
. 0: 0: 0:
metals cO'mbine with fluO'rine either in cold O'r on heating forming /ioAF /ioACI ~~
F CI Br Br
fluO'rides. ChlO'rine combines with large number O'f metals but
I
Fig. 12.2
(d) Oxyaclds: Fluorine does not form any oxyacid as it is more electronegative than oxygen. Other ~alogen~ form oxyaci~s
of the type HXO, HX0 2, HX0 3 and HX04 . Some of the acids are quite unstable and are known only m solutlOns or as theIr
salts. List of oxyacids is given below:
Oxidation number
Oxyacids of !
! General name Acidity Stability Oxidising nature
of halogen Cl Br I
+1 HCIO HBrO HIO Hypo-halous
+3
+5
HCI02
HCI0 3 HBr03
- -
HI0 3
Halous
Halic
11 l~] 1J
+7 HCI0 4 I HI04 (H sI06) . Perhalic I
-- Acidity~decreases_=-t ..... .
Note: Greater is the oxidation state of central balogen atom more will be the acidic character.
General properties 6NaOH + 3X2 ---7 5NaX +NaX0 3 + 3H20

Hot and cone. Halide Halate
(inn oxyacids, the hydrogen is a part of an -OH group
,~-- arid -notdifedl5i attacnedio'th'tnialogen atom:-'Tlleoxyacfds--
6NaOH ± - 31...2--_~
. ~.~.--~--~- . 5N~..±_
. . . . . NaI03
',' + 3H2Q . _~ . . ~
...~._'~_
Sod. iodide Sod. iodate
are monobasic and form one series of salts.
(f) Interhalogen compounds: The halogens on account
(ii) In oxyacids of the same halogen in different oxidation
of difference in their electronegativities combine with each
states, the acidic nature and thermal stability increase while
other to form compounds of type ABn where A is always
oxidising nature decreases with the increase of oxidationstate
bigger atom and B is smaller atom and 'n' may have values 1,
of the halogen. For example, for the four oxyacids of chlorine,
3, 5 and 7. These are covalent compounds and called inter-
the acidic character and thermal stability 'are in the order:
halogen compounds. TOe value of 'n' increases with the increase
HCIO < HCI0 2 < HCI0 3 < HCI04 of size of halogen A. Maximum value of 'n' for chlorine is 3,
while the oxidising power is in the order: for bromine 5 and for iodine 7. The known interhalogen
HCIO > HCI0 2 > HCI0 3 > HCI04 compounds are listed below:
i.e., increasing oxygen content leads to : AB type ClF, BrF, BrCI, ICI, ffir
(a) an increase in thermal stability AB3 type ClF3, BrF3, ICl3
(b) an increase in strength of the acid AB5 type lF5' BrF5
(c) a decrease in oxidising power. AB7 type IF7
(iii) In the oxyacids of different halogens in the same oxidation
state, the thermal stability and acidic nature, in general,decrease The interhalogen compounds are gases or liquids. These are
with increase of atomic number. However, in HX0 3, HI03 is volatile and fume in air. In general, these compounds are more
most stable. reactive than pure halogens except fluorine because
(e) Reaction with alkalies: Fluorine reacts with cold A-B bond is weaker than B-B bond. These are hydrolysed
dilute alkalies yielding OF2 (oxygen difluoride) and with conc. and act as oxidising agents. The compounds of iodine and
alkalies evolve oxygen. fluorine ate thermally more stable while the compounds of
iodine and chlorine or iodine and bromine are less stable.
2NaOH + 2F2 ---7 2NaF + OF2 + H20
(Cold and dilute)
12*11 ANOMALOUS BEHAVIOUR OF
4NaOH + n~ FLUORINE
(Cone.)
Fluorine differs from other members of its own sub-group due
C1 2, Br2 and 12 behave similarly but differently than fluorine, to the following reasons:
with cold dilute alkalies, they form a mixture of halide and (i) Small size of the atom in comparison to the sizes of CI,
hypohalite and with concentrated hot alkalies a mixture of Br and I atoms.
halide and halate. (ii) Highest electronegativity.
2NaOH + X2 ---7 NaX + NaXO + H20 (iii) Absence of d-orbitals in its valency shell.
Cold and dilute Halide Hypohalite
(iv) Highest positive reduction potential.
2NaOH + Cl 2 ---7 NaCI + NaCIO + H20 The main points of difference are:
Sodium Sodium (1) Fluorine shows only a negative oxidation state of -1 due
chloride hypochlorite
to maximum value of electronegativity. It never shows any
Elements of Group VilA or 17 (Halogens) 581
positive oxidation state. The other halogens show negative as 1 FLUORINE
well as positive oxidation states, i.e., between -1 and +7.
(2) Fluorine is most·reactive as bond dissociation energy of Occurrence: Fluorine is extremely reactive and, hence does
F-F bond is low. X-:-X bond is stronger in Cl2 and Br2. not occur in free state. It is widely found in the combined state
(3) Maximum covalency of fluorine is one as there is no d- as fluorides. The important minerals are:
orbital in its valency shelL Other members can have maximum (i) Fluorspar (Fluorite) CaF2
covalency of 7 because of vacant d-orbitals. (ii) Cryolite Na3AlF6
(4) HF is a weak acid in comparison to HCI, HBr and ill
(iii) Fluorapatite CaF2·3Ca3(P04h
under similar circumstances. HF is a liquid (b.pe 19°C) while
HCI, HBr and HI are gases under ordinary conditions. This is It is present in small amount as fluorides in plant-ashes, soil,
due to presence of hydrogen bonding in HF while hydrogen sea water, bones and teeth of animals. It constitutes nearly
bonding is not present in HCI, HBr and HI. 0.054% of earth's crust.
(5j~Hydrofluoric-acid~isa-dib1[slc-acld-(H2F2rWhileHCI, Isolatton~:~ -Fluonne~presented-man:y~ ·oiIficultiesin~
HBr and HI are monobasic in nature. Thus, hydrofluoric acid isolation. It remained a difficult problem in chemistry for many
forms two series of salts such as NaHF2, Na2F2. Most of the years and after a hard labour of many chemists for about 75
fluorides are ionic. These contain F- ion while other halides years it coul4 be isolated finally by Moissan in 1886. The
_______ J1:ave frequen~!y molecular latti~es.~~~_. _.~. .___. ccc:-~~1e~()p.s..JQPts-late-Aiscov.e.ry-wenhits-hlghcFeactivity7.and~-
(6) AgF is soluble in water while AgCl, AgBr and AgI are non-conducting nature ofhydrotluoric acid. Fluorine attacked
insoluble in water. Similarly, calcium fluoride is insoluble and the material of the vessels used for its isolation. Carbon vessel
other halides of calcium are soluble. was attacked with formation of CF4 and platinum vessel was
(7) Fluorine combines with sulphur to form SF6 but no reduced to chocolate powder. The vessels of other metals
other halogen forms the hexahalide with sulphur. were also affected. The platim,lm and carbon could not be used
(8) Fluorine does not ~orm any oxyacid but other halogens as electrodes. Another difficulty experienced was that when
form a nu~ber of oxy.aclds. . . the electrolysis of aqueous hydrofluoric acid was carried out,
(9) It directly combmes Wl~ carb~~ while other halogens hydrogen and oxygen (ozone) were obtained and when
do not react even under drastlc condItIOns. anhydrous hydrofluoric acid was tried it was found to be a bad
(10) Ozone . is formed when fluorine decomposes . conduc tor 0. f e1ec tn"t
Cl y.
water. Ozone IS not formed when other halogens react WIth M . fi all I ed h bl d' 1 d fl . b
water. Olssan III y so v t e pro em an ISO ate uonne y
(11) Fluorine does not form any oxysalt when it reacts with the electrolysis of anhydrous hydrofluoric acid in the presence
alkalies while other halogens form oxysalts with alkalies. of potassium hydrogen fluoride using Pt-Ir alloy vessel at
(12) Fluorides are more stable than corresponding chlorine -23°C, The electrodes used were also of Pt-Ir alloy.
compounds. For example, UF6 is more stable than UCI6. NF3 Modern methods of isolation: In modern methods,
is non-explosive while NCl 3 is highly explosive. fluorine is prepared by electrolysis of a fused fluoride (usually
(13) The fluoride ion has a great tendency to form complex potassium hydrogen fluoride, KHF2)· The electrolytic cells are
ions, e.g., [AlF6]3-, [FeF6]3-. The remaining halide ions show made of copper, nickel or monel metaL The anode is generally
this tendency to a much lesser extent. of graphite and the fluorine set free contains some carbon
(14) Fluorine does not have vacant d-orbital in valence shell tetrafluoride.
therefore it does not combine with F ion to form polyfluoride Reactions in the electrolytic cell
ions like CI3", Br3", 13". IS, etc. KHF2 ~ KF + HF
Similarities between oxygen and fluorine: ,Il
1. Atomic and ionic radii of both elements are very similar. K++F
2. Both exist in gase.ous stat~ at room temperature.
3. Hydrides of both elements form associated species due Cathode / ~ Anode
to hydrogen bond formation. K++ e ~ K
K+HF~KF+H
(HF)x , (H 20)x 2H ~ H2
4. Hydrides of both elements have abnormally high b.pts. The precautions given ahead should be taken in the
5. Hydrides of both elements are ionizing solvents. preparation of fluorine :
582 GR.B. 1i10rganic Chelnistry for Competitions
(i) The electrolyte must be completely dry. In presence of KCI0 3 + F2 + H20 ~ KCI04 + H2F2
moisture, the evolved fluorine reacts with moisture to form O2 KI03 + F2 + H20 ~ KI04 + H2F2
and 0 3,
2NaHS04 + F2 ~ Na2S20g + 2HF
.(H) The parts of the apparatus which come in contact with
fluorine must be free from oil and greese. (vi) It attacks glass at about 100°C fonning SiF4, However,
(iii) The vessel in which fluorine is collected should also be the attack of dry fluorine is slow. At low temperatures, dry
absolutely dry. fluorine can be stored in dry glass vessel.
. (iv) The gas must be made free from HF before storing by (vii) It reacts with hydrocarbons explosively and forms
passing through sodium fluoride (NaF) otherwise HF will attack fluorinated hydrocarbons.
vessel.
F2 F2 F2
[Note: HF is more corrosive and reactive than fluorine.] CH4 CH3F CH2F2 CHF3 CF4
The electrolytic cells used are : Fluorine reacts with NH3 to form nitrogen and H 2S forming
Ca) Dennis-ceUs-and-(b)-Whytlaw::Gray-cell - - - - - SF - (HiS-burns).- -_. . . . . . . . . . . . . ._ -
6
2NH3 + 3F2 ~ N2 + 6HF
II Properties
H2S + 4F2 ~ SF6 + 2HF
. (a) The gas is pale greenish yellow in colour. It can be ... ..
,------€ondens@d-to-yelww..Jiquid-at-188.<:C-and-pale-yeHowsolid-'8.t----___~Vlll) It ~ombmes wIth xenon to form XeFb XeF4 and
-223°C. (b) It has pungent odour resembling that of a mixture Xe~6TSee l~ert. gases).
of ozone and chlorine. (c) It is a poisonous gas but less (IX) FluonnatlOn of methanol.
poisonous than HF gas. (d) It is the most reactive element. AgF2
(i) It can displace all the halogens from their halides. CH30H + 4F2 ~CF30F + 4HF
F2 + 2NaX ~ 2NaF + X CF30F is very strong oxidising agent.
2
=(X CC Br- or Il (X2= CIl- Br2 or 12)
Ii Uses
(ii) It combines with most of the metals and non-metals to
form fluorides. 1. It is used as an insecticide.
2Ag + F2 ~ 2AgF 2. It is extensively used for the preparation of various fluorine
2Al + 3F2 ~ 2AlF3 compounds which have wide applications.
(a) Freon, CCl2F 2 (dichloro difluoro methane), is used in
Mg+F2~MgF2
refrigerators and cold storage plants.
Hydrogen explodes violently in fluorine even in the dark.
(b) Teflon (C2F4)x, a new plastic, has a very high electrical
H2+F2~ H2F2
resistance and is used as insulating material in cables. Teflon
A mixture of oxygen and fluorine explodes in presence of is not affected by acids, alkalies and strong oxidising agents.
silent electric discharge. (c) H2F2 is used for etching of glass and for removing silica
O2 + F2 ~ 02F2 (Dioxygen difluoride) from iron castings.
It reacts with wood charcoal, phosphorus, arsenic, antimony,
boron, silicon producing a flame. Si02 + 2H2F2 ~ SiF4 + 2H20
235
C+2F2 ---:; CF4 Si + 2F2 ~ SiF4 (d) UF6 is used in the separation of U from natural
2P + 3F2 ~ 2PF3 ; 2As + 3F2 ~ 2AsF3 uranium by diffusion method.
2B + 3F2~ 2BF3 . (e) SF6 has insulating properties. It is used in X-ray and
However, fluorine does not react with oxygen, nitrogen and high voltage machines.
inert gases directly under ordinary conditions. (f) Sodium fluoroacetate is used as a rat poison.
(g) NaF and Na3AlF6 (cryolite) are used as insecticides.
(iii) Fluorine reacts vigorously with water giving O2 and
(h) CuF2 is used in the ceramic industry and as a flux in
0 3,
soldering, welding and glazing.
2H20 + 2F2 ~ -4HF + 02 .
3H20 + 3F2 ~ 6HF + 0 3 CHLOR1NE
(iv) Fluorine reacts with dilute alkalies to form oxygen
difluoride (OF~ and with conc. alkalies O2 is formed. Chlorine was discovered by Scheele in 1774 by the action of
2F2 + 2NaOH ~ OF2 + 2NaF + H 20 HCl on Mn02. Berthollet named this gas oxymuriatic acid gas
since he thought it to be an oxide of muratic acid (old name
2F2 + 4NaOH ~ 4NaF + 2H20 + O2
of HCl). In 1810, Davy established its elementary nature and
(v) It acts as a strong oxidising agent. It oxidises chlorates named it chlorine on account of its greenish yellow colour
to perchlorates, iodates to periodates and bisulphates to peroxy- (Greek, chloros = greenish yellow).
sulphates.
Elements of Group VIlA or 17 (Halogens) 583
Occurrence: Chlorine is widely distributed in nature in (i) By the Action of HCI on Mn02
the combined state in the form of chlorides of various metals.
The common method of preparing chlorine in the laboratory
Common salt (NaCI) is the most important chloride which
is by heating concentrated hydrochloric acid with manganese
occurs in sea water, lakes and in r5'cks. The other important
dioxide in a round-bottom flask fitted with a thistle funnel and
chloride minerals are:
a delivery tube (Fig. 12.3).
(i) Sylvite (potassium chloride), KCI
Mn02 + 4HCI ~ MnCl 2 + Clz + 2H20
(ii) Carnallite, KCl, MgC12·6H20
(iii) Chlorapatite, 3Ca3(P04h·CaCI2
(iv) Hom silver, AgCl
Preparation: (i) By the oxidation of hydrochloric
.. acid. The oxidising agents which can be used are Mn02,
Pb02, Pb 30 4 (red lead), KMn04 (Potassium permanganate),
K 2Cri()7(PotassiumdiCltr<ffuate);·NaCrO (SOdi1.lmhYpo-
chlorite), 0 3, etc.
(a) Mn02 + 2HCI ~ MnCl2 + H 20 + 0
2HCI + 0 ~ H20 + Cl2
(b) Pb0 2 + 4HCl~ PbCl2 + 2H20 + Cl2

(c) Pb 30 4 + 6HCl ~ 3PbCl2 + 3H20 + 0
2HCI + 0 ~ H 20 + C12 Fig 12.3
Pb 30 4 + 8HCl ~ 3PbCl2 + 4H20 + Cl2
Small quantity of Mn02 is taken in the flask. Concentrated
(d) 2KMn04 + 6HCI ~ 2KCI + 2MnCl2 + 3H20 + 5[0] HCI is so adjusted that the end of the thistle funnel remains
WHCI + 50 ~ 5H20 + 5Cl2 dipped in it. The contents are heated slowly. The yellowish
green gas is evolved. The gas is usually contaminated with
2KMn04 + 16HCI ~ 2KCI + 2MnCl2 + 8H20+5C12 water vapours and HCl gas. The evolved gas is first passed
(e) K2Cr207 + 8HCI ~ 2KCI
+ 2CrCl3 + 4H20 + 3[0] through water (to remove HCI gas) and then through cone.
H2S04 (to remove water' vapours). The chlorine is finally
6HCI + 30 ~ 3H20 + 3Cl2
collected in a jar by upward displacement of air.
II (ii) By the Action of HCI on KMn04

(f) NaClO ~ NaCI +0
2HCl + 0 ~ H20 + Cl2 This is a convenient method to prepare chlorine in the
laboratory. It consists the addition of cold concentrated HCI on
NaCIO:+ 2HCl ~ NaCI + H20 + Cl2 potassium permanganate crystals.
(g) . 0 3 + 2HCl - : O2 + H20 + Cl2 2KMn04 + 16HCI ~ 2KCI + 2MnCl2 + 8H20 + 3Clz
(ii) By the action of mineral acids or carbon dioxide on The apparatus used is shown in Fig. 12.4.
bleaching powder.
CaOCl2 + H2S04 ~ CaS04 + H20 + Cl2
CaOCl2 + 2HCl ~ CaCl2 + H20 + Cl2
CaOCl2 + CO2 ~ CaC03 + Cl2
(iii) By heating any chloride with concentrated H2S04 in
presence of Mn02' .
Mn02 + H 2S04 ~ MnS04 + H 20 + 0
[NaCl + H 2S04 ~ NaHS04 + HCI] x 2
2HCI + 0 ~ H20 + C12
Fig. 12.4
2NaCI + Mn02 +3H 2S04---7 2NaHS04+MnS04+2H20+ Cl2 A small quantity of potassium perinanganate is placed in the
Laboratory preparation: The following methods are flat-bottom flask fitted with a dropping funnel and a delivery
used in the laboratory for the preparation of chlorine: tube. HCI is added drop by drop from the dropping funnel. A
brisk reaction occurs and yellowish-green gas is evolved. It is 2CU2Cl2 + 02(Air) ---1 2CU20Cl2
passed through water and conc. H2S04 and finally, dry and Copper oxychloride
pure chlorine is collected in a jar by upward displacement. CU20Cl2

, + 2HCI 2CuC12 + H20
Pure chlorine: It may be obtained by heating dry platinic The cycle' is then repeated, the gaseous products being
chloride(PtCI4) or gold chloride (AuCI 3) in a hard glass tube. steam and chlorine.
PtCl4 -~ PtCl2 + Cl2 S82°C )Pt + 2C12 The mixtur~ of air and hydrochloric acid, preheated to 220°C,
is introduced into a chamber containing a shelves
I8SOC on which is placed pumice stone soaked in chloride
2AuCl3 ..:;;..:..::...~2AuCl + 2C12~ 2Au + 3Cl2
. . 1 ~ solution in HCI. This chamber is surrounded
Manufactqre: Bulk of chlorine required for commercial which hot gases at 450°C are passed.
purposes is obtained as a by-product in, the manufacture of
caustic soda by electrll>lysis of brine solution or in the manu-
fac_tureoLsQdium_b_y_IJ:~lektr.Ql)'sis_Qf _fuKed_sodium chlQride.
These processes have: already been described in Chapter 6
under caustic soda and sodium. Air
Catalyst
The other methods used for its manufacture are: pumice stone
(i) Weldon's process + Cu2 C12
(ill) Nitrosyl chloride process

These chemical methods are bit costlier and only the nitrosyl
chloride process is used these days to manufacture chlorine.
Hot
II (i) Weldon's Process
Cooling
This process involves the heating of pyrolusite mineral chamber
(Mn02) with concentrated hydrochloric acid in stone-ware Fig. 12.5
stills. .
Mn0 2 + 4HCI ---1 MnCl2 + 2H20 + Cl2 The gaseous mixture which escapes from the top of the
The manganese chloride present in the waste liquor is catalyst chamber consists C12, HCI, air and steam. It is freed
converted into a product which can be used instead of fresh from HCI by washing it with water in the washing tower and
pyrolusite for oxidising more of hydrochloric acid. The man- then dried by passing through the drying tower packed with
ganese chloride solution is mixed with excess of lime and air pieces of flint and concentrated H2S04 flows down from the
is blown in the heated mixture. The following changes occur: top. Finally, dry mixture 'of chlorine and air is obtained.
MnCl2 + Ca(OH)z ---1 Mn(OH)2 + CaC12 III: (iii) .NltrosyiChloride Process

2Mn(OH)2 + 02 (Air) ---1 2Mn02 + 2H20
In this process, common salt (NaCI) is treated with
Mn02 + Ca(OHh ---1 CaMn03 + H20 concentrated nitric acid, when a mixture of chlorine and nitrosyl
Calcium manganite
chloride is evolved.
Calcium manganite settles down to the bottom as a dark [NaCI + HN0 3 ---1 NaN03 + HCll x 3
coloured mud. This is used for oxidation of fresh quantities of
HN03 + 3HCI ---1 NOCI + Cl2 + 2H20
hydrochloric acid.
CaMn03 + 6HCI ~ CaCl2 + MnCl 2 + Cl2 + 3H20 3NaCI + 4HN0 3 ---1 3NaN03 + NOCl + C12+2H20
The gaseous mixture is oxidised with oxygen .
• (ii) Deacon's Process 2NOCI + 02 ---1 2N02 + Cl2
This process is superior to Weldon's pr?fess. In this process, The gases are liquefied and chlorine distilled out. Nitrogen
chlorine is ob~ned by the oxidation of HC\with air in presence dioxide is absorbed in water in presence of oxygen to form
of cupric chloride heated to 400°C. \ nitric acid which can be used again.
, CuCI ~
4HCI + 02 4000~ ) 2Cl2 + 2H 20 4N02 + O2 + 2H20~ 4HN03
Storage and transportation of chlorine: Chlorine is
The catalytic action of cupric chloride can be explained stored and transported in the liquid state. The liquid is stored
with the following mechanism. in large steel tanks which are kept in heat-insulated cold storage
2CuCl2 High temp. ) Cu2Cl2 + Cl2 rooms.
Elements of Group VIlA or 17 (Halogens) 585-
II Properties of Chlorine . 1. When ammonia in excess: The products are nitrogen
and ammonium chloride.
Physical: (a) Chlorine is a yellowish green gas with a
2NH3 + 3Cl2 ----7 N2 + 6HCI
pungent suffocating smell. (b) It is heavier than air and oxygen.
It is 2.S times heavier than air. (c) It is poisonous in nature. It [NH3 + HCI ----7 NH4Cl] x 6
produces headache if inhaled in small quantity. It affects throat, 8NH 3 + 3Cl2 ----7 N2 + 6N:H4CI
nose and lungs. Large quantities prove fatal. 2. When chlorine in excess: The products are nitrogen
(d) It can be easily liquefied by cooling under pressure. The trichloride and HCl.
liquid chlorine is a yellow liquid (b.pt. -:-34.6°C). (e) It is fairly NH3 + 3Cl2 ----7 NCl3 + 3HCI
soluble in water. The aqueous solution is called chlorine water. (iv) It removes hydrogen from H 2S.
It has yellow colour and smells of chlorine. At O°C, crystals H 2S + Ch ----7 2HCI + S
of chlorine hydrate C12·8H20 are formed. . (d) Oxidising and bleaching nature: In presence of
Chemical: (a) Combustibility: Chlorine does not bum moisture, _chlorine_actsJis_an_oxidising_and_a_bleaching_age~~
aildalsodoes nofheIpin-buming.-- Chlorine reacts with water forming HCI and HCIO (hypo-
(b) Combination with elements: It combines with all chlorous acid). -HCIO is not so stable and decomposes giving
the non-metals except nitrogen, oxygen, carbon and inert gases. nascent oxygen which is responsible for oxidising and bleaching
It combines with hydrogen in light (but not in dark) with properties of chlorine. .
- - :-explosiontoJon:nllCl--How-ffi1er.-in-presence-Of..cbar£'oal-as-a-~-. .. .... . eli + H 0 -rnCf+HCRJ
2
catalyst, the reaction is safe. HOO ----7 HCI + 0
H2 + Cl2 ---72HCI
Arsenic, boron, sulphur, phosphorus (red), etc., combine CI 2+H 20 ---7 2HCI + 0
with chlorine when heated. Coloured matter + Nascent oxygen ----7 Colourless matter
2As + 3Ch ----7 2AsCl3 The bleaching action is permanent. The delicate articles
Arsenic trichloride should not be bleached with chlorine.
2B + 3Cl2 ---7 2BCl3 1. It displaces bromine and iodine from bromides and iodides .
Boron trichloride respectively.
2S + Cl2 ---7 S2Cl2 2KBr + Cl2 ----7 2KCI + Br2
Disulphur dichloride 2KI + Cl2 ----7 2KCI + 12
2P + 3Cl2 ---7 2PCl3 2. Ferrous chloride/ferrous sulphate containing dilute H 2S04,
(Red) Phosphorus trichloride is converted to ferric chloride/ferric sulphate.
Yellow phosphorus readily catches fire in chlorine. Most of 2FeClz + Cl2 ----7 2FeC13
the metals directly react with chlorine to form corresponding 2FeS04 + H2S04 + Cl 2 ----7 Fe2(S04h + 2HCI
chlorides. Alkali metals bum brilliantly in chlorine. Iron, copper, 3. Moist sulphur dioxide is oxidised to H 2S04,
aluminium, magnesium, zinc, etc., when heated in chlorine S02 + 2H 20 + Cl2 ----7 H 2S04 + 2HCI
form corresponding chlorides. A trace .of moisture always 4. Sulphites are oxidised to sulphates.
catalyse the reaction.
Na2S03 + H20 + Cl 2 ----7 Na2S04 + 2HCI
2Na + Cl2 ----7 2NaCI 2Fe + 3Ch ---7 2FeCl3
S. Sulphur is precipitated· from sodium thiosulphate.
2AI + 3C12----7 2AICl3 Cu + Cl2 ----7 CU02
Na2S203 + H 20 + Cl2 ----7 Na2S04 + 2HCI + S
(or Al2C16)
or
Mg + O 2 ---7 MgCl 2 Zn '+ Cl 2 ----7 ZnCh
Na2S203 + 4Cl2 + SH20 ----7 2NaHS04 + 8HCI
(c) Aff'mity for hydrogen: It has great affinity for
(e) Action of alkalies: When passed into cold dilute
hydrogen. It decomposes several hydrogen compounds forming
solution of alkalies, it forms chlorides and hypochlorites.
HCl.
2NaOH + Cl2 ----7 NaCI + NaCIO + H 20
(i) Turpentine bums in chlorine forming IrCI and carbon. .
2KOH + Cl 2 ----7 KCI + KCIO + H 20
C lOH 16 + 8Cl2 ----7 lOC + 16HCI
2Ca(OH)z + 2Cl2 ----7 CaCl2 + Ca(CIOh + 2H20
(ii) It reacts with water in the presence of sunlight and Cold and dilute
forms O 2, With hot concentrated alkali solutions, chlorates are formed.
2H 20 + 2Cl2 ----74HCI + Oz 6NaOH + 3Cl2 ----7 SNaCl + NaCI03 + 3H2
Chlorine water loses its yellow colour on exposure to sUnlight. 6KOH + 3C12 ----7 SKCI + KCI03 + 3H20
This is due to the formation of HCl.
6Ca(OH)z + 6Cl2 ----7 SCaCl2 + Ca(CI03h + 6H20
(iii) It reacts with ammonia under two conditions: Hot and cone.
However, when chlorine is passed over dry slaked lime, Mn02 + H2S04 ~ MnS04 + H20 + 0
bleaching powder is obtained. [KBr + H2S04 ~ KHS04 + HBr] x 2
Ca(OH)z + Cl2 ~ CaOCI2·H20 2HBr + 0 ~·H20 + Br2
Slaked lime Bleaching powder
2KBr + Mn02+ 3H2S04~ 2KHS0 4+ MnS04+ Br2 + 2H20
(f) Addition reactions:
Chlorine forms addition com-
pounds with S02, CO and unsaturated hydrocarbons. This reaction is commonly used in the laboratory for the
S02 + Ch ~ S02Ch ; CO + Cl2 ~ COCl2 preparation of bromine. The apparatus used has been shown
Sulphuryl chloride Carbonyl chloride in Fig. 12.6.
(Phosgene)
Phosgene is highly poisonous gas.

C2H4 + Cl2 ~ C2H4Cl2
_______ __ ___ Ethylene chloride
IQ Uses of Chlorine
It is used : (i) in the manufacture of bleaching powder,
tetrachloride and a number of synthetic organic compounds.

(ii) in the purification of drinking water. (iii) as a bleaching
agent for cotton fabrics, paper and rayon. (iv) in the extraction
of gold and platinum. (v) as an oxidising agent. (vi) as a To
~======-- sink
germicide and disinfectant. (vii) for the manufacture of
poisonol.ls gases like phosgene (COCl 2), tear gas (CCI 3·N02) Fig. 12.6
and mustard gas (CI-C2~----S-C2H4-Cl).
A mixture consisting 5 g of potassium bromide and 14 g of
manganese dioxide is taken in a glass retort. 30 mL concentrated
sulphuric acid to which 180 mL of water has been added, is
Bromine was discovered in 1826 by the French chemist Balard
poured over the mixture in the retort. The contents are heated
in the mother liquor left after the crystallisation of common salt
slowly. The reddish brown vapours of bromine are evolved.
from sea water. The name bromine was given due to its bad
These vapours are collected in a receiver which is cooled
and pungent odour (Greek: Bromos, a stench).
under cold water. Bromine vapours condense to give a dark
Occurrence: It is never found in free state in nature. The
red liquid.
chief sources of bromine are:
(i) Sea water contains bromides such as NaBr, KBr, MgBr2' Since the bromine vapours are poisonous, the preparation is
CaBr2, etc., in minute amounts. either carried out in a fuming cup board or in a well ventillated
(ii) The mother liquor left after the crystallisation of potassium laboratory.
chloride from carnallite, KCl, MgCI 2·6H20 (found in Stassfurt,
Germany) contains some bromocarnallite, KBr·MgBrz-6HzO.
!II Manufacture
(iii) The bromides such as NaBr, MgBrz, etc., are found in 1. From carnallite mother liquor: The mother liquor
small amounts in mineral springs and salt lakes. left after the crystallisation of potassium chloride from carnallite
(iv) Bromargyrite : a mineral, AgBr. contains about 0.25% of bromine as magnesium bromide and
Preparation: The following reactions can be used for its potassium bromide.
preparation. The hot mother liquor is made to flow down a tower packed
(i) By passing chlorine through the solution of potassium or with earthen-ware balls (Fig. 12.7). A current of chlorine and
magnesium bromide. steam is introduced from the bottom of the tower. The vapours
2KBr + Clz ~ 2KCI + Br2 of bromine set free are condensed in a condenser.
MgBrz + Cl z ~ MgCl z + Brz MgBrz + Clz ~ MgClz + Brz
(ii) By adding hydrochloric acid to the mixture containing The vapours which do not condense are allowed to pass
potassium bromide and potassium bromate. through a tower packed up with moist iron filings, forming
iron bromides.
5KBr + KBr03 + 6HCl ~ 6KCl + 3Brz + 3H zO
Fe + Brz ~ FeBrz
(iii) By heating mixture of potassium bromide and man- . 3FeBrz + Brz ~ Fe3Brs
ganese dioxide with conc. HZS04. Ferroso-ferric hromide
This is used for manufacture of potassium bromide. a yellowish brown solid. (b) It has irritating bad odour. The
The bromine so obtained contains chlorine and iodine as vapours attack the eyes and mucous membrane of nose and
impurities. It is purified by distilling it with potassium btomide throat. It brings blisters on the skin which take a very long time
and zinc oxide. The bromide reacts with chlorine while zinc to heal. It is I>0isonous. (c) It is fairly soluble in water (about
oxide reacts with iodine. 3.6% at 20°C). The solution is termed bromine water. A
r;:===- Hot mother saturated solution of bromine when cooled in a freezing mixture
liquor gives bromine hydrate, Br2·8H20. (d) It is more soluble in
chloroform, carbon tetrachloride, benzene, carbon disulphide,
etc. The colour of solution is u!lually reddish brown.
Chemical: In chemical behaviour, bromine closely
resembles chlorine.
Tower packed (a) Combination with elements: "
_wth eartrum,:1I'.IanL ~.~.l=ooJ·L;:=I~· (i}Brominereac..J:sdirectlywith~hydrogen;~thoughless-readily-~
balls
than chlorine. The reaction,
H2 + Br2 2HBr
is slightly reversible. It combines with hydrogen at 200°C or
~~_ . __ ._~ . _-J.~,.~~~=~,.~~~I~. ~~~;:;;;;;:;;;;::;:;::~l!.=;:;:$team=~=~-..---.._aLroom_temper.atureill_pr.esenG~of-platil1Wfr,.as-eatalyst;-·=,~·-:
L _ _ _ _ _.,':::::::=:::::j 1====;=- Chlorine (ii) It combines with SUlphur, phosphorus, arsenic, etc.
Recovery 2P + 3Br2 ~ 2PBr3
1- chamber
2As + 3Br2 ~ 2AsBr3
2B + 3Br2 Red heat ) 2BBr3
(iii) It combines directly with many metals.
1- 2Na + Br2 ~ 2NaBr (Slow reaction)
Fig. 12.7 2K + Br2 ~ 2KBr (Fast reaction)
2. From sea water: Sea water is the most important 2Al + 3Br2 ~ 2AlBr3 (Violent reaction)
sour<:~ of commercial bromine. Zinc reacts in presence of moisture with bromine.
The sea water is slightly acidified and then treated with Zn + Br2 -:----7 ZnBr2
chlorine to liberate the bromine.
(b) Oxidising action: Bromine is a good oxidising agent.
Cl2 + Bromides ~ Chlorides+ Bromine It ordinarily does not react with water but in presence of an
(Sea water)
. oxidisable substance it forms hydrogen bromide and oxygen
The evolved bromine is blown out by means of a current of with water. .
air. The air carrying the bromine vapours are passed through
Br2 + H20 ~ 2HBr + 0
absorption towers down which a sodium carbonate solution is
sprayed. The bromide combines forming sodium bromate and X+O~XO
Oxidisable substance
sodium bromide.
3Na2C03 + 3Br2 ~ NaBr03 + 5NaBr + 3C02 (i) It oxidises S02 into sulphuric acid.
The solution containing bromide and bromate is distilled S02 + Br2 + 2H20 ~ 2HBr + H2S04
with H 2S04 to recover bromine. (ii) It oxidises sulphites into sulphates.
[2NaBr + H2S04 ~ Na2S04 + 2HBr] x 5 Na2S03 + Br2 + H20 ~ Na2S04 + 2HBr
2NaBr03 + H2S04 ~ Na2S04 + 2HBr03 (iii) It oxidisesarsenites into arsenates.
[HBr03 + 5HBr ~ 3Br2 + 3H20] x 2 Na3As03 + Br2 + H20 ~ Na3As04 + 2HBr
lONaBr + 2NaBr03 + 6H2S04 ~ 6Na2S04

. + 6Br2 + 6H20
or 5NaBr + NaBr03 + 3H2S04~ 3Na2S04 + 3Br2 + 3H20
. (iv) It oxidises thiosulphate into sulphate.
Na2S203 + Br2 + H 20 ~ Na2S04 + S + 2HBr
(v) Sulphur is formed by oxidation of hydrogen sulphide.
The vapours are condensed.
H2S + Br2~ 2HBr + S
11 Properties (vi) Iodine is liberated from iodides.
Physical: (a) It is a reddish brown, heavy mobile liquid. 2KI + Br2 ~ 2KBr + 12
Its density is 3.2. It boils at 58.5°C and freezes at ~7.2°C to
(c) Action with alkalies: The action of bromine on 12.~fi IODINE

,;;..'''''tj
alkalies is similar to that of chlorine, a hypobromite with a cold
Iodine was discovered by Courtois in 1812 from the ashes of
dilute solution and a bromate with a hot solution are fonned.
sea-weeds. Gay-Lussac established its elementary nature and
2KOH + Br2 ----; KBr + KBrO + H 20 named it iodine on account of the violet colour of its vapours
(Dil. and cold) Pot. hypo-
bromite (Greek; Ioeides = violet).
Occurrence: Iodine never occurs free in nature. In
6KOH + 3Br2 ----; SKBr + KBr0 3 + 3H20
(Conc. and hot) Pot. bromate combined state, it occurs as iodides and sodium iodate. Traces
6Ba(OHh + 6Br2 ----; SBaBr2 + Ba(Br03h + 6H20 of compounds of this element are found in plants and animals,
(Cone. and hot) Barium in certain minerals and in sea water.
bromate There are two main sources of iodine:
3Na2C03 + 3Br2 ----; SNaBr + NaBr03 + 3C02 (i) Certain deep sea-weeds (Laminaria species), These
(Conc. and hot) plants contain O.S% of iodine in their ashes (known as kelp)
However, with slaked lime (dry) it fonns a compound similar in toe f6rn orf6afdes. -~--~
to bleaching powder. (li) Caliche or crude chile saltpetre which contains about
0.2% of Nal03 (sodium iodate).
Ca(OHh + Br2 ----; CaOBr2 + H 20
Slaked lime The less important sources of iodine are:
~ _ _ _ _ ~_m (nr'!fY)J---~- {i)~Sodium,~potassiuULand-magnesiumjodidesjnmvery.small m_
(d) Action of ammonia: It is simiI2r to that of chlorine. amounts are found in ores of lead arid dolomite.
8NH3 + 3Br2 ----; 6NH4Br + N2 (ii) Sea water contains iodides and organic compounds
containing iodine.
(e) Action of organic compounds: It fonns addition
(iii) Thyroxine which is present in thyroid gland.
compounds with unsatnrated compounds' and substituted
(iv) Oil-well brines contain Nal.
products with the saturated compounds.
Preparation: The following reactions can be applied for
C2H4 + Br2 ----; C2~Br2 the preparation of iodine:
CH4 + Br2 ----; CH3Br + HBr (i) B~ passing chlorine through potassium iodide solution.
(f) Bleaching action: The bleaching action of bromine 2K1 +.CI2 ~ 2KCI + 12
is weaker than that of chlorine. The bleaching action is due to
(ii) By adding potassium iodide solution to copper sulphate
its oxidising property.
solution.
(g) Action of mercuric oxide: Bromine water reacts
with mercuric oxide to fonn mercury oxybromide. CUS04 + 2K1 ~ CuI2 + K2S04
2HgO + 2Br2 + H20 ----; HgBr2·HgO + 2HBrO 2CuI2 ~ CU212 + 12
Mercury oxy- Cupric Cuprous
bromide iodidc iodide
However, on passing bromine vapours over dry HgO at (iii) By adding conc. sulphuric acid to a mixture of sodium!
60°C, bromine monoxide is obtained. potassium iodide and sodium/potassium iodate.
HgO + 2Br2 ----; Br20 + HgBr2 [Nal + H 2S04 ~ NaHS04 + HI] x 5
Nal03 + H2S04 ~ NaHS04 + Hl03
iii! Uses of Bromine Hl03 + SHl ~ 3H20 + 312
(i) The chief use of bromine is in the manufacture of ethylene
Nal03 + 5Nal + 6H2S04 ----;
6NaHS04 + 3H20 + 312
bromide' (C2~Br2) which is extensively employed as a
component of anti-knock gasoline. (iv) By adding an oxidising agent such as hydrogen peroxide,
(li) It is used in the manufacture of NaBr and KBr (used in ozone, acidified potassium pennanganate or acidified potassium
medicine as sedative), and certain organic dyes. dichromate to potassium iodide.
(iii) Bromine water is used in organic chemistry to test the 2K1 + H20 2 ~ 2KOH + 12
un saturation of organic compounds. (v) By reacting sodium iodate with sodium hydrogen
(iv) It is used as germicide. sulphite.
(v) It is employed as an oxidising agent and in organic
synthesis. 2Nal03 + 5NaHS03 ----; 3NaHS04 + 2Na2S04 + 12 + H20
Elements of Group VIlA or 17 (Halogens) 589---
(vi) By heating mixture of potassium iodide and manganese [NaI + H2S04 ~ NaHS0 4 + HI] x 2
dioxide with Co~c .. H2S04. Mn0 2 + H2S04 - - - t MnS04 + H 20 + 0
2KI + 2HzS04 ~ 2KHS0 4 + 2HI 2HI + 0 ~ H20 + 12
Mn02 + H2S04 ~ MnS04 + H 20 +0 2NaI + Mn02 + 3H2S04---t 2NaHS04 + MnS04 + H20 + 12
2HI + 0 ~ H20 + 12 Pure iodine is obtained by sublimation.
2KI + Mn02 + 3H2S04 - - - t 2KHS04 + MnS04 + 2H20 + 12 (n) From caliche: Chile saltpetre is dissolved in water.
The solution is concentrated and cooled to separate sodium
Iodine, in the laboratory, is usually prepared by this reaction. nitrate crystals. The mother liquor is treated with a calculated
The following materials are taken in a beaker, KI (3.S g), amount of sodium hydrogen sulphite* solution to precipitate
Mn02 (7.0 g) and 6N H 2S04 (100 mL). out iodine.
Cold water [NaI03 + 3NaHS04 ~ NaI + 3NaHS04] x S
. NaIOi=t-NaHS04~ -NaZS04 THIO}
[NaI + NaHS04 ~ Na2S04 + HI] x S
HI03 + SHI ~ 3H20 + 312
or 2NaI03+ SNaHS03* - - - t 3NaHS04 + 2Na2S04+ H20+I2

Purification: Commercial iodine obtained in the above
processes may contain iodine chloride (lCI) , iodine bromide
(IDr) and iodine cyanide (ICN) which are difficult to be removed
by sublimation. The impure iodine is distilled with potassium
iodide which removes the impurities and pure iodine vapours
Fig. 12.8 are condensed.
KI + ICI~ KCI + 12
The contents are heated and the vapours of evolved iodine KI + IDr - - - t KEr + 12
are condensed on a watch glass, cooled by ice as shown in KI + ICN ~ KCN + 12
Fig. 12.8. KCI, KEr and KCN are non-volatile substances.
II Manufacture !III Properties
(i) From sea-weeds: The sea-weeds are collected, dried Physical: (a) It is a black (dark violet) shining solid, i.e.,
and burnt in shallow pits. The ash left is called kelp. The ash it has metallic lustre. (b) It melts at 114°C and boils at 184°C.
is extracted with hot water which dissolves out chlorides, However, it sublimes rapidly below melting point giving violet
carbonates, sulphates and iodides of sodium and potassium. coloured vapours. (c) Iodine produces stains on skin. Its
vapours are pungent and irritating and very dangerous to inhale.
Iron retort (d) Its specific gravity is 4.98. It is diatomic in nature and
Aludels Iodine when heated at 1700°C,it is converted into atomic form.
!,""~"""~"~
1700°C
12 , \ I +I
(e) !tis slightly soluble in water giving alight brown solution.
Its solubility increases in water in presence of potassium iodide
due to formation of potassium tri-iodide. KI3 easily breaks
down and thus the solution has all the properties of free
Fig. 12.9 iodine.
KI+12~KI3
The solution on concentration and cooling separates out
(f) It is soluble in many organic solvents such as chloro-
chlorides, sulphates and carbonates while iodides remain in
form, carbon tetrachloride, alcohol, ether and carbon disul-
solution. The solution is mixed with manganese dioxide and
phide. The solution in CS 2, CHCl3 and CC4 is violet in colour.
concentrated sulphuric acid in iron retorts. Iodine is liberated
Chemical: Iodine is chemically less reactive in com-
and condensed in series of earthen-ware receivers known as
parison to chlorine and bromine.
Aludels.
*NaHS03 if present in excess, HI is produced, NaHS0 3 + 12 + H20 ~ NaHS04 + 2HI
(a) Combination with elements: It combines directly (f) Action of NH3: Iodine forms a mild explosiv~ with
with many elements. ammonia.
H2 + 12 Heat) 2HI 2NH3 + 312 ~ NI3·NH 3 + 3HI
Pt Explosive
2P + 312 Heat) 2PI 3 8NI3·NH 3 ~ SN2 + 912 + 6NH41

2K + 12~ 2KI (g) Reaction with strong oxidising agents: Strong
oxidising agents convert iodine to iodic acid (HI0 3).
2Fe + 312 Heat) 2Fel3
(i) With conc. RN0 3.
(b) Oxidising properties: It is a weak oxidising agent.
12 + lOHN0 3 ~ 2HI0 3 + lON02 + 4H20
The following reactions show its oxidising nature.
(ii) With ozone.
(i) H 2S + 12 ~ 2HI+ S
12 + H 20 + 503 ~ 2HI03 + 502
(ii) SO~~_I~+_ ~1I1Q ~ 1I~~C:>±-+ 2IiI __ _
(iii) With cll.lorifieWatef.
(ui) Na2S03 + 12 + H 20 ~ Na2S04 + 2HI
12 + SCl2 + 6H 20 ~ 2HI03 + lOHCl
(iv) Na3As03 + 12 + ?20 ~ Na3As04 + 2HI
(h) Reaction with freshly precipitated mercuric oxide:
(v) 2FeS04 + H2S04 + 12 ~ Fe2(S04h + 2HI Io dine f orms h ypOlO
. d ous aCI'd'th "OXl
WI mercunc de.
- ------{c}-Reaction-with-alkalies-:--Iodine reacts-witll-cold-dilute-------
2HgO + 212 +- H2O ~ Hglz-HgO + 2HrO
solution of NaOH forming hypoiodite. The colour of the solution
becomes faint yellow. However, hypoiodite undergoes hydro- (i) Iodine when warmed with alcohol and alkali forms
lysis forming HIO. iodoform.
2NaOH + 12 ~ NaIO + NaI + H 20 C2H sOH + 6KOH + 412~ CHI3 + HCOOK + SKl + SH20
NaIO + H 20 ~ NaOH + HIO (j) Reaction with chlorine: When chlorine is passed
over iodine, at first iodine monochloride, ICI (dark liquid) and
NaOH + 12 ~ NaI + HIO finally iodine trichloride, ICl3 (yellow solid) is formed.
Hypoiodous acid
(k) Reaction with starch: Iodine turns starch solution
Iodine when heated with concentrated alkali solution, iodide blue. This is one of the tests of iodine.
and iodate are formed. The colour of iodine disappears. (I) Action on unsaturated organic compounds: Addi-
6NaOH + 312 ~ SNaI + NaI03 + 3H20 tion products are formed with unsaturated organic compounds.
~
Colourless C2H4 + 12 ~ C2H412
(d) Iodine does not displace chlorine and bromine from
chlorides and bromides, respectively but it displaces them from ~ Us~s of Iodine
their oxy salts.
(a) It is used in medicine, e.g., tincture of iodine [~oz.
2KCI03 + 12 ~ 2Kl03 + Cl2
2KBr03 + 12 ~ 2Kl03 + Br2
j
iodine, oz. Kl and 1 pint rectified spirit] and iodex as antiseptic
and analgesic. Solutions of iodine in Kl are used in the treatment
(e) Reaction with sodium thiosulphate: Iodine solu-
of goitre.
tion is decolourised by sodium thiosulphate (hypo) as sodium
(b) It is used in the preparation of iodoform, iodIdes, dyes,
tetrathionate and sodium iodide are formed. Both are colourless
etc.
and soluble.
(c) It is used in the analytical chemistry.
2Na2S203 + 12 ~ 2NaI + Na2S406 (d) It is used in the preparation of photosensitive papers,
Sodium thiosulphate Sodium tetrathionate
films and plates.
This reaction is involved in iodometric titrations in presence
of starch indicator.
Elements of Group VIIA or 17 (Halogens) 59L
COMPARISON OF HALOGENS (F2• C1 2• Br2 and 12)
S.No. Property Fluorine Chlorine Bromine Iodine
1. Physical state at Gas; Gas Liquid Solid
ordinary
temperatures
2. Colour Pale greenish yellow Pale greenish yellow Reddish brown Violet.
3. Solubility in water
Decomposes water to form Soluble to form OCl- Less soluble than chlorine Less soluble than bromine
• HF, Oz and 0 3
I
4. Density of the solid . 1.3 1.9 3.4 4.93
(g mL- 1)
5. Boiling point (0C) -187 -34.6 58.78 183 .
6. Electronegativity i 4.0 3.0 2.8 2.5
(Pauling scale)
--7~- Tl1emical reactivity - Highlireactive-~ Quite active Less active than chlorine Less active than bromine
8. Reaction with
(i) hydrogen Combines explosively even Explosive in light, slow in Only on hea.ting On heating and in presence
in the dark dark of a catalyst
__ ~ __. _.,.J_.(.'=-cii).Vic:i"acter:~~..-c~..--I.~I>~~J?Os~s.. forming.. fI5,~, .. ~o.pnLchlorinehydrate~ ..Decomposes-slowlyin---- --Nocastien--.---·~~'~ --
-" O2 and 0 3 with ice-cold water presence of light forming
Decomposes slowly HBr and HBrO or HBr and
forming HCI and HCIO or Oz
HCl and Oz
(iii)alkalies With dilute alkalies, F20 Forms chlorides and hypo- Same as chlorine Same as chlorine
and alkali fluorides are chlorites with cold dil 2NaOH + Brz -----> 2NaOH + 12 ----->
formed. With conc. alkalies, alkali solution. Chlorides dil. NaI + NaIO + H20
alkali fluorides and Oz are and chlorates are formed NaBr + NaBrO + H20 6NaOH + 31z ----->
formed with hot conc. solutions 6NaOH + 3Brz -----> 5NaI + Nal0 3 + 3HzO
2NaOH+2Fz~ 2NaOH (dil.) + Clz -> conc.
FzO + NazFz + H20 NaCl + NaClO + HzO 5NaBr + NaBr03 + 3H20
6NaOH + 3Cl2 -> 5NaCI -t
cone.
4NaOH+ 2F z ~ NaCIO) + 3H2O

2NazF2 + 2H20 + O 2
(iv) halides Displaces other halogens Displaces Br2 and 12 from Displaces 12 from iodides
bromides and iodides
I (v) metals Reacts with all metals to Reacts with almost all Many metals are acted upon React only with few metals
form fluorides metals forming chlorides and bromides are formed to form iodides
i (vi) non-metals Combines with all non- Combines with many non- Combines with many non- I Combines with only few
metals except N 2, 02 and metals (except C, N2, 02 metals ' non-metals such as P, As,
lower inert gases and inert gases) etc.
9. Oxidising nature Very strong oxidising agent Strong oxidising agent Good oxidising agent Mild oxidising agent
10. i Bleaching action Destroys the reducible Bleaches vegetable colours Mild bleaching agent
j coloured substance easily I
12.i} $<)
HALOGEN ACIDS OR HYDRACIDS III Preparation (HCI, HBr and HI)
All the halogens combine with hydrogen and form the covalent (0 By the direct combination of elements: Hydrogen
hydrides of HX type (X ;:: F, el, Br or I). These hydrides are chloride (Hel) is formed by burning chlorine in excess of
called hydracids or halogen acids. hydrogen .
.Hydrogen fluoride (HF) H2 + e12~ 2HO
Hydrogen chloride (Hel) HBr can be prepared by passing a mixture of H2 and Br2
Hydrogen bromide (HBr) over a platinum spiral heated to redness by an electric current.
Hydrogen iodide (ll) Pt
H2 + Br2 ~ 2HBr
m can also be prepared in small quantities by passing are gases. They fume in air and have pungent odour. These are
hydrogen and iodine vapours over red hot fine platinum. colourless. All are heavier than air and can be liquefied to
colourless liquids.
H2 +12 2m Their melting and boiling points increase with increase in
(li) By heating a halide with acid: Hydrogen chloride is atomic mass of the halogen. The low values are due to covalent
prepared by heating sodium chloride with concentrated sulphuric nature.
acid. HCI HBr HI
2NaCl + H2S04 ~ Na2S04 + 2HCl Melting point eC) -Ill -86 -50.8
Boiling point eC) -85 -67 -35.5
HBr and ill cannot be prepared by heating bromides -
and iodides with conc~ntrated H 2S04 because HBr and ill H2F2 is a liquid with boiling point 19.5oC. This behaviour
are strong reducing agents and reduce H 2S04 to S02 and is due to association of HF molecules through hydrogen
get themselves oxidised to bromine and iodine, respectively. bonding.
KBr + H2S04 ~ KHSQ4 +HBr H-F----H-F-----H-F'------H-R----- -~---
KI + H2S04 ~ KHS0 4+ m (ii) Constant boiling mixtures: These are fairly soluble
H2S0 4 + 2HBr ~ S02 + Br2 + 2H20 in water. They fonn constant boiling mixtures with water
H2S04 + 2m ~ S02 + 12 + 2H20 called azeotrope. .
H-lfiUS~r and RIare prepared l:lylieatingC"ffiomides ahd----dlydmgeiHJ.alide •.....~C~~siticuh.., ...• Jipilipg.-PQim:"".(."C~)= = =
iodides respectively with conc. orthophosphoric acid. H2F2 36% . 120
3KBr + H3P04 ~ K 3P0 4 + 3HBr HC! 20.4% 110
HBr 47% 126
HI 57% 127
(iii) HBr and m can be prepared by hydrolysis of corres-
ponding phosphorus trihalides. (iii) Stability: The bond strength H-X decreases from
2P + 3Br2 ~ 2PBr3 HF to HI. Thus, HF is most stable while m is least stable. The
decrease in stability is due to decrease in electronegativity from
2P + 312 ~ 2PI 3
F .to I. This is also observed in the values of dissociation
PBr3 + 3H20 ~ H3P03 + 3HBr energy of H-X bond.
PI3 + 3H20 ~ H3P0 3 + 3m H-F H-CI H-Br H-I
Hydrogen fluoride: It is an associated molecule and is Dissociation
represented by fonnula, H 2F 2. energy (kcal mol-I) 136 105 86 70
Pure anhydrous hydrogen fluoride is obtained by heating
HF and HCI are s~ble upto 1200°C, HBr dissociates slightly
potassium hydrogen fluoride (dry) in a platinum retort.
and m dissociates considerably (20%) at 440°C.
2KHF2 ~ K2F2 + H2F2 (iv) Acid strength: Hydrogen halides in the gaseous state
The vapours are condensed in a platinum condenser and are essentially covalent. In aqueous solutions, however, they
collected in a platinum receiver. In place of platinum, lead ionise and act as acids. HF is only slightly ionised but HCI, HBr
apparatus can also be used. and m are almost completely ionised, i.e., the relative strength
The aqueous solution of H2F2 can be obtained by heating increases from HF to m. HF is the weakest acid and HI is
calcium fluoride with 90% conc. sulphuric acid in a lead retort. the strongest· acid. On the basis of electronegativity, this
The vapours are condensed in a strongly cooled lead receiver. appears to be rather surprising. [The electronegativity difference
Aqueous acid of about 40% strength can be obtained by passing 'suggests that HF should be strongest and m should be weakest
the vapours through water in a lead receiver. acid.] The increase in strength is reflected from the dissociation
CaF2 + H2S04 ~ CaS04 + H2F2 constant values, K a , of these hydrogen halides.
The aqueous solution of H2F2 is kept in qutta-percha bottles HF HCI HBr HI
when dilute and in wax bottles when concentrated. The 7 X 10-4 7 x 108 7 x 1010 .7 X 1011
anhydrous acid is stored in well cooled platinum, gold or silver The anomalous behaviour is explained with the help of
vessels or steel cylinders. Born-Haber cycle. The various factors which determine the
strengths of the acids in aqueous medium can be represented
Properties in the fonn of Born-Haber cycle, as shown below:
(i) Physical state: Except H2F2, other hydrogen halides
Elements of Group V1IA or 17 (Halogens) 593··
Acid strength + _ H2S04 + 6HI ---7 S + 312 + 4H20
HX(aq.) H f'"
eat 0 lorusation
) H (aq.) + X (aq.)
(M) H2S04 + SHI ---7 H2S + 412 + 4H20
1 Heat of dehydration
(Mh)
HX(g)
. 2RN03 + 2m ---7 2N02 + 2H20 + 12
2RN02 + 2m ---7 2NO + 2H20 + 12
1
~r---.:L.--J WiiJ
Heat of dissociation
2FeC1 3 + 2m ---7 2PeC12 + 12 + 2HCl
2CUS04 + 4m ---7 CU212 + 2H2S04 + 12
'1
H(g)
Ionisation
energy (t:.H3)
X(g)
1 Electroh affInity
(t:.H4) Heat of
K2S20g + 2HI ---7 K2S04 + H2S04 + 12
Potassium peroxy-
disulphate
X~ ________~h~y~d~rn=ti=on~ (vi) Precipitation reactions: HCI forms insoluble
(Ml6) chlorides with the soluble salts of Ag, Pb and Hg(ous).
Heat of hydration (t:.Hs)
AgN03-+ RCl .. - -)AgCl.+HNOg--
Summation of all energy terms will be equal to !::J. (White)
!J.I = Mil + !J.H2 + Ml3 - !J.H4 - (!J.HS + !J.H6) Pb(N03h + 2HCI---7 PbCl2 + 2RN03
The values of !::J for various halogen acids as calculated are (White)
given belm\':. .. . ...'. , . . .. __. _' _._.. ___ m_.Hg2(NQ3)2_:t_2HCL_m)~g2-C12.+..2HN0-3

;A4U""''''*1iF 'Hff "~'-"~HBr~=e~m""""=" (White)
AI (kJ morl) -12 -59 -63 -57 AgCl is insoluble in RN03 but soluble in NH40H. PbCl2 is
The larger the negative value M, the greater is the soluble in hot water while Hg2Cl2 is soluble in aqua-regia.
•
feasibility of ionisation reaction and hence the greater is HBr reacts with soluble salts of Ag and Pb.
the strength of the halogen acid. AgN03 + HBr ---7 AgBr + RN03
The value of HF is small compared to other acids, hence HF (Pale yellow)
is .the weakest acid. The values also explain the gradual Pb(N03)2 + 2HBr ---7 PhBr2 + 2RN03
increasing strength of HCI and HBr but fail to explain the (White)
strength of m. This discrepency is explained on the basis of AgBr is insoluble in RN03 but sparingly soluble in
entropy changes (!J.S) accompanying the process of ionisation. NH40H. PbBr2 is soluble in hot water.
The lower strength of HF is largely due to its high bond m forms insoluble iodides with the salts of Ag, Pb and
dissociation energy as the bond length is very small (1.01 A). Hg (ic).
(v) Reducing nature: The reducing nature increases AgN0 3 + m ---7 AgI + RN03
from HF to m as the stability decreases from HF to m. HF (Yellow)
does not show reducing nature. It cannot be oxidised even by Pb(CH3COOh + 2m ---7 Phl2 + 2CH3COOH
strong oxidising agents. m is the strongest reducing agent. Its (Yellow)
aqueous solution gets oxidised even by atmospheric oxygen. HgCl 2 + 2m ---7 Hgl2 + 2HCI
. (Scarlet)
4m + O2 ---7 2H20 + 212
AgI is insoluble in RN0 3 and NH40H. Pbl2 is soluble in hot
The reducing action can also be explained on tpe basis of water.
increasing size of the halide ions from P- to r. The bigger ion (vii) Action of balogens: P2 can displace C12, Br2 and
can lose electron easily. 12 from HCI, HBr and m.
HCI can be oxidised by strong oxidising agents like Mn02,
2HCI + F2 ---7 2HF + Cl2
KMn04, K2Cr207, Pb02, Pb30 4, etc. (see reactions in
section 12.4). 2HBr + F2 ~ 2HF + Br2
HBr acts stronger reducing agent than HCI. It can be oxidised 2m + F2 ---7 2HF + 12
by H2S04 and atmospheric oxygen. Cl2 can displace Br2 and 12 from HBr and m and Br2 can
H2S04 + 2HBr ---7 S02 + Br2 + 2H20 displace only 12 from HI. Iodine can displace none.
4HBr + 02 ---7 2H20 + 2Br2 (viii) Reaction with ammonia: HCI, HBr and m
combine with ammonia giving white fumes of ammonium
HI is the strongest reducing agent.
halides.
It reduces H2S04 to S02. S and H2S, nitric acid to N02, NH3 + HCI---7 NH4Cl (Ammonium chloride)
nitrous acid to NO, FeCl3 to FeCI2, cupric salt to cuprous salt,
NH3 + HBr ---7 NH4Br (Ammonium bromide)
etc.
NH3 + m ---7 NH41 (Ammonium iodide)
.-, - --'---'
(ix) Acidic properties: All the three (HCI, HEr and ill) The etching of glass is based on these reactions.
react with certain metals, their oxides, carbonates, hydroxides, (vii) When hydrofluoric acid is heated with a mixture of
etc., and fonn salts. . Mn02 and H2S04, no gas is evolved. On the other hand, in
Mg + 2HX~ MgX2+H2 case of HCI, HEr and HI acids, C12 (yellowish green), Br2
MgO+ 2HX~ MgX2 + H20 (reddish brown) and 12 (violet) gases are evolved.
CaC03 + 2HX ~ CaX2 + H 20 + 'C02 Mn02 + H2S04 ~ MnS04 + H20 + 0
NaHC03 + HX ~ NaX + H 20 + CO2 2HX+ O~ H20 + X2
NaOH + HX ~ NaX + H20 HX = HCI, HEr or ill X2 = C12, Br2 or 12
[HX =HCI, HEr or ill] (viii) With AgN0 3 solution, hydrofluoric acid gives no
,(x) Action of salts: HCI, HEr or ill decompose the salts precipitate since AgF is fonned which is soluble in water. On
of weaker acids. the other hand, HCI, HEr and HI give the precipitates of AgCl,
Na2S + 2HX ~ 2NaX + H 2S AgBr and AgI respectively.
CajP2T-6H-X-- ) 3CaX'2+ 2PHj' (ix}Leaga~tate does nQLfo@!l.nYPIecipi1l!tf:_w~
hydrofluoric acid while other halogen acids fonn precipitates
Na2S03+ 2HX ~ 2NaX + H20 + S02
ofPbCl2 (white), PbBr2 (white) and PbI2 (yellow) respectively.
2NaN02 + 2HX ~ 2NaX + NO + N02 + H 20
(x) With barium chloride solution, H2F2 fonns a white
Na2S203 + 2HX ~ 2NaX + S02 + S + H20 precipitate of BaF2 while other halogen acids do not fonn any
----precipitate"sincec-BaXT(X--=Br-and-iJ,are-soluble-.~-
Abnormal Properties of Hydrofluoric Acid
H2F2 + BaCl2 ~ BaF2 + 2HCI
(White ppt.)
Hydrofluoric acid differs from other halogen acids in the
following respects: Same thing happens with the solutions of calcium chloride
(i) Anhydrous hydrogen fluoride is a liquid at ordinary and strontium chloride as CaF2 and SrF2 are also insoluble.
temperature while other halogen acids are gases. This is due
Uses of halogen acids
to strong hydrogen bonding in hydrogen fluoride.
(ii) It is very stable. It does not dissociate on heating while (i) Hydrofluoric acid is used : _
other halogen acids dissociate at definite temperatures. (a) in the etching of glass.
Hel HBr HI (b) in the manufacture af fluorine.
Dissociation temp. (0C) 1500 800 180 (c) for removing silica from artificial graphite and other
It is due to decrease in the electronegativity and bond castings.
energy. (d) as an antiseptic in brewing industries.
(iii) It exists as associated molecule, H2F2, even in gaseous (e) for making fluorides. NaF is used as an insecticide.
state. It fonns two series of salts, i.e., KHF2, K2F 2. Other AlF3 is used in the extraction of aluminium. Fluorides of
halogen acids have molecular fonnula, H X and fonn one series alkali metals and antimony are used as mordants in dyeing
of salts. industry. UF6 is used for separation ofU235 isotope by diffusion
HCI; Chlorides, e.g., NaCl, AgCl, FeCIJ, BaCI 2,etc. method.
HEr; Bromides, e.g., NaBr, AgBr, FeBr3, BaBr2, etc. (li) Hydrochloric acid is used :
HI; Iodides, e.g., NaI, AgI, FeI J, BaI2, etc.
(a) in the preparation of chlorine, chlorides and aqua-regia.
(iv) It isa weak acid but is extremely stable. It is not
(b) as a laboratory reagent.
oxidised by strong oxidising agents. On the other hand all other
(c) for cleaning iron sheets during tin plating and galvani-
halogen acids are oxidised.
sation.
(v) Hydrofluoric acid is highly poisonous and has a very
(d) for extraction of glue from animal tissues and bones.
high corrosive action on skin.
(e) in medicines.
(vi) Unfike other halogen acids, hydrofluoric acid attacks
silica and glass. With silica, it fonns silicon tetrafluoride and (iii) Hydrobromic add is used :
hydrofluosilicic acid. (a) as a laboratory reagent for preparing bromo derivatives
Si02 + 2H2F2 ~ SiF4 + 2H20 of unsaturated organic compounds.
SiF4 + H2F2 ~ H 2SiF6 (b) for making NaBr and KBr which are used as sedatives.
Hydrofluosilicic acid (c) for making AgBr used in photography.
Glass being a mixture of sodium and calcium silicates reacts (iv) Hydroiodic acid is used :
with' hydrofluoric acid forming sodium and calcium fluro-
(a) as a reducing agent in organic chemistry.
silicates respectively.
(b) for making KI which is used in medicines.
Na2Si03 + 3H2F2 ~ Na2SiF6 + 3H20
(c) for making AgI which is used in photography.
CaSi03 + 3H2F2 ~ CaSiF6 + 3H20
COMPARISON OF HALOGEN ACIDS (HF, HCI, HBr and HI)
S.No. Property HF Hel HBr HI
1. Physical state at ordinary Liquid Gas Gas Gas
temperature
2. Colour Colourless Colourless Colourless Colourless
3. Smell Choking Choking Irritating Irritating
4. Stability Stable Stable Less stable than HCI Muchiess stable
S. Strength of the acid A weak acid ·Gaseous HCI is not acidic Greater than HCI Strongest.
(Weakest) but aqueous solution is
highly acidic
6. Reducing nature No reducing nature Acts as a reducing agent Stronger reducing agent Strongest reducing agent
and is oxidised to Ch than HCI and is oxidised to of all the halogen acids
Brz
7.~ ~ .. Actionof~Mn02~and~--~~- ..... No-gas~isevolved- ~GhlQrine~is~evol:ved--- 13f{)mine~gas--is~evolved--~·
-Iodine-(violet)-':vapollf
~~
H 2SO4 Turns starch paper yellow
are evolved. Tums starch
paper, violet
8. Action with AgN03 No precipitate White precipitate, soluble Pale yellow precipitate Yellow precipitate,
solution in~OH sparingly soluble in ~OH insoluble in ~OH
~ Action of lead acetate c~!'lJ:!_precipit<lte.~ ~WhitJLllrecipitate~dissolves ~e~precipitate_dissolveL -Yellow--precipitate
""'. solU:ti~;~'~- "',~ in hot water in hot water dissolves in hot water
10. Action" of X2 Cl2 is liberated only by F2 Br2 is liberated by F2 and I2 is liberated by F2, Clz
Cl2 ! and Br2
11. Confmnation test With silica forms Sif4 . ChromyI chloride The aqueous solution on The aqueous solution on
which on hydrolysis treatment with chlorine treatment with chlorine
gives white deposit water in presence of water in presence of
chloroform gives brown chloroform gives violet
colouration icolouration
12.S"d OXIDES OF CHLORINE (ii) Chlorine dioxide, CI0 2 : Pure CI02 is obtained by
passing dry Cl2 over AgCI0 3 heated to 90°C.
Chlorine forms a number of oxides such as C120, CI02, Cl206
and C120 7• All of them are unstable and highly reactive. 2AgCI03 + CI2(dry)--? 2AgCI + 2CI~+ O2
(i) Dichloro oxide, C120: It is prepared by passing dry It can also be obtained by the action of Cl2 on sodium
chlorine over freshly precipitated yellow mercuric oxide. chlorite.
HgO + 2CI2(dry) ----? HgCl2 + Cl20 2NaCI02 + Cl2 ---'7 2NaCI + 2CI02
It is a brownish yellow gas which condenses to an orange It can be condensed by cooling to a coloured liquid (b.pt.
coloured liquid in a freezing mixture (b. pt. == 2°C). It has 11°C). The gas explodes and is decomposed to Cl2 and 02 by
characteristic penetrating odour. Liquid Cl20 explodes readily an electric spark. It dissolves in water giving a mixture of
on heating or sparking forming Ch and O2. It also undergoes chlorous acid and chloric" acid.
photochemical decomposition. . 2CI02 + H20 ----? HCl02 + HCI03
2Cl20 ~" 2Cl2 + O2 With alkalies, it gives a mixture of chlorite and chlorate ..
It dissolves in water giving golden yellow solution of hypo- 2CI02 + 2KOH ~ KCI02 + KCI03 + H20
chlorous acid, HCIO. It is thus anhydride of hypochlorous
It is a powerful oxidising and bleaching agent.
acid.
It has an angular structure with O--CI-O bond angle of
Cl20 + H20 ~ 2HCIO 117.6°C. The molecule is supposed to contain a three electron
Its gaseous mixture with ammonia explodes violently. bond. Its structure is believed to be a resonance hybrid of the
3Cl20 + !PNH3'~ 2N2 + 6Nl4CI + 3H20 following two structures:
It is a strong oxidising agent. It oxidises HCI to C12. XXX
Cl20 + 2HCI ~ 2Cl2 + H20

Cl20 has V-shaped structure. The oxygen atom undergoes
sp3 hybridization. The CI-O--CI bond angle is 110.9°.
sl
~
o/ The structure arises from d hybridi£.tcion of Cl-atom.
..;,
II 0.9" .0'0 The molecule is paramagnetic due to tb ~presence of three ..
electron bond.
Cl Cl
(iii) Dichlorine hexoxide, C1 20 6 : It is obtained by Commercially, it is obtained by passing C02 through

mixing chlorine dioxide with ozonised air at O°C. suspension of bleaching powder and then distilling.
2CI02 + 203 ~ Cl206 + 202 2CaOCl2 + H20 + C02 -----7 CaCl2 + CaC03 + 2HCIO
It is a dark red liquid. It is unstable and decomposed into It is a weak acid. Its concentrated solution is yellow in
CI02 and O2. It is a strong oxidising agent. It reacts with water colour while dilute solution is colourless. It is unstable and
forming chloric and perchloric acids. decompos~s.
Cl206 + H20 ~ HCI03 + HCI04 2HClO ~ 2HCI + 02
It reacts with alkalies to give chlorates and perchlorates. It dissolves magnesium with evolution of hydrogen.
Cl206 + 2KOH ~ KCI0 3 + KCI04 + H20 Mg + 2HCIO ~ Mg(CIOh + H2
With HF, it gives HCI0 4 and chloryl fluoride. With alkalies, it fonns salts called hypochlorites.
Cl20 6 + HF ~ HCI04 + Cl02F It acts as a powerful oxidising and bleaching agent. This is
-In-the
- va-I!our state it exists as CIO3
molecule which has odd
---------- --
due to release of nascent oxygen easily.
-------- - - - --- - - - - - - - - - - - - - - - - -- ----- -
number of electrons and hence paramagnetic while in liquid HCIO ~ HCI + 0
state it is in dimeric fonn having even number of electrons and ClO- ion has linear shape. Linear shape resuft~from sl
hence diamagnetic in nature. hybridization of Cl-atom.
2CI03 ~ Cl20 6
The exact structUre· is unknown. However, the following • 0
structure containing CI-Cllinkage is proposed in which each

chlorine is sl
hybridized.
Bleaching powder, CaOCI 2 oH 2 0
Bleaching powder is also called calcium chlorohypochlorite
because it is considered as a mixed salt of hydrochloric acid
and hypochlorous acid. It is represented as:
The molecule is diamagnetic and has no unpaired electron.
(iv) Chlorine heptoxide, C120 7 : It is fonned by
dehydration of perchloric acid with P20S at -woe.
0
ca< CI
(Odling fonwla)
OCI .
2HCI04Cl20 7 + H20
P2 5)
It is manufactured by the action of chlorine on dry slaked
It is a colourless oily liquid which is explosive in nature. It lime, Ca(OHh, at 40°C.
slowly reacts with water forming perchloric acid. It is, thus, Ca(OHh + Cl2 ~ Ca(OCI)CI + H20
anhydride of perchloric acid. This is the Odling view about its fonnation. There is another
Cl20 7 + H20 ~ 2HCl04 view proposed by Clifford according to which bleaching
It is less reactive in comparison to lower oxides of chlorine. powder is a mixture of calcium hypochlorite and basic calcium
Cl20 7 has the structure 03CI-O-CI03 in which two chloride.
tetrahedral are sharing one O-atom. 2Ca(OHh + 2Cl2 ~ Ca(OClh + CaCl2 + 2H20
o • CaCl2 + Ca(OHh+ H20 -----7 CaCI2·Ca(OHhH20
o '''1\.\~~~~· ,,~ 0
~ y 119
0
~\~ 2Cl2 + 3Ca(OHh-----7 Ca(OClh + CaCI2·Ca(OHhH20 + H20
/,Cl", /,C!~ \ ,
o 0 0 0 Bleaching powder
The manufacture of bleaching powder is carried out in any

12-f§jj
~''':'-~.::::
OXY-ACIDS OF CHLORINE one of the following plants:
(i) Hasenclever's plant (Old process),
r"'1 (A) Hypochlorous Acid, HCIO (ii) Beckmann's plant (Modem process).
The acid is known only in solution. It is obtained by shaking (i) Hasenclever's plant: It consists of a number of
cast-iron horizontal cylinders, each provided with a rotating
precipitated HgO with chlorine water.
shaft fitted with blades and arranged as shown in Fig. 12.10.
2HgO + 2Cl2 + H 20 -----7 Hg20Cl2 + 2HCIO The dry slaked lime is introduced through the hopper in
Oxychloride
of mercury the uppennost cylinder. It is pushed onwards with the help of
the blades when the shaft rotates. A stream of chlorine is
Elements of Group VIIA or 17 (Halogens) 597
Waste
which Slowly moves upwards. Bleaching powder is collected
Rotating shaft gases Lime in a barrel at the base.
~w_it~hb_la_de_s______~tU+~ The chlorine used in the manufacture of bleaching powder
I
should be dilute and the temperature should be maintained
below 40°C.
Properties
(a) It is a pale yellow powder. It has a strong smell of
chlorine. It is soluble in water but a clear solution is never
formed due to the presence of impurities.
(b) On long standing, it undergoes auto-oxidation into calcium
chlorate and calcium chloride.
6CaOCIz ----7Ca(CI03h +SCaCi z
, (c) In presence of cobalt chloride, CoClz, it loses its
oxygen.
CoCI 2
. _~.._ _. . .___ Fig~~2.10 ~_. .~_..._ _...____ , _ . . _____ 2CaO"C12-)....2CaCI2.....+--O~-~~~
admitted from the bottom and passes upwards. The chlorine Cd) In presence of a slight amount of a dilute acid, it loses
is completely absorbed by the time till it reaches the top cylinder. ' oxygen. ...
. Bleaching powder is collected in a barrel placed below an outlet 2CaOCl2 + H2S04 ----7 CaCl2 + CaS04 + 2HCte'
in the lowermost cylinder while the waste gases escape from HOO ----7 HCI + 0
the top. On account of the formation of nascent oxygen, it shows
(ii) B,~kmann's plant (Modern process): It consists oxidising and bleaching properties.
of a vertical cast-iron tower. The tower is provided 'with a (i) Oxidising properties:
hopper at the top, two inlets near the base (one for chlorine and CaOCl2 + H2S ----7 CaCl2 + H20 + S
other for hot air) and an exit for waste gases near the top CaOC12 + 2FeS04 + H S04 ----7 Fe2(S04h + CaC12 + H20
4
(Fig. 12.11). CaOC12 + KN02 ----7 CaCl2 + KN0 3
Slaked lime and
...... compressed air
3CaOC12 + 2NH3 ~ 3C,aC12 + 3H20 + N2
CaOC12 + 2KI + 2HCI ----7 CaC12 + 2KCI + H20 + 12
Na3As03 + CaOCl2 ----7 CaCl2 + Na3As04
(ii) Bleaching· action :
Rotating Coloured matter + [0] ----7 Colourless product ~
rakes
(e) It loses its chlorine by the action of dilute acids (in
excess) or carbon dioxide.
CaOCl2 + 2HCI ----7 CaCl2 + H20 + Clz
Shelves CaOCl2 + H2S04 ----7 CaS04 + H20 + Cl2
CaOClz + CO2 ----7 CaC03 + Clz
The amount of chlorine obtained from a sample of
bleaching powder by treatment with excess of dilute acids
or carbon dioxide is called available chlorine. A good sample
of bleaching powder contains 35-38% of available chlorine.
(f) Bleaching powder converts acetone or ethyl alcohol into
chloroform.
" 'Bleaching
powder CaOCl2 + H20 ----7 Ca(OH)z + Cl2
CH3 ) CCI3 )
CO -+- 3Cl2 ----7 . CO + 3HCl
Fig. 12.11 CH3 ' CH3
The tower is fitted with eight shelves at different heights CCI3~ CH3COO~
each equipped with rotating rakes. The slaked lime is introduced 2 / , 0 + Ca(OH)z ----7' / , a + 2CHC13
through the hopper and it comes in contact with chlorine CH3 CH3C O O ' Chloroform
Calcium acetate
598 GR.B. Inorganic Chemistry for. Competitions
Uses of Bleaching Powder Ba(CI02)z + H 2S04 ---7 BaS04 + 2HCI02

It is used (i) as a disinfectant and germicide especially in the The freshly prepared solution is colourless but it soon
sterilisation of drinking water. (il) for manufacture of decomposes to CI02 which makes the solution yellow.
chloroform. (iii) for making wool unshrlnkable. (iv) as an 5HCI02 ---7 4CI0 2 + HCI + 2H 20
oxidising agent in industry. (v) mainly as bleaching agent for The acid undergoes auto-oxidation.
cotton, linen and wood pulp. However, delicate articles like
2Haaz ---7 HCIO + HCI03
straw, silk, ivory, etc.~ are not bleached by bleaching powder..
The acid liberates iodine from KI.
Estimation of available ch lorine 4KI + HCI02 + 2H20 ---7 4KOH + HCI + 212
The maximum percentage of available chlorine as calculated Chlorite ion, CI02", has angular shape. This shape is due to
from Odling's formula comes to 49%. sp3 hybridization of a-atom. .
CaOCh·H20 + H 2S04 ---7 CaS04 + 2H20 + Cl2 xXX
M. mass;,;r45 71
145 g of bleaching powder contains = 71
g chlorine -~
71
100 g " " " " .. " .." = 145 x 100 O' . :g:-
= 49 g chlorine
The estimation of availaolecIilorine-h{ a given sample or-~:
bleaching powder is done volumetrically by . III (C) Chloric Acid, HCI0 3
(ifIodometric method or (li) Arsenite method. This acid is only known in solution. The acid is prepared by
Iodometric method:' A weighed quan9ty of bleaching the action of dilute H 2S04 on barium chlorate.
powder is suspended in water and treated with excess of
Ba(CI03h + H2S04 ---7 BaS04 + 2HCI03
acetic acid and potassium iodide. The liberated iodine is
estimated by treating with a standard solution of so.dium . BaS04 is filtered off.
thiosulphate using starch as an indicator. Concentrated acid is colourless apd pungent smelling liquid.
CaOCl2 + 2CH3COOH ---"------7 (CH3COOhCa + Cl2 + H20 It decomposes in light. However, it is stable in dark. It acts as
2KI + Cl2 ---7 2KCI + 12 a strong oxidising "and bleaching agent in light. Organic
substances like paper, cotton, wool, etc., catch fire in contact
2Na2S2~ + 12 ---7 2NaI + NaZS406
with the acid.
N Chlorate ion, CIO), has pyramidal shape. The shape results
Let V mL of - Na2S203 be used for W g of a sample of
x
due to sp3 hybridization of Cl-atom.
bleaching powder. ..
V mL !'i Na2S2~ = V. mL!'i Iodine
CI
x
= V mL !'i
x
x
Chlorine .0 ···/11 ~ ...-
:0:
0.·
= x x 1600 g Chlorine
m (0) Potassium Chlorate, KCI03
Thus, % of available chlorine
::::
355xVx100 355xV Potassium chlorate is the salt of chloric acid, HCI0 3. HCI03
xxlOooxW xxW
is known only in solution but its salts are quite stable in free
The percentage of available chlorine in the commercial
state under ordinary conditions.
samples of bleaching powder is usually between 33-38%. The
Potassium chlorate is formed in laboratory by Passing chlorine
low value is due to the following factors:
gas through hot and concentrated solution of potassium
(i) Incomplete reaction between slaked lime and chlorine
hydroxide.
during its fonmltion.
(ii) Impurities present in the original slaked lime used for the 6KOH+ 3Cl2 ---7 5KCI + KCI03 + 3H20
manufacture. When the solution is cooled, crystals of KCI0 3 are obtained.
(iii) Decomposition of bleaching powder when kept in air.
Manufacture
III (B) Chlorous Acid, HCI0 2 (i) Old process: This process involves chlorination of
It- is obtained in aqueous solution when barium chlorite lime with the formation of calcium chlorate.
suspension in water is treated with H2S04' The insoluble barium 6Ca(OHh + 6Cl2 ---7 Ca(CI03h + 5CaCl2 + 6H20
sulphate is filtered off.
(x) Structures;
Total number of electron Hybridized state of Geometry and
Molecule Bond pairs Lone pairs
pairs around 'A' central atom 'A' actual shape
AB 3 4 Tetrahedral (Linear)
(ClF, BrF, BrCI,
leI, ffir)
--AB3-~---:-~----~J
Trigonal bipyrarnid
(elF 3, BrF3, (T-shaped)
IeI 3) B
B
5 6 Octahedral
(Square pyramidal)
B r ------- --------- r B
I I
r r
I r
I I
1
I
A :
I
I I
B -------- -------- B
B
7 o 7. Pentagonal
bipyramidal
12.{i~ POL YHALIDES

~'~:<l
ICI + KCl - - 7 K[ICl2]
Halide ions often react with molecules of halogens or interhalogen ICh + KCI - - 7 K[ICI4]
and fonn polyhalide ions. Iodine is only slightly soluble in ICI + KBr - - 7 K[IBrCl]
water. Its solubility is greatly increased if some iodide ions are Polyhalides are typical ionic compounds (crystalline, stable
present in the solution. The increase in solubility is due to and soluble in water, conduct electricity when in solution)
fonnation of a polyhalide ion, 13. though they tend to decompose on heating. The products of
r + 12 - - 7 13 decomposition are governed by the lattice energy of the products. .
The lattice energy of the alkali metal halides is higher for the
This ion is stable in aqueous solution and in ionic crystals. smaller halide ions, so the smaller halogen remain bonded to
More complex ions such as Is, I7 and 19 have also ~en the metal.
prepared. The Br3" and Cl3 ions are much less stttble than
Rb[ICI2] Heat) RbCI + ICI
13 .
Many polyhalides are known which contain two or three K[BrICI] Heat) KCl + IDr
different halogens, for example K[IC12], K[IC4], Cs[IDrF] and Cs[I3] - - 7 CsI + 12
K[mrCl]. These are fonned from interhalogens and metal All polyhalides are coloured. The bromo iodides are red and
halides. chlorobromides are yellow, i.e., the depth of the colour increases
..
with increase of atomic number of the halogen atoms present. are soluble in water but the silver salts are insoluble. The
Trihalide anions like ICI2, 13", [IBrCW have symmetrical linear hydrogen compounds are acids like the halogen acids, HX.
shape.' This shape results from sp3 d hybridization of central The pseudohalide ions are:
atom. Similarly the structures of the pentahalide ions [ICI4f Cyanide ion (CN) Isocyanide ion (NC)
and [BrF4f are square planar. This shape results from sld2
Cyanate ion (OCN) Fulminate ion (ONe)
hybridization of central atom. Thiocyanate ion (SCN) Isothiocyanate ion (NCS)
Selenocyanate ion (SeCN) Tellurocyanate ion (TeC~)
CI Azide ion (N3) Azido carbon disulphide ion
1 (SCSN3)
:" I: The salts formed by above ions are called pseudohalides.
"I As the dimers of halide ions are called halogens, the covalent
CI dimers of the pseudohalide ions are called pseudohalogens or
Structure of IC1 2 halogenoids. Sofar-only few of pseudohalogenshave-bee-n
isolated and characterised. The pseudohalogens known are:
12,1~ BASIC PROPERTIES OF IODINE Cyanogen (CNh Oxycyanogen (OCNh
Thiocyanogen (SCNh . Selenocyanogen (SeCN)2
In general, metallic or basic properties in halogens increase on Tellurocj'anogen (TeCNh Azido carbon disulphide
moving down the group. Iodine shows maXimum basic (SCSN3h
properties in halogen family elements although it is not"a metal. The best known pseudohalide is C~. This resembles
The compounds in which iodine functions as cationic constituent Cl-, Br- and r in the following respects:
are numerous and well established. Some examples are given (i) It forms an acid, HCN.
below: (li) It can be oxidised to (CNh molecule. .
Compounds containing unipositive iodine (1+) (Ui) It forms insoluble salts with Ag +, Pb2+ and Hgi+.
ICI, IBr, IN03 , [I(pyh]N03, [I(pyh]CI04, I 2S04 (iv) It forms large number of complexes similar to halide
Compounds containing tripositive iodine (13+) complexes, e.g.,
I(CI04h, I(CH3COOh,. IP04, I(N0 3h, ICl 3 [Cu(CN)4f- and [CUCI4f-, [Co(CN)6]3- and [CoCI6]3-
(v) Inter-pseudohalogen compounds CICN, BrCN and ICN
12.1a~ PSEUDOHALIDES AND can be formed.
,"£! PSEUDOHALOGENS} (vi) AgCN is insoluble in water but soluble in ammonia like
AgCl.
A few ions are known, consisting of two or more electro-
(vii) HCN is oxidised like HCI.
negative atoms of which at least one is nitrogen, that have
properties similar to those of halide ions. These ions are called Mn02 + 4HCN ~ Mn(CNh + (CNh + 2H 20
pseudohalide ions. Pseudohalide ions are univalent and these Mn02 + 4HCI----7 MnCl2 + Cl 2 + 2H20
form salts resembling halide salts. For example, sodium salts
Example 1. Which of the halogens (F, Cl, Br or /) provides (c) The smallest ionisation potential is of iodine.
an example of ? (d) The strongest oxidising agent is fluorine.
(a) the .weakest acid, HX, (e) The highest electron affinity is of chlorine.
(b) the largest atom, (f) Fluorine has the highest electronegativity.
(c) the smallest ionisation potential, (g) Bromine is in liquid state under ordinary conditions.
(d) the strongest oxidising agent, Example 2. Arrange the halogen hydrides in the increasing
(e) the highest electron affinity, order of:
(f) the highest electronegativity, (i) dipole moment, (ii) reducing power, (iii) thermal stability,
(g) liquid state under ordinary conditions. (iv) bond length, (v) ionic character.
Solution: Solution:
(a) The weakest acid is HE Thus, fluorine forms the weakest (i) HI < HBr < HCI < HF (Increasing dipole moment)
acid. (li) HF < HCI < HBr < ill (Increasing reducing nature)
(b) The largest atom is of iodine. (Ui) ill < HBr < HCI < HF (Increasing thermal stability)
Elements of Group VIIA or 17 (Halogens) 603
(iv) HF < HCl < HBr < HI (Increasing bond length) bromate). The mixture with conc. H 2S04 on distillation gives
(v) HI < HBr < HCl < HF (Increasing ionic character) the liquid bromine again.
Example 3. Give relevant chemical equations for the 3Br2 + 3Na2C03 ---7 SNaBr + NaBr03 + 3COz
preparation of: SNaBr + NaBr03 + 3H2S04 ---7 3Na2S04 + 3Br2 + 3H20
(i) Chlorine from sodium chloride. Example S. Gradual addition of KI solution to Bi(N03h
(ii) Iodine from Kelp.
solution initially produces a dark brown precipitate which
(iii) Hydrobromic acid from potassium bromide.
dissolves in excess of KI to give a clear yellow solution. Write
(iv) Bleaching powder from slaked lime.
chemical equations for the· above reactions. [LI.T. 1996)
(v) KCl03 from sodium chloride.
Solution: Solution:
Bi(N03h undergoes hydrolysis. Nitric acid is formed. HN03
(i) Chlorine is obtained from sodium chloride by carrying
oxidises KI, i.e., 12 (brown ppt.) is formed. The precipitated
the electrolysis of its aqueous solution.
iodine-dissolves in €xcessof-KI and forms a yeHowcoloured-
NaCl···~uNa+ +
. solution of K13'
H20 W+OH-
Bi(N03h + H 20'---7 Bi(OH)(N03h + HN03
At Cathode : W + e- ---7 H
6KI + 8HN03 ---7 6KN03 + 2NO + 312 + 4H20
2H ---7 H2! J3rown ppt.
At Anode: cr~ CI+ KI + 12 ---7 KI3
2Cl ---7 Cl2! Yellow soln.
(ii) The ash of sea-weeds (Kelp) is extracted with water, the Example 6. An inorganic compound (X) gives a brick red
sulphates and chlorides of Na and K present in it are removed flame on peiforming flame test. This compound gives the
by crystallisation. The mother liquor is now heated with Mn0 2 following tests also.
and conc. H2S04, The iodine vapours are collected in earthen (a) Smells of chlC!.rine when placed in moist air:
jars... (b) If KI and CH3COOH are added to the suspension in
2NaI + 3H2S04 + Mn02---7 2NaHS04 + MnS04 + 2H20+ 12 water, a brown colour is obtained.
(iii) HBr is prepared by heating KBr with conc. phosphoric Identify (X) and write down equations for reactions at steps
acid. (a) and (b).
3KBr + H 3P04 ---7 K 3P04 + 3HBr Solution:
Compound (X) gives a brick red flame in flame test. Thus,
(iv) Slaked lime is treated with chlorine gas by slowly moving
it is a calcium compound. It smells of chlorine on exposure
forward dry. slaked lime in a series of shelves provided with
suggests that it is bleaching powder. It is confmned by reaction
rotating rakes.
(b).
Ca(OHh + C12 ---7 CaOCI2·H20
(a) 6CaOCl2 ---7 SCaCl2 + Ca(CI03h
(v) Sodium chlorate is fIrst obtained by carrying electrolysis
CaOCl2 + CO2 ---7 CaC0 3 + Cl2
of hot concentrated solution of sodium chloride in an electrolytic
celL (b) CaOCl2 + 2CH3COOH ---7 (CH3COO)zCa + H 20 + Cl2
Electrolysis H 2KI + Cl2 ---7 2KCI + 12

NaCl ) 2 + Cl2
Solution Cathode Anode
(i) In the preparation of HI from KI, phosphoric acid is
Na+ + Olr ---7 NaOH
preferred to sulphuric acid.
Cl2 reacts with NaOH forming NaCI0 3. (it) Boiling point of HCI is lower than HF. [M.L..N.R. 19921
6NaOH + 3Cl2 ---7 SNaCI + NaCI03 + 3H20 (iii) F-F bond in fluorine is weaker than CI-Cl bond in
KCI is added to form sparingly soluble KCI03. chlorine. [M.L,.N.R.1993}
NaCI0 3 + KCI---7 KCI~ + NaCI (tv) Fluorine exhibits only oxidation state -1 while other
halogens exhibit negative as well as positive oxidation states.
Example 4. A liquid A is treated with Na'2C03 solution.
(v) Bleaching powder loses its bleaching property when
A mixture of two salts B and C are produced in the solution. kept in an open bottle for a long time.
The mixture on acidification with sulphuric acid and distillation Solution:
produces the liquid A again. Identify A, B and C and write the
(i) Besides acidic nature of sulphuric acid, it acts as an
equations involved. [IJ.T.l9!n]
oxidising agent. H 2S04 oxidises HI (reducing agent) formed
Solution: from KI into iodine. Thus, H 3P04 is preferred as it does not
The liquid A is bromine which on treatment with sodium
oxidise HI.
carbonate forms a mixture of NaBr and NaBr03 (sodium
2KI + 2H2S04 -----.. 2KHS04 + 2HI Each of the three singly occupied orbitals overlap with p-
H2S04 + 2HI -----.. 12 + S02 + 2H20 orbital of each of the three fluorine atoms to form ClF3 (trigonal
(ii) In HF, there· is hydrogen bonding. It is, therefore, an bipyramidal geometry, T-shaped molecule).
associated liquid. No hydrogen bonding is present in HCl. Only No d-orbitals are present in the valency shell of fluorine and
van der Waals' forces are present. This is the reason why thus excitation is not possible. Fluorine, therefore, does not
boiling point of HCI is lower than HF. exhibit positive oxidation state and so the formation of FC13 is
not possible.
(iii) The dissociation energy of F-F bond is lower than
(b) In NO, the size of nitrogen atom is small and the odd
Cl-Cl bond.
electron is attracted by only one oxygen atom while in 002•
F-F bond· 38 kcal mor l the size of chlorine atom is comparatively large and odd electron
CI-Cl bond 57 kcal mol-1 is attracted by two oxygen atoms. As aresuIt, the odd electron
The low dissociation -energy of fluorine is due to high inter- on N in NO is localised while the odd electron on chlorine in
electronic reptdsions between non-bonding ele0tronsinthe2p- CI02 is delocalised~ Thus, NOhasa·tendency todimerisebut-
orbitals as the size of fluorine atom is small. As a result CI02 does not.
F-F bond is weaker than CI-Cl bond. Example 10. Assign appropriate reasons for each of the
(iv) Fluorine is the most electronegative element. It shows followingstritements. .
only -1 oxidation state as it saturates its valency shell. It (a) More metal fluorides are ionic in natureJhan p~etal.~~
cannot show any positive oxidation state as d-orbitals are not chlorides.
present in valency shell while d-orbitals are present in rest of (b) Addition of Cl2 to KI solution gives it a brown colour
the halogens. but excess of Cl2 turns it colourless.
(v) Bleaching action of bleaching powder is due to release (c) Perchloric acid is a stronger acid than sulphuric acid.
of Cl2 at the time of application. Chlorine is lost by bleaching (d) Fluorine does not undergo ~disproportionation reactions
powder on long standing in open by the following two processes. but other halogens do.
(a) CaOC12 + CO2(air) -----.. CaC03 + Cl2 Solution:
(b) 6CaOCl2 -----.. 5CaCl2 + Ca(CI03h (a) A bigger anion is more easily polarized than a smaller
anion by the same metal cation according to Fajan's rules. p-
Thus, CaCl2 and Ca(CI03h do not release Cl2 at the time
ion is smaller in size in comparison to CI- ion. Thus, the metal
of use. Hence, bleaching property is lost by bleaching powder
fluoride is more ionic than the metal chloride for the same
on exposure for long time.
metal cation.
. . Example 8. Fluorine does not form oxy-acids but other (b) Chlorine being more stronger oxidising agent than 12,
halogens do, why? displaces iodine from KI which brings brown colour to the
Solution: solution. In excess of C12, the liberated iodine is further oxidised
In oxy-acids, the central element always exhibits positive to iodic acid and solution becomes colourless.
oxidation states. Fluorine, being the most electronegative, never Cl2 + 2KI -----.. 2KCI + 12
shows positive oxidation states, hence F does not form oxy- (Brown)
acids. 12 + 5Cl2 + 6H20 -----.. 2HI03 + lOHCI
Other halogens have the tendency to show positive oxidation (Colourless)
states and hence form oxy-acids. (c) The oxidation state of chlorine in HCI04 is +7 while that
Example 9. (a) Explain why CIF3 exists whereas FCl3 of S in H2S04 is +6. Thus O-H group in HCI04 is easily
does not? broken than in H2S04' Hence, HCI0 4 is a stronger acid in
(b) Both NO and CI02 are odd electron species. NO dimerises comparison to H2S04'
but C102 does not. Why? (d) F being the most electronegative element shows only
Solution: -1 oxidation state while other halogens show both negative
(a) elF3 is known because chlorine can exhibit +3 oxidation (-1) and positive (+1, +3, +5, +7) oxidation states. Thus,
state due to promotion of 3p-electron to 3d vacant orbital. fluorine dOes not show disproportionation reactions.
3s 3p 3d
Ground state chlorine
[liJ Iit Iu I i I '-------'---'---'---'------J atom
lliJ~~~;_'_'_-'--'----'---' Excited state
sp3 d-hybrldization
Elements of Group VllA or 17 (HalogeTJs) 6o.5~
t' SUMMARY AND IMPORTANT POINTS TO REMEMBER t'

1. 17th or VIlA group of the periodic table consists of fluorine, The low value of electron affinity of fluorine is probably
chlorine, bromine" iodine and astatine. These elements are due to small size of fluorine atom, i.e., electron density is
collectively called as halogens as their salts are found in sea high which hinders the addition of an extra electron.
water (Halogen is a Greek word meaning sea salt). 9. Bond length (X-X) increases from F to I.
2. Halogens are p-block elements as the last differentiating . Bond energy of F2 molecule is, however, low inspite of shorter
electron is accommodated on np subshell. These elements bond length.
have seven electrons in their outermost shell, i.e., they have F-F Cl-Cl Br-Br I-I
ns2np5 configuratlon.
.
38 keal mor l 57 455 35.6
ns np Lower value of bond dissociation energy of fluorine is due
.~~~ -~-~Lm~~ul-tJ~I~1'~I--·· to high interelectronic repulsions betweennon.;;bonding----
electrons in 2p-orbitals of fluorine.
They are allpararnagnetic atoms.
10. (a) All halogens show a common oxidation state of -1 since
3. These are highly reactive elements and never found free in
each halogen having seven electrons in the valency shell
nature but always in combined state. The salts of chlorine,
tries to accept one more electron to attain 8 electrons
bromine and iodine are found in sea water. The most common
.when combines with less electronegative· element.
compounds ofchlorlne found on earthcsulface are common
(b) Fluorine being most electronegative, always shows -1
salt or table salt or rock salt (NaCl), sylvine (KCI), hom salt
oxidation state only.
(AgCl), carnallite (MgCI2·KCI·6H20), etc. Ashes of certain
(c) Chlorine, bromine and iodine show positive oxidation
deep sea-weeds (Laminaria species) contain 0.5% of iodine
states +1, +3, +5 and +7, +3, +5 and +7 oxidation states
as iodides. Chile saltpetre (caliche) contains NaI~ in minute
due to the promotion of valency electrons to d-orbitals
quantity (0.2%). Bromine is usually obtained from sea water.
which are vacant.
The last member, astatine, is radioactive in nature.
4. All halogens exist as diatomic molecules (X2). At room (d) Besides +3, +5 and +7 oxidation states, +4 and +6
temperature, Ch and F2 are gases, Br2 is a fuming liquid while oxidation states are also shown by these elements in
12 is a volatile solid. The intermolecular forces are weak oxides and oxyacids.
van der Waals' forces, whose magnitude increases from F2 11. Standard reduction potentials of halogens are positive and
to 12- The meltinglboiling points of halogens increase down decrease from F to I. Thus, halogens act as strong oxidising
the group. agents and their oxidising power decreases from F to I.
5. Atomic radii are smallest within their respective periods. The In general, a halogen of low atomic number will oxidise the
atomic radii increase from F to I in moving down the group. halide ion of higher atomic number.
They readily form X- ions and the ionic radii also increase 12. F- ion does not show any reducing nature but CC Br- and
fromFtoT. r ion act as reducing agents and their reducing nature is in
6. These elements have high ionisation energies. The values increasing order.
decrease in moving down the group. Iodine forms positive 13. Nearly, all metals combine with fluorine either in cold or on
ions, i.e., it shows metallic nature. In the group, non-metallic heating to form fluorides. Chlorine combines with a large
decreases from F to I. number of metals but slowly. Bromine and iodine do not react
7. All the halogens are coloured. with noble metals and even with less active metals. The
reactivity of halogens towards metals decreases on moving
Fz C1 2 Br2 12 down the group. The halides are predominantly ionic in
Pale yellow Greenish yellow Dark red Violet
nature. For a particular metal the ionic character decreases
The colour of the halogens. is due to. absorption of some from F to I. With metals in higher oxidation states, the halides
wavelengths of visible light by their molecules to cause the are covalent in nature.
promotion of electrons to higher energy molecular orbitals. Halogens also combine with a number of non-metals. The
8. (a) The· halogens have high electronegativity values. The reactivity decreases from F to I.
values decrease from F to I. 14. Fluorine decomposes water very readily even in dark at low
F(4.0) Cl(3.Q) Br(2.8) 1(2.5) temperature, forming a mixture of Oz and 03' Chlorine
(b) The values of atomic volume and density increase decomposes water in presence of sunlight while bromine
steadily from F to I. decomposes water slowly in presence of sunlight. Iodine
(c) Halogens have high values of electron affinities. does not decompose water.
15. All the halogens react' with hydrogen to form volatile
F (-3.6) Cl(-3.8) Br(-3.5) 1(-3.2)
covalent hydrides of the formula HX. The activity of halogens
toward hydrogen decreases from F to I. These hydrides ,are (e) All the three monoxides, viz., OFz, ClzO and Br20 have
called hydracids or halogen acids, tetrahedral structure involving' sp3 hybridization of
(a) The hydracids are formed by direct combination of oxygen, bond angle increases with increase in size of the
halogens and hydrogen. halogen atom.
The aqueous solution of HF can be obtained by heating (f) Oxides of iodine 120 4 and 409 are not true oxides but
CaF2 with conc. H2S04 in a lead retord. Hydrogen iodates, 10(103) and I(I0 3h respectively.
chloride can be prepared by NaCI with conc. H ZS04• 17. Except fluorine, all other halogens form oxyacids of the type
However, HBr and m cannot be prepared by heating HXO, HXOz, HX0 3 and HX04. Some of these acids are quite
bromides and iodides with conc. H2S0 4 because HBr unstable.
and m are strong reducing agents and oxidised by CI Br I
conc. H 2S04 into Brz and 12 respectively. HBr and m are HClO HBrO mo hypohalous
obtained by heating bromides and iodides with H 3P04 . HCI0 2
or hydrolysis of corresponding phosphorus trihalides. HCl0 3 HBr03 HI0 3 Halic
z
... ··(OYhxcepfHrcir!f2F ;otheYhillidesare gases~-They -rome -HCl~rm-r04-HIO,i-PerITalic----
in air and have pungent odour, All are heavier than air.
(a) All these acids are monobasic and the halogen atom is
HZF2 is a liquid due to association of molecules through sp3 hybridized. .
hydrogen bonding, The boiling points vary as : (b) Acidic character increases with increase in oxidation
HCl·<-HBF <:·····H[·<HF number of the halogen. '
(-8S'C) (-6rC) (-3S.5°C) (l9.5"C)
HClO <: HCl02 <: HCl~ <: HCl04
(c) The bond strength decreases from HF to m. The decre- (c) In any series, acidic character decreases as the electro-
as~ iIi stability is due to decrease in electronegativity. , negativity decreases.
The dissociation energy of H-X bond dec~eases.
HCI04 > HBr04 > m04
H-F > H-CI > H-Br > H-I (d) Oxidising nature for the same halogen decreases.
1
136 keal mol- 105 86 70
(d) The reducing nature increases from HF to HI. HF does HClO > HClOz > HCl03 > HCl04
not shoW reducing nature. (e) Stability for the same halogen increases.
(e) Dipole moment of these hydrides decreases from HF to HClO <: HClOz <: HCl~ <: HCl04
·ffi.
18. Fluorine reacts with cold dilute alkalies yielding OF2 and with
(i) Acidic nature of these hydrides is m > HBr > HCI > HF.
conc. alkalies evolve oxygen.
This .is because of the fact that the strength of the
conjugate base increases as : • 2Fz + 2NaOH ---:--'t 2NaF + OFz + HzO ;
Cold +dil.
1- '< Br- <: Cl- <: p-
2Fz +4NaOH~4NaF+02 +2H20
Cone,
(g) HCI, HBr and m form one series of salts while
hydrofluoric acid forms two series of salts MHF z and C12, Br2 and Iz behave similarly towards alkalies. With dilute
Ivt'2F2 (M is monovalent). and cold alkalies form a mixture of halide and hypohalide
16. Halogens and oxygen do not combine directly with each while with hot and conc. alkalies form a mixture of halide and
other. However, these compounds have been obtained . halate.
indirectly. The known compounds are : 2NaOH+X2~NaX+ NaXO+H20;
Cold+dil. Hypohalite
OF2 ClzO . Br20 120 5 6NaOH + 3X2~ 5NaX + NaX03+ 3H20
OzF2 ClOz BrOz Hot + cone, Halate
Clz06 Br~ 19. The halogens on account of difference in the electro-
ClzO, .
negativities combine with each other to form compounds of
The compounds of oxygen and fluorine are not called oxides the type ABn where A is always bigger atom and B is smaller,
but fluorides as fluorine is more electronegative than oxygen. atom and n may have values 1,3,5 and 7. These are covalent'
(a) Oxides of CI, Br and I are acidic and acidic character compounds and called interhalogen compounds.
increases with increase.of percentage of oxygeJ;l in them. AB type ClF, BrF, BreI, ICI, IBr
• (b) All the oxides of halogens are powerful oxidants, highly AB3 type ClF3, BrF3, ICI3 ~sp3d hybridization of A.
reactive and unstable towards heat. In general, higher Two lone pairs
oxides are relatively more stable than lower oxides for a ABs type IFs,BrFs ~ 2 hybridization of A .
sld
._particular halogen. One lone pair
(c) Oxygen fluorides do not form oxyacids. AB7 type IF7 ~ sp3d3hybridization of A.
(d) In these oxides, bonds are mainly covalent due to small
Interhalogen compounds are gases or liquids. These are
difference in the electronegativity of oxygen and
volatile and fume in air. These compounds are more reactive
halogens.
than halogens except fluorine because A-B bond is weaker Pb304. KMn04, K2Cr207, 03, NaCIO, etc. (ii) by heating dry
than B-B bond. These are hydrolysed and act as oxidising platinum chloride (PtC14) or gold chloride (AuCI 3) in a hard
agents. glass tube. It gives pure chlorine.
20. Halide ions often react with molecules of halogens or The methods used for its manufacture are :
interhalogens and form polyhalides. (a) Weldon's process (Mn02 + HCI) (b) Deacon's pfocess-
r-+I2~I3
chlorine is obtained by air oxidation of HCl in presence
of CuCh as a catalyst (c) Nitrosyl chloride process
13" (polyhalide) ion is stable in aqueous solution and in
(d) By-product in the manufacture of caustic soda or sodium.
ionic crystals. More complex ions such as Is. Ii and 19" have
Chlorine is stored and transported in liquid state.
been prepared. The Br3" and C13 ions are much less stable
25. Chlorine is a yellowish green gas with. pungent suffocating
than 13. and poisonous nature. It is fairly soluble in water. The
Many polyhalides are known in which two or three different
aqueous solution is called chlorine water which gives crystals
halogens are present such as ICli. ICI4. (ffirF)- and (ffirCl)-.
of chlorinehydrate (C12·8H20) !l.t 9°C. InJ>!~sen~Qf mois~~_
21. SQme of the milll9xalenUonsmade_oLelectronegati¥eatoms
and possessing properties similar to halide ions are known
itaciS-as-all oXidisingand bleaching agent.
26. Chlorine is used in the manufacture of bleaching powder,
which are called pseudohalide ions. The corresponding
chlorates, hypochlorites, HCI, chloroform, CCI4, phosgene
dimers having no charge of these pseudohalide ions are
(COCI2), tear gas (CCI3·N02) and mustard gas (CI-C2.H4-
talled p~eudohalogens.
S~2IIA-:;-;·q). It i~us~inpurificationofdrinking water and=c=
·Psetidohalide:i5nK· . ··Pseuoonalogens . as a bleaching agent for cotton fabrics, paper and rayon.
Cyanide ion (CN-) (CNh Cyanogen 27. Bromine was discovered by BaJard in 1826. It is obtained
Thiocyanate ion (SCN) (SCNh Thiocyanogen either from the mother liquor obtained after crystallising KCl
Cyanate ion (OCN) (OCNh Oxycyanogen from carnallite or from sea water by passing Cl2 gas. The
22. The important minerals of fluorine are : vapours are absorbed in Na2C~ solution when a mixture of
(i) Fluorspar (CaF2); (ii) Cryolite (Na3AlF6); (iii) Fluorapatite NaBr and NaBr03 is obtained which is distilled with H2S04
[CaF2·3Ca3(P°4hJ to recover bromine.
In small amounts, it is present as fluorides in plant ashes, 28. Iodine Was discovered by Courtois in 1812. Two main sources
soil, sea water, bones and teeth of animals. of iodine are :
The isolation presented many difficulties. It was fmally . (a) Deep sea-weeds' ashes known as kelp contains 0.5%
isolated by Moissan in 1886 by electrolysis of anhydrous iodine in the form of iodides.
hydrofluoric acid in potassium hydrogen fluoride (KHF2) (b) Caliche or crude chile saltpetre which contains 0.2% of
using Pt-Ir vessel at -23°C. The electrodes used were also NaI°3·
of Pt-Ir alloy. 29. 12 is slightly soluble in water. The solubility can be increased
In modem methods, fluorine is prepared by electrolysis of by addition of Kl.
fused KHF2. The electrolytic cells are made of copper, nickel Kl + 12 ~ Kl3 (Soluble)
or monel metal. The anode is generally of graphite. The It is soluble in organic solvents such as chloroform, carbon
fluorine set free contains some carbon tetrafluoride. The tetrachloride, alcohol, ether, etc. It oxidises Na2S203 into
methods used are: (i) Dennis and (ii) Whytlaw-Gray. sodium tetrathionate. This reaction is useful in iodometric
23. The fluorine compounds have wide applications : titrations.
(a) Freon, CF2Ch (dichlorodifluoro methane) is used in 30. Tincture of iodine is a mixture of 12 and Kl dissolved in
refrigerators and cold storage plants. rectified alcohol. It is used as antiseptic. Iodex-a product
(b) Teflon (C2F4)x, a new plastic, has a very high electrical containing iodine is used as 'antiseptic and analgesic.
resistance and is used as insulating material. It is not Although iodine does not displace chlorine or bromine from
affected by acids, alkalies and strong oxidising· agents. the solutions of their s.alts, yet it displaces them from their
(c) H2F2 is used for etching of glass~ oxysalts.
(d) SF6 has insulating properties. It is used il1 X-ray and high
2KCI03 + 12 ~ 2Kl0 3 + Ch
voltage machines.
2KBr03 + 12 ~ 2Kl03 + Br2
(e) NaF and Na3AlF6 are used as insecticides.
(f) CuF2 is used in ceramic industry. 31. Bleaching powder (CaOCI 2·H20) is also called calcium
(g) UF6 is used for separation of U 235 isotope from natural chlorohypochlorite because it is a mixed salt of hydrochloric
uranium. acid and hypochlorous acid. It is represented as :
(h) Sodium fluoroacetate is used as a rat poison.
<
OCI
24. Chlorine was discovered by Scheele in 1774. The old name
Ca
is oxymuriatic acid gas. Common salt (NaCl) is the most
important chloride which occurs in sea water, lakes and in . CI
rocks. It is prepared (i) by oxidation ofHCl with Mn02> Pb0 2, It is obtained by the action of Cl 2 on slaked lime.
Bleaching powder loses its chlorine content by the action of 34. Iodine shows electropositive nature as it has lowest
dilute acids or carbon dioxide. The amount of chlorine ionisation potential among halogens. It has the tendency to
obtained from the sample of a bleaching powder by this way lose electron or electrons to form 1+ and 13+ cations.
is termed available chlorine. A good sample of bleaching Compounds such as ICl, ICN, ICI3, IP04, I(CH3COOh. etc.,
powder contains 35-38% of available chlorine. are known.
On long standing bleaching powder undergoes auto- 35. Some of the products of halogens have been given special
oxidation into calcium chlorate and calcium chloride. names.
6CaOCI2~ 5CaCl2 + Ca(CI03h Mg(CI04h Anhydrone
The products do not have available chlorine. Thus, bleaching KO~ Berthelot's salt
powder loses available chlorine with time. KHF2 Ferming's salt
32. When a chloride is heated with cone. H2S04 in presence of Aq. soIn. of NaOCI Javelle water
solid K2Cr207 in a dry test tube, deep red vapours of chromyl eaOO2·H20 Bleaching powder
chlQride .... ar~ ~y()l.Ye<:l, Wh~l! tllJ~Se,,-ap()l1rs_/.l1'~J)~sed Cl2 and CI02 mixture Euchlorine
through NaOH solution, the solution becomes yellow due to . SoIn. ofHCl'~'-~-=~-Spiritcif salf~·-··-.
formation of sodium chromate. The solution is neutralised C03NOz Tear gas
with acetic acid and on addition of lead acetate solution, a 02 Oxymuriatic acid gas
yellow precipitate of lead chromate is formed. This is a test,
36. Cl2'and F2 do not react with starch solution. Br2 gives yellow
bichloride ion and is known as chroniyl chloride test.
colour with starch solution and 12 gives deep blue.colour Witlb~
33. Warming KCI0 3 with conc. HCI gives a mixture of Cl2 and
starch solution.
CI02 known as euchlorine which is a bleaching agent.
-- - - -- ~ ~,..
- • •. ,. -
, ""~, _
PRACTICE PROBLEMS ~. ~ ",.,~
_, ;_.t';;,~.~ : ",.~_ '- .•~_
• Subjective Type Questions (v) Write the two important minerals of fluorine. '
(vi) Name four oxyacids of chlorine. Give their molecular
1. Name the element of group 17, which has the following formulae.
properties: (vii) Name the halogen which gives ozone with water.
(a) highest electron affinity (viii) Name the oxide of chlorine which has odd number
(b) strongest oxidising agent of electrons and pl'\l'amaglietic in nature.
(c) radioactive (ix) Give one example each of the compound of chlorine
(d) violet solid in which it shows +1, -1, +3, +4, +5, +6 and +7
(e) does not exhibit positive oxidation state oxidation state.
2. Among the hydrides of halogens predict the hydride having: (x) Name the halogen which has highest bond energy
(a) highest boiling point amongst halogens.
(b) strongest reducing agent (xi) Name the compound which on electrolysis gives
(c) most stable fluorine gas at anode.
(d) least acidic (xii) Name the fluoro carbon used in refrigerators.
(e) lowest boiling point (xiii) Name two poisonous gases of chlorine used in the
3. Complete and balance the following chemical reactions: warfare.
(i) 12 + NaCI03 ~ (xiv) What is the atomicity of halogens?
(n) 103' +r + H+ ~ (xv) What is the percentage of available chlorine in a good
(iii) Br2+NaI~ sample of bleaching powder?
(iv) 12 + S20~- ~ (xvi) Name two interhalogens of AB3 type.
(xvii) What are the constituents of tincture of iodine?
(v) Br0 3+ F2 + OH- ~
(xviii) What is the colour of vapours obtained when an
4. Answer the following: iodide is heated with conc. H 2S04?
(i) Write the general electronic configuration of halogens (xix) What is the shape of HCI04?
in the valence shell. (xx) What is the shape of CIF3?
(n) Name the halogens. 5. Complete the following reactions and give balanced
(iii) Name the radioactive (last) element of VIlA or 17th equations:
group. (i) CI2 +OH- ~ .......... + CI03- +; ....... ..
(iv) Write the physical states of halogens under ordinary
(li) Mn02 +HCl ~ MnCl2 + .......... + ........ ..
conditions.
Elements of Group VilA or 17 (Halogens)
(ill) NH3 + CI2(excess) -----:-" .......... + HCl (i) F, CI, Br, I in order of increasing electronegativity or
(iv) KMn04 + KCl + H2S04 ~ reactivity.
K2S04 + MnS04 + .......... + ......... . (j) F, Cl, Br, I in order of increasing electron affinity.
(v) K2Cr207 + HCI ~ KCI + CrCl3 + .......... + ......... . 8. Write chemical formula and uses of the following:
(i) Muriatic acid (ii) Freon (iii) Hypo solution
[I.I.T. 1992]
(iv) Caliche (v) Kelp (vi) Bleaching powder.
(vi) CUS04 + KI ~ CU212 + .......... + ........ ..
9. Give equations only:
(vii)NH3 + NaOCI ~ N2 + NaCI + ......... . (i) How chlorine is obtained from the following substances?'
(viii) O 2 + H20 + HgO ~ HgCI2·HgO + ........ .. (a)HCI (b) NaCI (c) KCI03 (d) Bleaching powder
(IX) P4 + 12 + H 20 ~ H3P03 + ......... . (Ii) How bromine is obtained from the following substances?
(x) NaBr + Mn02 + H2S04 ~ (a) NaBr0 3 (b)HBr (c)KBr
NaHS04 + .......... + H20 + ........ .. -(ill) How iodine is obtained from the following substances?
(xi) H2S04 +ffi ~ .......... + .......... + ........ .. (a)KI (b) NaI03 (c)m
~[Roorkeel998] 10; ·What-is-the~xidation~numberof-th:evarioushalogen ·atoms--
(xii) CaOCI2+NaI+HCI ~ ..: ....... +CaCIz+H20+NaCI present in the following?

[Roorkee 19981 (i)CIF (ii)ICI (iii)PCls (iv)Clz (v) KCI03 (vi) K004
6. What happens when? (Give balanced equations) (vii) HCI02 (viii)CI 20 (ix)F20 (X)CI2~'
(i) Sodium iodate is treated with sodium bisulphite 11. What is the geometry and hybridization of the central atom
solution. of the follOWing moleCules or ions?
(li) Chlorine is passed through hot N aOH solution. z
(i) CIOi (ii) CIO] (iii) IF7 (iv) ICl (v) IC14 (vi) Cl 20
[M.L.N.R. 1990] (vii) IF3 (viii) CI02.
(ill) Chlorine is passed into aqueous potassium hydroxide. lZ. Write short notes on:
(iv) Chlorine gas is bubbled through a solution of ferrous (i) Available chlorine.
bromide. (li) Interhalogen compounds.
(v) Iodine reacts with conc. HN03. [M.L.N.R f992] (Iii) Pseudohalogens.
(vi) Chlorine is passed over slaked lime. (iv) Basic properties of iodine.
(vii) Sodium chloride is heated with K2Cr2~ and conc. (v) Use of bleaching powder in textile industry.
HzS04. [I.I.T.1990] (vi) Relative acid strength of the hydracids of halogens.
(viii) Potassium iodide is heated with Mn02 and conc. (vii) Relative oxidising nature of halogens.
H2SO4. (viii) Relative acid strength of the oxyacids of chlorine.
(IX) Chlorine reacts with NaZS03 solution. 13. (i) Describe the iodometric method for estimating available
(x) Iodine is added to stannous chloride solution. chlorine in the given sample of bleaching powder..
(xi) Chlorine is passed through a suspension. of iodine. (ii) Give the chemistrY of the test of fluoride.
(xii) O 2 is passed through a suspension of CaC03. (ill) Give the chemistry of chromyl chloride test.
(xiii) Chlorine gas is passed through dry and aqueous (iv) Give the chemistry of chloroform test for the detection
sulphur. dioxide. of bromide and iodide ions. --
(xiv) Bromine reacts with Na2C03 solution. 14. Explain the following with proper reason:
(xv) Potassium iodide is added to bleaching powder con- (i) Fluorine cannot be prepared from fluorides by chemi -
taining dilute acetic acid. cal oxidation.
7. Arrange the following: [Hint : The standard reduction potential of fluorine is
maXimum.
(a) HCIO, HCI02, HCI03, HCI04 in increasing order of
thermal stability. .. ..
(b) HCIO, HCI02, HCI03, HCI04 in order of increasing acid ..
:F. + e- ---7: F:-
strength.
Thus, it cannot be oxidised by any other reagent.
.(c) HClO, HCI02, HCI03, HCI04 in order of increasing P- ion is very stable due to small size and high
oxidising power. electronegativity of fluorine atom.]
(d) F, CC Br-, r in order of increasing reducing nature.
(li) Anhydrous HCI is a bad conductor of electricity while
(e) 12, m, mo4, ICI in order of increasing oxidation number
aqueous HCI is a good conductor. [I.I.T.1995]
of iodine. [Bint : In anhydrous state, HCI is a covalent molecule. In
(t) HOF, HOCI, HOBr, HOI in order of increasing acid aqueous solution, HCI combines with water
strength. molecule to form H30+ and CI- ions.
(g) Fz, Clz, Brz, 12 in order of increasing oxidising power.
HCI + H20 ~ H30+ + Cl- ]
(h) HF, HCI, HBr, HI in order of increasing acid strength.
(iii) Halogens are coloured. [Hint : ill is a strong reducing agent. It is even oxidised by
[Hint : Halogens absorb part of the light in the visible oxygen of the air. The iodine is liberated which is
region which cause excitation of outer electrons to dissolved imparting a brown colour to solution.]
higher energy levels. The excitation energy depends (xi) Iodine dissolves more in KI solution than in water.
on the size of the halogen atom, the smaller the [Dhanbad 1992]
atom, the greater is the excitation energy. Thus, [Hint : 12 is a covalent molecule. Thus, its solubility is less
fluorine absorbs violet light and thus appears in polar solvent, i.e., water. Potassium iodide com-
yellow (complementary colour). As different bines with iodine and forms a polyhalide which is
colours are absorbed by halogens, they display an ionic compound. Being ionic, KI 3 is more soluble.
different complementary colours also.]
KI + 12 ~ KI3(K~3)]
(iv) Halogens are strong oxidising agents. 2
(xii) Iodine is liberated in the reaction between KI and Cu +
[Hint : Halogens act as strong oxidising agents because they
but chlorine is not liberated when KCI is added to
have high tendency to accept electron, i.e., they have
Cu 2+ ion.
high electron affinity values. Their reduction 2
_____________potentials_are_hig~(positi\'e)_and-decIeaseJromE [Hint : r ion is a strong reducing agent. It reduces Cu +
-------- Ion to -C-u+ ion. -TIt-e-cF-Ton-Is-ii- weak -reaucing
to I. Thus, oxidising nature decreases from F to I.]
agent. Thus, it does not reduce Cu 2+ ion.
(v) When a blue litmus is dipped into a solution of
2Cu 2+ + 4KI ~ CU2I2 + 12 + 4K+ ]
hypochlorous acid, it fIrst turns red and then later gets
decolourised. (xiii) KHF2 is well known whereas KRCl2 or KHBr2 does not
[Hint: HClO is an acid,' thus tums blue litmus into red. exist.
HClO is also an oxidising agent. The nascent oxygen [Hint : Hydrofluoric acid exists as dimeric molecule (H2F2)
given by HClO bleaches the red litmus. due to hydrogen bonding. It, thus, exhibits dibasic
Red litmus + 0 ~ Colourless] nature and forms two series of salts, KHF2 as [K+
and F- - - - - H-F] and KF[K+ and Fl. HCl and
(vi) The bleaching action of chlorine is pennanent while RBr exist as monomeric molecules as hydrogen
that of sulphur dioxide is temporary. bonding is not present.]
[Hint : Chlorine bleaching action is due to oxidation while
(xiv) A fresh iodine stain can be removed by washing with
that of sulphur dioxide is due to reduction. Hence,
the substance bleached by S02 is reoxidised by the hypo solution.
oxygen of the air to its original state.] [Hint : Hypo reacts with iodine to form water soluble
colourless sodium tetrathionate and sodium iodide.
(vii) The brown colour of an acidifIed dilute solution of
2Na2S203 + 12 ~ 2NaI + Na2S406 ]
iodine in aqueous potassium iodide is intensifIed by
addition of a nitrite but is discharged by the addition (xv) Dry chlorine does not bleach clothes.
of sulphite. [Hint : The bleaching action of chlorine is due to the
[Hint : Nitrite ions oxidise iodide ions to iodine and thus
liberation of nascent oxygen from water (moisture).
brown colour is intensified. H20 + Cl2 ~ 2HCl + (0) ]
4H+ + 2N0 2- + 2r ~ 2NO + 12 + 2H20 (xvi) Ferric iodide is very unstable but ferric chloride is
Iodine acts as an oxidising agent with sulphite and stable.
converted into C i.e., the solution becomes [Hill' r ion is a strong reducing agent. Iodide thus reduces
colourless. ferric into ferrous. Cl- ion is a weak reducing agent
and does not reduce Fe3+ to Fe2+.]
12 + SO~- + H20~SO~- + 2H+ + 2r]
(viii) Fluorine is a non-metal whereas iodine shows some
(xvii) HF is least volatile and HCI is most volatile amongst
metallic properties as well. hydrogen halides.
[Hint : In covalent compounds, the boiling point increases
[Hint : Ionisation potential decreases on moving down from
with increase of molecular mass as van der Waals'
F to I. The iodine can lose electron/electrons and
form positive ions and hence shows metallic forces increase. The volatility thus, decreases in
covalent compounds with increase in molecular
character.]
mass. However, hydrogen bonding is present in HF.
(Ix) Colour of potassium iodide solution containing starch Due to which, the boiling point of HF is higher and
turns blue when chlorine water is added. the· volatility is less. Thus, the volatility of
[Hint : Chlorine being more reactive displaces iodine from hydrogen halides can be represented as:
KI. Iodine is absorbed by starch and thus blue HCl > RBr > ill > HF ]
colour is developed. Most volatile Least volatile
2KI + Cl2 ~ 2KCl + 12 (xviii) Fluorine does not form F3 (polyhalide) ion.
~ + Starch ~Blue colour] [Hint : ~o d-orbitals are present in fluorine while d-orbitals
(x) Pure HI kept in a bottle acquires a brown colour after are presc:nt in other halogens. The formation of Xi
. ion involves·sp3a -fi-ybndizatiori.] .
sometime.
o
Elements of Group VIIA or 17 (Halogens)
(xix) Fluorine gives fumes with moist air. powder. Explain the chemical reactions involved with
[Hint : Fluorine reacts with water to fonn HF. equations.
2H20 + 2F2 ---7 4HF + O2 17. A sodium salt is heated with concentrated sulphuric acid.
HF, being liquid, absorbs liquid droplets to fonn The evolved gas is found to turn moist litmus paper red and
fumes.] produce white fumes in contact with a glass rod moistened
(xx) Interhalogens are more reactive than halogens. with anunonia solution. It also gives white precipitate when
[Hint : The bond in the interhalogen A-X is weaker than passed through AgN03 solution. When the salt is heated
X-X bond in the halogens. This is on account of with Mn0 2 and conc. H 2S04, a gas with an irritating smell is
less effective overlapping between orbitals of evolved which turns starch-iodide paper blue. Identify the
dissimilar atoms than those of similar atoms.] salt and the gaseous product evolved from it Explain your
(XXI) HF is not stored in glass bottles but kept in wax answer with relevant chemical equations ..
bottles. 18. A certain compound (X) shows the following reactions.
[Hint : HF attacks glass bottles. The sodium and pota- (i) When KI is added to an aqueous suspension of (X)
~sium-silicates-are-convertOO-jnt{)-fluomsilicates, . . containing-aceticacid;-iodine-is-liberated;-
Na2Si03 + 6HF ---7 Na2SiF6 + 3H20 ] (li) When CO 2 is passed through an aqueous suspension
(xxii) HF has a greater electronegativity difference and more of (X), the turbidity transforms to a precipitate.
ionic character than HCI, HEr and ill but it is the (iii) When the paste of (X) in water is heated with ethyl
weakest acid. alcohol, a product of anaesthetic use is obtained.
is
[ltiDt : The weakest acidic nature ofHF due to following Ideiltify(X) a.ildwrite downchenncal equations=rur
three factors; reactions at step (i), (ii) and (iii). [Roorkee 1992]
(i) Strong bond as the dissociation energy 19. A colourless inorganic compound imparts a green colour to
is high. flame. It's solution does not give any precipitate with H2S,
(ii) Large heat of dehydration due to hydrogen It's solution gives white precipitate with H2S04' When it is
bonding.
heated with K2Cr207 and conc. H2S04, a red gas is evolved.
(iii) Low value of electron affinity.]
The gas when passed through aqueous NaOH solution turns
15. The following statements are correct under certain it yellow. Identify the compound and give chemical reactions.
conditions. Mention the conditions.
(i) Chlorine is a good bleaching agent. • Matching Type Questions
(li) A mixture of H2 and Cl2 explodes.
(iii) Cl2 reacts with NaOH solution to produce sodium Match the following:
chloride and sodium hypochlorite (along with water). [A]
(iv) Cl2 reacts with NaOH solution to produce sodium (i) Fluorine (a) Carnallite
chloride and sodium chlorate (along with water). (ii) Chlorine (b) Hydrogen bonding
(v) Cl2 substitutes hydrogen atoms of a molecule of (iii) Bromine (c) Beckmann's process
methane. (iv) Iodine (d) Reducing agj;nt
(vi) Cl2 reacts with anunonia to form nitrogen and anuno- (v) Bleaching powder (e) Pseudohalogen
nium chloride. (vi) HF (f) Dennis process
(vii) Cl2 reacts with lime to form bleaching powder. (vii) HI (g) Seacweeds
(viii) Iodine dissolves freely in water. (viii) (CNh (h) Deacon's process
(ix) Chlorine forms an addition product with S02. [B]
16. A black powder when heated with NaCI and conc. H2S04 (i) Moissan (a) Chlorine
gives off a greenish yellow gas. The gas on passing through (li) Scheele (b) Bleaching powder
liquor ammonia liberates N2 and on passing through boiling (iii) Balard (c) Iodine
KOH yields compounds one of which when heated with the (iv) Courtois (d) Fluorine
black powder evolves oxygen. Name the gas and the black (v) Odling (e) Bromine
Answers : Subjective Type Questions 4. (i) nini (ii) Fluorine, chlorine, bromine, iodine (iii) Astatine
1. (a) CI (b) F (c) At (d) I (e) F (iv) Fluorine and chlorine are gases, bromine is liquid and iodine is
2. (a) HF (b) HI (c) HF (d) HF (e) HCI solid. (v) Fluorspar (CaF2); cryolite (Na3A1F6) (vi) Hypochlorous
3. (i) 12 + 2NaCI03 ~ 2NaI03 + CI 2 acid (HCIO), Chlorous acid (HCI02); Chloric acid (HCI0 3);
(ii) 103 + 51- + 6W ~ 312 + 3H20 Perchloric acid (HCI04) (vii) Fluorine (viii) Chlorine dioxide, CI02
(iii) Br2 + 2Nal ~ 2NaBr + 12 (ix) Cl20 (+1), HCl (-1), ClF3 (+3), CI02 (+4), HCI03 (+5),
(iv) 12 + 2S201- ~ S40~- + 2r C120 6 (+6), HCI04 (+7) (x) chlorine (xi) Fused anhydrous
(v) Br03 + F2 + 20W ~ Br0 4 + 2F + H20 potassiurr1 hydro:;.m fluoride (KHF2) (xii) Freon (CF2CI2 )
•
(xiii)Phosgene (COC12), Tear gas (CCl~02) (xiv) two (v) Kelp NaI In small amount for the
(xv) 35-38% (xvi) Chlorine trifluoride (ClF3); iodine trichloride (lC13 manufacture of iodine
or 12C1 6) (xvii) Iodine, potassium iodide and ethyl alcohol (vi) Bleaching powder CaOClz As a bleaching agent and
(xviii) Violet (xix) Tetrahedral (xx) T-shaped. gennicide
5. (i) 3CI2 + 60Ir ----7 5Cl- + CI03 + 3H20 9. (i) (a) By heating conc. HCI with manganese dioxide.
(ii) Mn02 + 4HCl ----7 MnCI2 + CI2 + 2H20 Mn02 + 4HCI ~ MnCI2 + 2H20 + Cl z
(iii) NH3 + 3CI2(Excess) ----7 NCI3 + 3HCI (b) By doing electrolysis of NaCI solution.
(iv) 2KMn04 + IOKCI + 8H2S.04 ----7
(c) By treating KCI03 with iodine.
6K2S04 + 2MnS04 + 5Cl2· + 8H20
.(v) K2Cr207 + 14HCI ----7 2KCl + 2CrCb + 7H20 + 3Cl2 2KCI0 3 + 12 ~ 2KI0 3 + Clz
(vi) 2CUS04 + 4KI 2K2S04 + CU212 + 12' (d) Bleaching powder is treated either with mineral acids or COz.
(vii) 2NH3 + 3NaOCl----7 .3NaCl + N2 + 3H20 CaOClz + H2S04 ~ CaS04 + HzO + Cl2
(viii) 2Cl2 + H20 + 2HgO ----7 2HCIO + HgO·HgC,12 CaOC12 + CO2 ~ CaC03 + C12
.. __(ix)--.J>4_±.JiI2..±..12H20>..4H#03.+..l2IDLLL.._ _ ~ti)~(a)Byheati:rrg-ml.xture-cofltai.nlngNaBr and~NaBf{l3-wi~·
(x) 2NaBr + Mn02 + 3H2S04 ----7 hydrochloric acid.
2NaHS04 + MnS04 + 2H20 + Br2
5NaBr + NaBr0 3 + 6HCl ~ 6NaCI +3Brz + 3H20
(xi) H2S04 + 2ID ----7 12 + S02 + 2H20
(xii) CaOC12 + 2NaI + 2HCl----7 12 + CaCl2 + H 20 + 2NaCl
(b) By heating HBr with MnOz
6. (i)2NaI03 + 5NaHS03----73NaHS04 + 2Na2S04'+ H 20 + 12 MnQ2c+ 4~r ---:7 MnBr2 +. Br2 +21;120
(ii)3C12 + 6NaOH(conc.) Hot) 5NaCl + NaCI03 + 3H20 or by passing Cl2 through HBr.
(iii) Ch + 2KOH(aq.) ----7 KCl + KCIO + H20 CI2 + 2HBr ~ 2HCl + Br2
(iv) 2FeBr2 + 3C12 ----7 2FeCl3 + 2Br2 (c) By heating KBr with Mn02 and conc. H2S04 or by passing
(v) 12 + IORN03 2ID03 + lON02 +4H20 C12 through KBr solution.
(vi) Ca(OHh + Cl2 ----7 Ca(OC1)Cl + H20 (iii) (a) By heating mixture of KI and Mn02 with conc. H2S04 or
(vii)4NaCl + K2Cr207 + 6H2S04----7 by treating Kl with H20 2.
2Cr02CI2 + 4NaHS04 + 2KHS04 + 3H20 2Kl + H 20 2 ~ 2KOH + 12
(viii) 2KI + Mn02 + 3H2S04 ----7 2KHS04 + MnS04 + 2H20 + 12
(b) Sodium iodate is.treated with calculated quantity of sodium
(ix) C12 + Na2S03 + H20 ----7 2HCI + Na2S04 bisulphite.
(x) SnCl2 + 2HCl + 12 ----7 SnC4 + 2ID 2NaI03 + 5NaHS03 ~ 3NaHS04 + 2Na2S04 + HzO + 12
(xi) 12 + 5Cl2 + 6H20 ----7 2ID0 3 + IOHCl ' (c) By passing Clz through ID.
(xii) 2CaC03 + 2C12 ----7 CaCl2 + Ca(CI0h + 2C0 2 2ID + Ch ~2HCI + 12
(xiii) S02 + Cl2 ----7 S02Cl2 10. 0) Cl +1, F =-1 (ii) 1= +1, CI = -1 (iii) Cl =-1 (iv) Cl =0
'-.;--' = =
(v) +5 (vi) Cl +7 (vii) Cl = +3 (viii) Cl + 1 (ix) F -1
Dry (x) Cl +7.
S02 + Cl 2 + 2H20 ----7 H2S04 + 2HCl 11. (i) Angular, sp3 hybridization of CI-atom
(xiv) 3Br2 + 3Na2C03 ----7 5NaBr + NaBr0 3 + 3C02 (ii) Pyramidal, sp3 hybridization of CI-atom
(Cone. and hot) 3
(iii) Pentagonal bipyramidal, sp i hybridization of I-atom
(xv) CaOCl2 + 2CH 3COOH + 2Kl ----7 (iv) Linear, sld hybridization of I-atom
(CH 3COOhCa + 2KCl + 12 + H20 (v) Square planar, sldz hybridization of I-atom
7. (a) HCIO < HCI0 2 < HCI0 3 < HCl04 (vi) V-shaped, sp3 hybridization of O-atom
(b) HCIO < HCI02 < HC103 < HCI04 (vii) T-shaped, sp3d hybridization of I-atom
(c) HCI04 < HC103 < HClOz < HClO (viii) Angular, sld hybridization of Cl-atom.
(d) F < Cl- < Br- < r
12. See text
(e) ID < 12 < ICI < ID04 13. See text
(0 HOI < HOBr < HOCI < HOF 15.. (i) In presence of moisture (ii) On exposure to direct sunlight
(g) Iz < Brz < CI2 < Fz (iii) When NaOH solution is cold and dilute (iv) When NaOH
(h) HF < HCl < HBr < ID
solution is concentrated and hot (v) In diffused sunlight (vi) When
(i) I < Br < CI < F
NH3 is in excess (vii) When Cl2 is passed over dry slaked lime
G) I < Br < F < Cl
(viii) When Kl is present (ix) When both are dry.
8. Ci) Muriatic acid HCI Laboratory agent
16. The black powder is Mn02 and greenish-yellow gas is chlorine.
As an acid Mn02 + 2NaCl + 3H2S04 ----7 2NaHS04 + MnS04 + Cl2 + 2H20
(ii) Freon CF2Cl2 As a refrigerant
3C12 + SNH3 + 6N~Cl
(iii) Hypo soIn. Na2S203 (i) Used in photography
3Cl2 + 6KOH ----7 KCI0 3 + 5KCl + 3H20
(ii) As a volumetric reagent
2KCl03 + [MnOil ----72KCl + 302 + [MnOil
(iv) Caliche NaI0 3 For the manufacture of 17. The salt is NaCl and the evolved gas is HCl.
(main constituent) iodine
NaCl + H2S04 -----7 NaHS04 + HCI C2HSOH + Clz -----7CH3CHO + HC!.

HCl + Blue litmus -----7 Red litmus CH3CHO + 3Cl2 -----7 CChCHO + 3HCI
HCI + NH3 -----7 NH 4CI 2CCl3CHO + Ca(OHh -----7 2CHCI3 + (HCOOhCa
White fumes 19. The compound is BaCI2.
HCl + AgN03 -----7 AgCI + HN03 BaCl2 + H2S04 -----7 BaS04 + 2HCI
White ppt. White ppt.
2NaCI + MnOz + 3H2S04 -----7 2NaHS04 + MnS04 + 2H20 + C12 2BaC12+ K2Cr207 + 3H2S04 -----7
Cl 2 + 2KI -----7 2KCI + 12 K2S04 + 2Cr02Cl2 + 2BaS04 + 3H20
Turns starch iodide paper blue. Red
IS. The compound (X) is bleaching powder, CaOC12. Cr02Cl2 + 4NaOH -----7 Na2Cr04 + 2NaCI + 2H 20
(i) Ca0Cl 2 + 2CH3COOH + 2KI -----7 YeJlow soln.
Ca(CH3COOh + 2KCI + H20 + 12 Answers : Matching Type Questions

(li) CaOCl2 + C02 -----7 CaC03 + Cl2 - .. ..
~".--------- --~~~. ----tA}(i-f:f,-(ii-h);-(iii-a);-Eiv-g);---(V"'i:);-tvi=b);-{vll=d);-(-viii=e-);-- .
--~(iii)-CatOC1)cr+-H20 -----7~Ca(OHh +<::1 2-
[B] (i-<1); (ii-a); (iii=e); (iv"'i:); (v=b).
1. The property of halogen acids, that indicated incorrect is : 5. When chlorine water is added to an aqueous solution of
(a) IfF> HCI > HBr> In ..... acidic strength sodium halide in the presence of chlorofonn, a violet
(b) In> HBr > Hel > HF ..... reducing strength colouration is obtained. When more of chlorine water is
(c) In> HBr > HCI> IfF ..... bond length added, the violet colour disappears and solution becomes
(d) IfF > HCI> HBr> In ..... thennal stability colourless. This confmns that sodium halide is :
Ans. (a) (a) chloride (b) fluoride
[Hint : HI is the strongest acid while HF is the weakest acid. The (c) bromide (d) iodide
order of acidic strength is : Ans: (d)
HI > HBr > HCI > HF ] [Hint : 2Nal + Cl2 - - 7 2NaCI' + 12 (violet colouration);
2. The property of halogens, that indicated incorrect is : 12 + 5Cl2 + 6H20 - - 7 2HI~ + lOHCn
Colourless
(a) F> CI > Br > I ..... ionisation energy
(b) F > CI > Br> I ..... electron affinity 6. As the atomic number of the halogens increases, the
(c) F> CI > Br > I ..... electronegativity halogens:
Cd) I> Br > CI > F ..... density in liquid state (a) lose the outermost electrons less readily
Ans. (b) (b) become less dense
[Hint : The electron affInity of Cl is maximum. The trend is : (c) become lighter in colour
CI> F > Br> JJ (d) gain electrons less readily
3. 409 is alan : Ans. (d)
(a) covalent compound (b) coordinate compound [Hint : The electron affInity decreases down the group as atomic
t
(c) ionic compound (d) double salt size increases.]
Ans. (c) 7. The halogen that is most readily reduced is :
[Hint : 1409 is actually 1(l03h which gets ionised. (a) fluorine (b) chlorine
1(103h p e+ + 3(103)- ] (c) bromine (d) iodine
Ans. (a)
Cold and dilute NaOH (A) + NaCI+ H2 0 [Hint : The reduction potential of fluorine is maximum and
thus, it is easily reduced, i.e., it acts as strongest oxidising
4. 0,-1 No< .... "",c. N.ON : (B) + Nael + H,O agent.]
Corppounds (A) and (B) are : 8. Which has maximum pH in aqueous solution ?
(a) NaCI0 3,NaClO (b) NaOC12,NaOCI (a) NaCIO (b) NaCI(h
(c) NaCl04,NaCl~ (d) NaOCI, NaCI0 3 (c) NaCI03 (d) NaCI04
Ans. (d) Ans. (a)
[Hint : NaCIO+H20~NaOH + HClO; HClO is the weak-
[Hint: Cl 2 + 2NaOH ~ NaCI + NaOCl + H20
Cold and diL (A) est acid among the oxyacids _of chlorine and thus, the
solution of NaCIO has maximum pH.]
3Cl 2 + 6NaOH ~5NaCI+NaCI03 +3H20]
Hot and cone. (B)
9. In the known interhalogen compounds, the maximum number 15. What products are expected from disproportionation
of halogen atoms are : reaction of hypochlorous acid? [A.I.E.E.E.2006]
(a) 4 (b) 8 (a) HCI0 3 and Cl 20 (b) HCI02 and HCI04
(c) 5 (d) 7 (c) HClandCl20 (d) HClandHCI0 3
ADS. (b) ADS. (d)
10. Which of the following oxyacids of chlorine is formed on [Hint : 3HCIO ---7 HCI0 3 + 2HCI]
shaking chlorine water with freshly precipitated yellow oxide 16. The number of lone pairs of electrons present in central atom
of mercury? of ClF3 is : [J.E.E. (Orissa) 2006}
(a) H00:3 (b) HO~ (a) 0 (b) I (c) 2 (d) 3
(c) Hoo (d) H004 ADS. (c)
3d
Ans. (c)
[Hint : CI in first excited state
[Hint : HgO + 2Cl2 + HzO ---7 HgClz + 2HCIO]
11._The_substance,_which_is~0Iid at room . t~mR~ture-,_j()rrIl~ . _,sp3d_by~ __ .
ionic compounds and reacts with hydrogen forming a 17. Fluorine is the best oxidising agent because it has:
hydride, the aqueous solution of which is acidic, may be : [M.P.(P.M.T.) 2005)
(a) AI (b) Na (a) highest electron affinity (b) highest E~ed
(c) 12 (d) Br2 (c) highest E~xid (d) lowest electron affinity
-Ans.(c) ADS. (b)
[Hint : Iodine is a solid at room temperature, can form ionic 18. When F2 reacts with hot and conc. alkali, then following will
compounds. It forms HI with hydrogen which is an acid be obtained: [M.U.(CE.T.) 2005}
in aqueous solution.]· (i) OF2 (ii) ~ (iii) H20 (iv) NaF
12. Interhalogen compounds are more reactive than the (a) (i), (iii) and (iv) (b) (ii) and (iii) only
individual halogen because: (c) (ii), (iii) and (i v) (d) all of these
(a) two halogens are present in place of one Ans. (c)
(b) their bond energy is less than the bond energy of the (Hint: 4NaOH + 2~ ---7 4NaF + 2H zO + Oz ]
(conc.+hot)
halogen molecule 19. The hybridization present in IF3 is : [PJ\t.T. (Raj.) 20(5)
(c) they are more ionic (d) they carry more energy
ADS. (b)
(a) sld (b) sl
13. Tincture iodine is : [A.IJ.M.s~ 20(6)
(c) sli (d) sp3~
(a) aqueous solution of 12 ADS. (a)
(b) solution of iodine in aqueous KI 20. Shape of ClF3 is : [J.E.E. (Orissa) 2007}
(c) alcoholic solution of 12 (d) aqueous solution of KI (a) equilateral triangle (b) pyramidal
Ans. (b) (c) V-shaped (d) T-shaped
14. Which two of the following substances are used for ADS. (d)
preparing iodized salt? [AJ.l.M.S. 2:0061 21. Predict the product of the following reaction:
(i) KI0 3 (ii) KI (iii) 12 (iv) HI Cl 2 + HgO--'7 (J.E.E. (Orissa) 2007}
(a) (i) and (ii) (b) (i) and (iii)
(a) HgCl 2 + O 2 (b) Hg + Cl207
(c) (ii) and (iv) (d) (iii) and (iv)
(c) HgCI2 +C}z0 (d) Hg + HgC12+ 02
ADS. (a)
ADS. (c)
... -
Set I: This set contains questions with only one correct answer.
-
1. Halogens are: 14. The solubility of iodine in H20 may be increased by the
(a) gases under ordinary conditions 0 addition of:
(b) electronegative in nature 0 (a) Na2SZ03 o (b) CHCl3 o
(c) fuming liquids 0 (c) KI o (d) CS2 o
(d) the gases found in atmosphere 0 15. The colour of iodine solution is discharged by shaking with:
2. Halogens show usually: (a) aqueous sulphur dioxide 0
(a) electro-valency 0 (b) sodium sulphide 0
(b) covalency 0 (c) sodium sulphate [J (d) sodium chloride 0
(ct hoth_electro::-_valency ...an~cov.alenc-y-- - -- 0 16. Whenchlorine-is-passed-through concentrated hotsoluttoo-----~···
(d) coordinate valency 0 of KOH, the compound formed is:
3. The most powerful oxidising agent is: [C.B.S.E. (PM.T.) 2009] (a) KClO 0 (b) KCIOz o
(a) fluorine 0 (b) chlorine 0 (c) KCl03 0 (d) KCl04 o
(c) bromine 0 (d) iodine 0 17. Chlorine is prepared in the laboratory by the action of:
4. How-many electrons are present in the outermost orbit of
c
(a) Zn and Hel 0 (b) CaC03 and HCl 0---=-
halogens? (c) Pb(N03)z andHCI 0 (d) Mn02 and HCI o
(a) 1 o (b) 3 o 18. Which among the following is paramagnetic?
(c) 5 o (d) 7 o (a) Cl2~ 0 (b) Cl206 o
5. Which one of the hydracids does not form any precipitate (c) ClDz 0 (d) ClzO o
with AgN03?
19. Pure chlorine is obtained:
(a) HF o (b) HCl o (a) by heating PtC14 0
(c) HBr o (d) HI o (b) by heating Mn02 with HCI 0
6. The strongest reducing agent is:
(c) by treating bleaching powder with HCI 0
(a) P- 0 (b) Cl- o
0 (d) r (d) by heating mixture of NaCI andMn02 withconc.H2S04D
(c) Br- o
7. Which one of the following is the strongest acid? 20. Chlorine gas is dried over:
(a) HF 0 (b) HI o (a) Cao 0 (b) NaOH 0
(c) HBr 0 (d) HCI o (c) H2S04 0 (d) HBr 0
8. Which one of the following is the most volatile acid? 21. On heating a mixture of NaCI, K2Cr207 and conc. H2S04 .........
(a) HF 0 (b) HCl o is obtained.
(c) HBr 0 (d) HI o (a) chromic chloride o (b) chromyl chloride o
9. The acid which cannot be kept in glass bottles is: (c) chlorine o (d) none of these o
(a) HI 0 (b) HBr o 22. The catalyst used in the Deacon's process for the
(c) HF 0 (d) HCl o manufacture of chlorine is:
10. Which one of the following is the strongest acid? (a) Cu 0 (b) An alloy of copper 0
(a) HClO 0 (b) HCl(h 0 (c) CuClz 0 (d) CuS 0
(c) HCl~ 0 (d) HCl04 0 23. Which one of the following acts as an antichlor?
11. Which one of the following is the strongest oxidising agent? (a) Mn02 [] (b) Na2S203 []
(a) HCIO 0 (b) HCI02 0 (c) K2Cr2~ 0 (d) Na2S04 0
(c) HCl03 0 (d) HCI04 0 24. One gas bleaches the colour of flowers by reduction and
12. Consider the following oxides: other by oxidation. These gases are:
1. OP2 2. CI20 3. Br20 (a) SOz and Cl2 0 (b) CO and Cl2 o
The correct sequence of X-O-X bond angle is : (c) NH3 and S02 0 (d) H2S and Br2 o
(a) 1> 2> 3 0 (b) 3> 2> I o 25. Bromine occurs as a bromide in a mineral called:
(c) 2> I > 3 0 (d) 1 > 3 > 2 o (a) nitre 0 (b) tineal o
•• •• ••
[Hint: •0 • 0 : •0 • (c) common salt 0 (d) carnallite o
~ /toACl ~ 26. Bromine is prepared in the laboratory:
Br Br CI F F (a) by heating KBr with conc. H 2S04 []
13. Which one of the following has hydrogen bonding?
(a) HI 0 (b) HBr o (b) by heating KBr and Mn02 with cone. H2S04 o
(c) HF 0 (d) HCl o (c) by heating KBr with HCI o
(d) by passing 12 vapours through KBr solution o
27. Caliche is: 40. A substance X when heated with conc. H 2S04 liberates a
(a) impure nitre D (b) impure carnallite 0 gas which turns starch paper blue. The substance X is:
(c) crude saltpetre D (d) ashes of sea-weeds D (a) NaI D (b) NaBr D
28. Iodine is manufactured from: (c) NaO D (d) NaN0 3 D
(a) sea~weeds D (b) carnallite [] 41. The chemical name of bleaching powder is:
(c) nitre D (d) pure sodium iodide D (a) calcium hypochlorite D
29. Iodine displaces chlorine from which one of the compounds: (b) calcium chlorohypochlorite D
(a) KO [j (b) CaCl2 D (c) calcium chlorate D
(c) CC4 0 (d) KCI0 3 [] (d) calcium perchlorate D
30. Elements of which one of the following groups will fonn 42. Identify the correct statements :
anions most readily? 1. On heating Rb(ICh) will decompose giving RbCI and ICI.
(a) Oxygen group D (b) Nitrogen group D 2. CsI3 will ionise to give Cs+ and 13.
(c) Halogens D (d) Alkali metals [J 3. KBrICI will give KCI and IBr on heating.
31~ ·":'Which-statement-is-correct-abollt-halogen'i'-- ---- 4. Inthe-reaction-l:-+ I2n--l I 3,-theLewis-acid-is-12.
(a) They are all diatomic and fonn univalent ions D (a) 1,3,4 D (b) 1,2,3 D
(b) They are all capable of exhibiting several oxidation states (c) 2,3,4 D (d) 1,2,3,4 D
D [Hint: CsI3 ---7Cs+ + r + 121
(c) They are all diatomic and fonn diatomic ions D 43. Oxidising action increases in the following order:
(d) They are all-reducing agents D (a) CI<Br< 1 < F D (b) Cl<I <cBr <- F ~~=-
32. Fluorine is the best oxidising agent because : (c) I < F < CI < Br D (d) I < Br < CI < F D
(a) it has the highest electron affInity D 44. Fluorine does not show positive oxidation state because:
(b) it has the highest electronegativity D (a) its atom is smaller in size D
(c) it has the highest E~x D (b) it is volatile D
(d) it has the highest E~ed D (c) it is a gas D
33. Iodine vapours are violet in colour because: (d) it has no d-orbital [J
(a) the molecules of iodine in vapour phase absorb green 45. Available chlorine is liberated from bleaching powder when:
and yellow radiations D W~~~~ed []
(b) the molecules of iodine absorb red and violet radiations (b) it is reacted with excess of acid solution D
and then emit them D (c) it is reacted with alkali solUtlon [J
(c) it is a solid D (d) it is easily volatile D (d) it is reacted with water D
34. Among the elements of group 17, fluorine is the most reactive 46. Bromine can be liberated from potassium bromide solution
owing to its: by the action of:
(a) electronegativity D (a) iodine solution D (b) chlorine water D
(b) small size D (c) sodium chloride D (d) potassium iodide D
(c) extremely high oxidising power and low dissociation 47. Which of the following is not oxidised by Mn02?
energy of F-F bond D (a) F- D (b) cr D
(d) all the above factors are responsible for high reactivity (c) Br-
-
D (d) r D
35.
of fluorine
Which one of the following reacts with chlorine to fonn
D
[Hint : The fluoride ion : r.: is extremely stable. Hence, it is not
phosgene? oxidised by chemical reagents.l

(a) S02 [] (b) ~ D 48. Bleaching properties of bleaching powder are due to its:
(c) NO D (d) CO D (a) oxidising properties [J. (b) reducing properties D
36. Which of the following elements does not show positive (c) basic properties D (d) disinfecting properties D
oxidation state? 49. Which one of the following halogens is purifIed by
(a) Fluorine [J (b) Chlorine D sublimation?
(c) Oxygen D (d) Sulphur D (a) F D (b) 0 D
37. Slaked lime reacts with chlorine to fonn: (c) Br D (d) I D
(a) Ca(OOh D (b) Ca(OCl)CI D 50. In a given sample of bleaching powder, the percentage of
(c) Ca(003h D (d) Cao2 D available chlorine is 49. The volume of chlorine obtained if
38. Iodine is liberated from KI solution when treated with: 10 g of the sample is treated with HCl at N.T.P. is:
(a) ZnS04 D (b) CUS04 D (a) 1.5litre D (b) 3.0 litre D
(c) NiS04 D (d) FeS04 D (c) 15.0litre D (d) 150litre D
39. Iodine may be liberated from sodium iodate by reacting with: 51. Conc. H2S04 is not used to prepare HBr from KBr because it:
(a) H2S04 D (b) NaHS0 3 D (a) reacts too slowly with KBr D
(b) reduces HBr D
(cfkMn04 D (d) HO D
Elements of Group VIlA or 17 (Halogens)
(c) oxidises RBr (a)fluorine 0 (b) chlorine 0

(d) oxidises KBr to KBr0 3 o (c) bromine 0 (d) iodine 0
52 Which one of the following is the strongest acid? 66. When 12 is passed through solutions of KCl KF and KBr
(a) SO(0H)2 0 (b) S02(0I::Jh /'0 respectively: [C.E.E.T. (Haryana) 2000]
(c) Cl~(OH) 0 '(d) ClQ;(OH) . 0 (a) CI2 and Br2 are evolved 0
53. Which of the following is the anhydride of perchloric acid? (b) Cl2 is evolved 0
(!!-yCl20 0 (b) Cl~ 0 (c) C12, Br2 and F2 are evolved 0
'(c) Cl20ti 0 Cd) Cl2~ 0 (d) none of the above 0
54. RBr and HI can reduce. H2S04 , HCI can ,reduce KMn04 and 67. Iodine deficiency in diet is known to cause:
HF can reduce: \ /.
. (a) beri-beri 0 (b) goitre 0
(a) K2Cr2~ 0 (b) KMn04 0 (c) rickets 0 (d) night blindness 0
(c) H2SO4 0 (d) none of these 0 68. Chlorine is mixed with drinking water so that:
55. Chlorine acts as a bleaching agent only in the presence of:
(a) bl1fleria ~k:illed~ Cl(b)dirtJsremo'led_
'(aJ-dry-airEl(b)~sunU-ghr-- El
(c) water is cleaned 0 (d) suspension is removed 0
(c) moisture 0 (d) pure oxygen 0
69. Which of the following has the greatest reducing power?
56. Which of the following pairs is not correctly matched?
(a) HBr 0 (b) HI 0
(a) A halogen which is liquid at room temperature-Bromine
(c) HCl 0 (d) HF []
o 70., Concentrated'HN03 reacts with iodine to give: .
(b) The most electronegative element-Fluorine o (a) HI 0 (b) HOI 0
(c) The most reactive halogen-Fluorine o
(d) The strongest oxidising agent-Iodine o (c) HOI02 0 (d) HOIO:; 0
57. Which of the following statements is correct for CsBr3? 71. The correct order of increasing bond angles in the following
(a) It is a covalent compound 0 species is :
(b) It contains Cs3+ and Br- ions 0 (a) CI20<CI02 <CIOi [] (b) CI02 <CI20<CI02" 0
(c) It contains Cs+ and Br)" ions 0 (c) Cl 20< CIOi' <CI02 0 (d) CIOi' <CI 20<CI02 0
(d) It contains Cs+, Br- and lattice Br2 molecule 0 72. Which of the following is not a pseudohalide ion?
58. Which of the following is most stable towards heat? (a) SCN- 0 (b) OCN- 0
(a) HCl 0 (b) HOCI o (c) ICli' 0 (d) CN- 0
(c) RBr 0 (d) HI o 73. The following acids have been arranged in order of
59. The silver halide, which is least soluble in ~OH is: . deCreasing acid strength. Identify the correct order:
(a) AgF 0 (b) AgCI o CIOH(I) BrOH(II) IOH(III)
(c) AgBr 0 (d) AgI o (a) r > II > m 0 (b) n > I > m 0
60. Fluorine reacts with water to give: (c)ill>II>I 0 (d)! >m>II 0
(a) hydrogen fluoride and oxygen o 74. The acid employed for etching of glass is:
(b) hydrogen fluonde and ozone o (a) H2S04 0 (b) HCl04 0
(c) hydrogen fluoride and oxygen fluoride o (c) HF D. (d) aqua-regia 0
(d) hydrogen fluoride, oxygen and ozone o 75. Hydrogenfluoride isa liquid unlike other hydrogen halides,
61. When bleaching powder is treated with carbon dioxide:
because:
(a) chlorine is evolved o (a) H-F bond is strong o
(b) calcium chloride is formed o (b) F-atom is small in size o
(c) no reaction occurs o (c) Hydrogen bonding is present o
(d) it absorbs the gas o (d) HF is a we.* acid o
62. Bleaching powder is an example of:
(a) an acidic salt 0 (b) a complex salt 0 76. Hydrogen bromide is dried by passing the gas through:
(c) a double salt 0 (d) a mixed salt 0 OO~~~ 0
63. The outermost electronic configuration of the most electro~ (b) anhydrous calcium chloride 0
negative element is: (c) potassium hydroxide pellets 0
(a) ninl 0 (b) ninp4 0 Cd) cone. H 2S04 0
(c) nini 0 Cd) ninp6 0 77. Sea-weeds is source of:
M. Among the halogens, the one which is oxidised by nitric acid (a) fluorine o (b) iodine o
is: [C.E.E.T. (Haryana) 2005] (c) chlorine o (d) bromine o
(a) fluorine 0 (b) chlorine 0 78. CI03' ion reacts with 12 to' form :
(c) bromine 0 (d) iodine 0 (a) Cl04 0 (b) ICI and O2 0
65. Mark the element which shows only one oxidation state (c) ICI and 0 3 0 Cd) 10}" and CI2 0
besides zero: [Hint: CI03' + lz ~ 2103' + C12]
79. Which of the following is a preparation of chlorine? 92. The structure of IF7 is:
(a) HCI acting on KMn040 (b) HCI acting on Na202 0 (a) trigonal bipyramid 0 (b) octahe'dral o
(c) Electrolysis of brine 0 (d) All of these 0 (c) pentagonal bipyramid 0 (d) tetrahedral o
80. The shape of 02F2 is similar to : [A.I.I.M.S. 2004] 93. Which of the following is the strongest acid?
(a) H202 0 (b) C2F2 0 (a) HBr 0 (b) HF 0
(c) H2F2 0 (d) C2H2 0 (c) H2S 0 (d) PH3 0
81. Bleaching powder is obtained by the interaction of chlorine 94, Which of the following has the highest value of dipole
and: moment?
(a) dilute solution of Ca(OHh 0 (a) HO o (b) HF o
(b) concentrated solution of Ca(OHh 0 (c) HI o (d) RBr o
(c) drycalciumoxide 0 (d) dry slaked lime 0 95. A radioactive halogen is:
82. Which amongst the following reactions cannot be used for (a) polonium 0 (b) radon 0 .
the respective preparation? (c) astatine 0 (d) iodine 0
z
(a) 2KBr'fH S04 (conc:) ~KiS04+2HBr EI -96. Which of the-following compounds contains-both chlorine----
(b) NaCI 'I' H 2S04 (conc.) NaHS04 'I' HCI 0 and fluorine?
(c) NaHS04 'I' NaCI ~ Na2S04 'I' HCl 0 (a) teflon 0 (b) bleaching powder 0
(d) CaF2 'I' H 2S04 CaS04 'I' 2HF 0 (c) freon 0 (d) cryolite 0
97. Which is fotmed when K2Cr2~' CaCl2 and conc. H 2S04 are
83. Which of the follo'\Vingp9sse's'se~ tllehighe(>t bomlenergy?
heated?
(a) F2 0 (b) CI2 0
(c) Br2 0 (d) 12 0 (a) Cr2(S04h 0 (b) OCl3 0
84. Astatine is the element below iodine in the group VIlA of (c) C~02 '0 (d) K2Cr04 0
the periodic table. Which of the following statements is not
98. Chlorine water on cooling deposits greenish-yellow crystals
of:
true for astatine?
(a) 02,2H20 0 (b) ChH20 0
(a) It is less electronegative than iodine 0
(b) It will exhibit only -I oxidation state .0 (c) Cl2,3H20 0 (d) 02·8H20 0
(c) Intetmolecular forces between the astatine molecules will
99. A white deposit fotms over the bottles containing conc. HCl
when kept for a long time in the laboratory. The white
be larger than between iodine molecules 0
deposit is due to the formation of:
(d) It is composed of diatomic molecules 0
(a) ammonium chloride 0 (b) sodium chloride 0
85. Order of boiling point is : [D.P.M.T. 2005]
(a) HF >HI >HBr>HCI ' 0 (c) sodium carbonate 0 (d) calci~mchloride 0
100. Dry Cl2 reacts with dry S02 to fOtm:
(b) HF >HBr >HI >HCI 0
(a) thionyl chloride 0 (b) sulphuryl chloride 0
(c) HCI>HBr>HI >HF 0
(d) HCI >HI >HBr>HF 0
(c) sulphur dichloride 0 (d) sulphur monochloride 0
101. Chlorine shows bleaching action in : [J.E.E. (Orissa) 2010]
86. Halogens exist in -1 , '1'1 , '1'3, '1'5 and '1'7 oxidation states.
(a) dry conditions 0 (b) presence of HCl only 0
The halogen that exists only in -1 oxidation state is :
[P.E.T. (Kerala) 2010] (c) moist conditions 0 (d) none of these 0
(a) I 0 (b) Br o 102. Which of the following statements is correct?
[8.H.U. 1997}
(c) F 0 (d) Cl o (a) All halogens fotm oxyacids 0
87. Which of the following is a pseudohalogen?
(a) IF7 0 (b) (CNh o (b) Only chlorine and bromine fotm oxyacids 0
(c) All halogens except fluorine fotm oxyacids 0
(c) 102 0 (d) 13 o (d) Only iodine fotms oxyacid 0
88. Which of the following polyhalides is not known?
(a) 0 3 0 (b) Bri o 103. Which of the following statements is not correct when a
o mixture of NaCI and K2Cr2~ is gently warmed with conc.
(c) Fi 0 (d) Ii
89. The iodine atom in ICI2" involves:
H2S04?
(a) sp3d hybridization 0 (b) sp3 d2 hybridization 0 (a) A deep red vapour is evolved 0
(c) sp2 hybridization 0 (d) sp3 hybridization 0 (b) The vapour when passed into NaOH solution gives a
90, When the vapours of chromyl chloride are passed through yellow solution of Na2Cr04 0
(c) Chlorine gas is evolved 0
NaOH solution. it turns yellow. This is due to formation of:
(d) Chromyl chloride is fotmed 0
(a) Na2Cr2~ 0 (b) Na2Cr04 0
104. Which of the following is correct about the reaction?
(c) Cr~ 0 (d) H2Cr04 0 Heat
91. The structure of CIF3 is: 3NaOO ---7 Na003 'I' 2NaCI
(a) pentagonal bipyramid 0 (b) trigonal bipyramid 0 (a) It is a disproportionation reaction 0
(c) octahedral 0 (d) tetrahedral 0 (b) Oxidation number of chlorine decreases as well as
increases in this reaction 0
(c) This reaction is used for the manufacture of halates 0 (a) Na2S406 0 (b) NaHS04 0
(d) All of the above 0 (c) NaO 0 (d) NaOH 0
105. On heating KCI03 we get: [C.P.M.T. 1999] [Hint: Na2S203 + 4C1 2 + 5H2O 2NaHS04 + 8HCI]
(a) KCI02 + 02 0 (b) KCl+02 0 112. Shape and hybrldisation of IFs respectively are:
(c) KCI+03 0 (d) KCI+02+03 0 [J.E.E. (Orissa) 2008]
106. The correct order of thermal stability of hydrogen halides (a) trigonal bipyramidal, sp3 d 0
(H-X) is: [A.I.E.E.E.2005] (b) see-saw, sp3d 0
(a) HI>HBr>HCI>HF 0 (b) HF> HCI> HBr> HI 0 (c) square pyramidal, sld 2 0
(c) HCb HF > HBr > HI 0 (d) HI> HCI> HF>HBr 0 (d) pentagonal pyramidal, sp3 d 3 0
107. The set with correct order ot' acidity is: [IJ.T. (S) 2001; 113. Na2S203 is reduced by 12 to: [J.E.E. (Orissa) 2008]
C.B.S.E. 2007.J (a) Na2S 0 (b) Na2S04 0
(a) HCIO < HCI0 2 < HCI03 < HCI0 4 0 (c) NaHS03 0 (d) Na2S406 0
(b) H004 < HCI0 3 < HCI0 2 < HCIO 0
L·D· 114, The~xidationstatesof io.dineln HI04,~H3]:nsand~slC4-
. -~c)ttCIO<HCI04 <·HCIOj<~HCI02 .....
are respectively: [A.I.I.M.S. 2008]
(d) HCI04 < HCI0 2 < HCI0 3 < HCIO 0
(a) +1,+3,+7 0 (b) +7,+7,+3 0
108. The reaction,
(c) +7,+7,+7 0 (d) +7, +5, +3 0
3CIO-(aq.) ~ CI03(aq.) + 2Cnaq.)
115. The electron affinity values (in k:J mol-i) of three halogens
is an example of: [I.I.T. (8) 20(1)
X, Yand Z are respectively -349, -333 and -325. X, Y andZ- o
...
(a) oxidation reaction 0 (b) reduction reaction 0 respectively are: [D.C.E. (Engg.) 2008]
(c) disproportionation 0 0
(a) F2, C1 2, Br2 0 (b) O 2, F2 and Br2
(d) decomposition reaction 0
(c) C1 2, Br2, F2 0 (d) Br2, Cl2 and F2 0
lW. Hydrogen bond is strongest in: {B.V. (Pune) 20(2)
116. Which one of the following reactions does not occur?
(a) F-H--O 0 (b) F-H--N 0
[E.AM.C.E.T. (Engg.) 2008]
(c) F-H-F 0 (d) all are equally strong 0
(a) F 2 +2Cr ~ 2F +Ch 0
110. Which of the following has highest bond strength?
[C.E.E. (Bihar) 2002] (b) C12 +2F ~ 2Ce +F2 0
(a) HI 0 (b) HCI 0 (c) Br2 + 2r ~ 2Br- + 12 0
(c) HF 0 (d) HBr 0 (d) O 2 + 2Br- ~ 2CI- + Br2 0
Ill. Aqueous solution of Na2S203 on reaction with Ch gives:
[1.1.1: 2008J
117. Which of the following halogens tum( s) starch iodine paper (d) H004 > H003 > H002 > HOO 0
blue? 124. The halogens, which are not attacked by conc. HN0 3, are:
(a) O 2 0 (b) Br2 0 (a) F2 0 (b) Cl2 0
(c) 12 0 (d) F2 0 (c) Br2 0 (d) 12 0
118. Select triangular planar species among the following: 125. Which of the following are pseudohalide ions?
(a) 003 0 (b) H30+ 0 (a) CNO- 0 (b) OCN- 0
(c) CHj 0 (d) ooi 0 (c) RCCXT 0 (d) N3" 0
119. Iodine reacts with hypo to give: 126. Which one of the following arrangements truely represent
(a) Nal 0 (b) Na2S03 0 the property indicated against it?
(c) Na2S406 0 (d) Na2S04 0 (a) Br2 < Cl2 < F2 bond energy 0
120. Which of the following salts will evolve halogen on (b) Br2 < Cl 2 < F2 electronegativity 0
treatment with conc. H2S04 ? (c) Br2 < C1 2 < F2 oxidising power 0
(a) NaCl 0 (b) ea02 0 (d) Br2 < Cl 2 < F2 electron affinity 0
(c) NaBr 0 (d) KI 0 127. Which one of the following arrangements does not give the
121. Electrolysis of aqueous solution of Brine (NaCl) gives: correct picture of the trends indicated against it?
(a) ~ 0 . (b) H2 0 [CoB.S.E. 2008)
(c) NaOH 0 (d) none of these 0 (a) F 2 > Cl 2 > Br2 > 12 : Bond dissociation energy 0
122. Cl 2 reacts with hot aqueous NaOH to give: (b) F2 > Cl 2 > Br2 > 12 : Electronegativity 0
(a) NaO 0 (b) Na003 0 (c) F 2 > Cl2 > Br2 > 12 : Oxidising nature 0
(c) NaO~ 0 (d) Na004 " 0 (d) F2 > Cl 2 > Br2 > 12 : Electron gain enthalpy 0
123. Select the correct order of acidity: [Hint : Cl2 > Br2 > > 12 :
(a) HI > HBr > HO > HF 0 Bond dissociation energy}
(b) H004 > HBr04 > HI04 0 Clz> > Br2 > 12 : correct trends]
(c) HOO < HBrO < HIO 0 Electron gain enthalpy
1. (b) 2. (c) 3. (a) 4. (d) 5. (a) . 6. (d) 7. (b) 8. (b) 9. (c) 10. (d)
11. (a) 12. (b) 13. (~,; 14. (c) 15. (a)·· 16. (c) 17. (d) 18. (c) 19. (a) 20. (c)
21. (b) 22. (c) 23. (~:' 24. (a) 25. (d) 26. (b) 27. (c) 28. (a) 29. (d) 30. (c)
31. (a) 32. (d) 33. (a) 34. (d) 35. (d) 36. (a) 37. (b) 38. (b) 39. (b) 40. (a)
41. (b) 42. (a) 43. (d) 44. (d) 45. (b) 46. (b) 47. (a) 48. (a) 49. (d) 50. (a)
51. (c) 52. (d) 53. (d) 54. (d) 55. (c) 56. (d) 57. (d) 58. (a) 59. (d) . 60. (d)
~f. (a) 62. (d) 63. (c) 64. (d) 65. (a) 66. (d) 67. (b) 68. (a) 69. (b) 70. (c)
71. (d) 72. (c) 73. (a) 74. (c) 75. (c) 76. (b) 77. (b) 78. (d) 79. (d) 80. (a)
81. (d) 82. (a) 83. (b) 84. (b) 85. (a) 86. (c) 87. (b) 88. (c) 89. (a) 90. (b)
--91.(b)- 92.(c)----93.(a)--~-94.(b)····· -95.(c)-----96.(~)-----9'7._{c)------98.__(il)- --99.-(a)--100.(b)'--·····
101. (c) 102. (c) 103. (c) 104. (d) 105. (b) 106. (b) 107. (a) 108. (c) 109. (c) 110. (c)
111. (b) 112. (c) 113. (d) 114. (c) 115. (b) 116. (b) 117. (a,b) 118. (c,d) 119. (a,c) 170. (c,d)
121. (a,b,c) 122. (a,b) 123. (a,b,d) 124. (a,b,c) 125. (a,b,d) 126. (b,c) 127. (a,d)
--~.- Objective Questions for liT ASPIRANTS ~-

1. A greenish yellow gas reacts with an alkali metal hydroxide 1
[Hint: Mn02 + K2C03 + 202 ----7 K2Mn04 +C02
to fOlm a halate which can be used in fIreworks and safety Black (Air) (B)
Green
matches. The gas and the halate are :
2K2Mn04 + Cl 2 ----7 2KMn04 + 2KCI ]
(a) Br2,KBr03 (b) CI2,KCI03 Pink
(c) 12, Nal0 3 (d) 12 , KI03 4. Euchlorine is :
[Hint : The hal ate used in fireworks and safety matches is KCI0 3.
(a) obtained by heating perchlorate with cone. HCI
Thus, the gas is C12.
(b) a chloride of europium
3C12 +6KOH----7 KCI03 +SKCI + 3H20] (c) a mixture of Cl 2 and Cl207
Greenish
yellow gas Cd) a mixture of Cl2 and CI02
[Hint : When KCI03 is heated with conc. HCl, a mixture of Cl2
2. When chlorine water is added to an aqueous solution of and Cl02 is formed. This mixture is known as euchlorine.
sodium iodide in the presence of chloroform, a violet 2KCI03 + 4HCI ----7 2KCI + 2CI02 + Cl2 + 2H20]
colouration is obtained. On adding· more of chlorine water
and vigorous shaking, the violet colour disappears. This 5. Which is incorrectly matched ?
shows the conversion of ...... into ...... . (a) CsBr3 ~ Cs+ + Bri Cs+ + Br- + Br2
(a) 12,m03 (b) 12,m 3
(b) 1409 ~ 1 + + 3(I03 r
(c) m,m0 3 (d) 12, mo (c) AgBr03 ~ Ag+ + BrO)
[Hint : Cl2 + 2NaI ----7 2NaCI + 12
(Violet colouration in chloroform) (d) 1204 ~ 10! + 102
SCl 2 +6H20+ 2HI03 +10HCI] [Hint : 120 4 ~ r- + 104 ]
Colourless
6. A certain compound (X) when treated with copper sulphate
3. For (A)+K2C03+air~ (B) solution yields a brown precipitate. On adding hypo solution,
(B) + Cl2 ---'? (C) pink the precipitate turns white. The compound is :
Which of the following is correct ? (a) K2~ (b) KI .
(a) (A) is black:, Mn02; (B) is bliIe, K 2Mn04 and (C) is pink, (c) KBr (d) K3P04
KMn°4 [Hint: CuS04 + 2Kl----7 CuI2 + K2S04 ;
(b) (A) is green, Cr203; (B) is yellow, K2Cr04 and (C) is pink, 2CuI2 ----7 CU212 + I2 ;
K2Cr2O, White Brown
(c) (A) is black, Mn02; (B) is green, K2Mn04 and (C) is pink, 12 + 2Na2S203 -:-----t Na2S406 + 2NaI 1
Colourless
KMn°4
(d) (A) is black, Bi20 3; (B) is colourless, KBi02 and (C) is 7. The products of the chemical reaction between N aZS203, Cl2
pink,KBi03 and H 20 are:
.;
(a) S, HC1, Na2S04 (b) S, HC1, Na2S 12. HCI04 + P20S ~ (A) + (B)
(c) S, HCI, Na2S03 (d) S, NaCI03 (A) and (B) are :
[Hint NaZSz03 + HzO + Clz ----7 NaZS04 + S + 2HCl]
~ (a) HCI03,H~4 (b) CI206,HP0:3
8. Fluorine on reaction with KI0 3(aq.) gives (A) and on reaction (c) CI02,H~4 (d) C120 7,HP03
with KHS04 gives (B). (A) and (B) are : [Hint: 2HCI04 + PZ0 5 ~ Clz~ + 2HP0 3]
(a) KI04,K2S2O:3 (b) KI,F20 13. AgCI03 + (A)~ (B) + (C) + (D)
(c) HF,K2S20 g (d) 12,K2S20g
[Hint: KI03 + Fz + HzO ----7 KI04 + HzFz; Mn0 + HC1--.J .
2
Cone.
2KHS04 + Fz ----7 KzSzOs + 2HF]
The substances (A), (B), (C) and (D) are : ,
9. KCI0 3 on reaction with S02 gives (A) and on reaction with
(a) C1 2,AgCI, CI02, O 2 (b) CI2,Ag, C1 206, c)Zi
conc. H2S04 gives (B). (A) and (B) are :
(c) H2,AgO,H20,02 (d) HCIO,AgCl,CI 20,02
(a) KQ,H004 (b) Cl b 002
(c) KO,H003 (d) 02,HCI04 [Hint: 2AgCI03 + Clz----7 2AgCI + 2ClO z + 0zT
. fA) -(B)~' -[Cr'~Tb)~'~
[Hint: . KCl03 +3S0z + 3HP~~KCl+3HiS04 ;
(A) 14. Select the correct statement(s) :
'---v------'
Products (a) 0 20 and CI02 are used as bleaching agents and as
3KCI03 + 3HzS04 ----7 3KHS04 + 3HCl03 germicides
2HCI03 ----7 2CIOz + HzO + 0 (b) CI0 2 is the anhydride of HCI02 andHCI0 3
-HCI03 + 0 ~HCI04 (c) 120 5 is use<fin the quantitative estimation of CO
(d) All of the above are correct
[Hint: 2ClOz + HzO ----7 HClOz + HCI03
120 5 + 5CO ----7 Iz + 5COz]
10. Br2 + OH- ~ (A) + (B) 15. Which one of the following represents the reaction between
Hot
fluorine and cold NaOH(dil.) ?
(A) + (B) + IV ~ Br2
(a) 2F2 + 4NaOH ~ 4NaF + 2H20 + O2
(A) gives yellow precipitate with AgN03. (A) and (B) are :
(a) Br-,BrO- (b) Br-,BrOi (b) 3F2 + 6NaOH ~ 5NaF + NaF03 + 3H20
(c) BrO-,Br03" (d) Br<J,Br04: (c) F2 + 2NaOH ~ NaF + NaOF + H20
(d) 2F2 + 2NaOH ~ 2NaF + OF2 + H20
[Hint : 3Brz + 60H- ----7 5Br - + Br03 + 3H zO 16. Which one of the following pairs of reactants does not form
(A) (B)
5Br- + Br03 + 6H+ ----7 3Brz + 3HzO] oxygen when they react with each other?
(a) F2, NaOH solution (hot, cone.)
11. 109 of bleaching powder on reaction with KI required 50 mL
(b) F2,H 20
of 2N hypo solution. Thus, % of bleaching powder is :
(c) C12, NaOH solution (cold, dilute)
(a) 100 (b) 80
(d) CaOCI2• H 2S04 (dilute, small amount)
(c) 63.5 (d) 35.5
[Hint : (a) 2Fz + 4NaOH ----7 4NaF + 2H20 + Oz
[Hint : 50 mL 2N hypo soin. "" 50 mL 2N Iz soin. (Hot, cone_)
E 50 mL 2N Cl z soin. 50 mL 2N CaOClz soin.
E 6.35 g CaOClz (b) 2Fz + 2H20 ----7 4HF + O2
(c) Clz + 2NaOH ----7 NaCI + NaCIO + HzO
;.. % 6i~5 x 100 635]
(d) 2CaOCl2 + HZS04 ----7 CaClz + caS04 + 2HCI + Oz]
1. (t) 2. (a) 3. (c) 4. (d) 5. (d) 6. (b) 7. (a) 8. (c) 9. (a) 10. (b) n. (c) 12. (d) .
lz..~~,.(aJ: i, 14. (d) 15. (d) 16. (c)
--:r."
622 . GR.B. Inorganic Chemistry for Competitions

The following questions consist of two statements each, 4. (A) All the halogens are coloured.
printed as Assertion (A) and Reason (R). While answering these (R) Halogen molecules absorb some wavelengths of visible
questions, you are required to choose anyone of the following light and the electrons are promoted to higher energy
responses: molecular orbitals.
(a) If both (A) and (R) are true and (R) is the correct 5, (A) Fluorine does not show oxidation number greater than
explanation of (A). zero.
(b) If both (A) and (R) are true but (R) is not the correct (R) The halogens chlorine, bromine and iodine can show
explanation of (A). positive oxidation states of +1, +3, +5 and +7.
(c) If (A) is true but (R) is false. 6. (A) The boiling point of HF is maximum among the hydracids
(d) If (A)is-false-but (R)-istrue. QLhalQge..ns.~
(e) If both the (A) and (R) are false. (R) The high boiling point of HF is due to H-bonding on
1. (A) HCI04 is a stronger acid than HCI0 3 . account of high electro negativity of fluorine.
(R) Oxidation state of chlorine in HCI04 is +7 and in HCI0 3 ; 7. (A) Fluorine forms a salt of an oxyacid when treated with
it is +5. NaOH solution.
2. (A) The bond between· F-F is stronger than between (R) Fluorine can be prepared by passing chlorine thrQU~=
a-a. sodium fluoride solution.
(R) Atomic size of F is smaller than that of Cl. 8. (A) Halogens do not directly combine with oxygen. However,
3. (A) Iodine displaces chlorine from KCI0 3 . oxides are obtained indirectly.
(R) Iodine is stronger oxidising agent than chlorine. (R) The oxides of fluorine form oxyacids with water.
1. (b) 2. (d) 3. (c) 4. (a) 5. '(b) 6. (a) 7. (e) 8. (c)
11111111 11111111
THOUGHT 1 [Hint: CaOCl2·H20 ~ Cl z
145 71
Bleaching powder is a mixed salt of hydrochloric acid and
% 1;5 x 100 == 49]
hypochlorous acid. It has the formula, CaOCI2·H20. It is
manufactured by the action of chlorine on dry slaked lime at 2. The percentage of available chlorine in commercial samples
40°C. There is also a view that bleaching powder is a mixture of of bleaching powder is usually between 33-38%. The low
calcium hypochlorite and basic calcium chloride [Ca(OClh + value is due to :
CaCI2·Ca(OHhH20). (a) incomplete reaction between slaked lime and Cl2 during
The amount of chlorine obtained from a sample of bleaching its formation
powder by the treatment with excess of dilute acids or CO 2 is (b) impurities present in the original slaked lime
called available chlorine. A good sample of bleaching powder (c) decomposition of bleaching powder when kept in air
contains 35-38% of available chlorine. On long standing, it (d) all of the above
undergoes auto-oxidation and the amount of available chlorine 3. 3.55 g of bleaching powder when treated with acetic acid and
decreases. excess of KI liberated iodine which required 60 mL of 0.5 N
The estimation of available chlorine is done volumetrically by sodium thiosulphate solution. The percentage of available
(a) iQdometric method or by (b) arsenite method. chlorine in the sample is :
In textile industry, the cotton cloth is mainly bleached with the (a) 30.0 (b) 25.0
help of bleaching powder. (c) 20.0 (d) 35.0
1. Maximum percentage of available chlorine on the basis of [Hint : 60 mL 0.5 N Na2SZ03 soln. 60 mL 0.5 N 1z soln.
=: 60 mL 0.5 N e12 soln.
CaOCI2·H20 formula is:
" .(a) 35 '" •..•. __ .... _... {b)-40 .--:~:~~.__ _ . 60x0.5x355
%avallableC1 2 = 1000x355 xlOO 30]
(c) 45 (d) 49
Elements of Group VilA or 17 (Halogens)
4. On long standing, the bleaching powder undergoes auto- (a) IF? (b) IPs
oxidation. The products formed are: (c) C1F3 (d) FCl3
(a) calcium chloride only 2. Which halogen shows maximum oxidation state in forming
(b) calcium chlorate only interhalogen compound ?
(c) calcium chloride and calcium chlorate (a) I (b) Br
(d) calcium chloride and calcium chlorite (c) CI (d) F
[Hint : 6CaOCl2 ~ 5CaC12 + Ca(CI0 3hl 3. How many lone pairs of electrons are present on chlorine in
5. The chemical name of bleaching powder is : CIF3 molecule?
(a) calcium hypochlorite (a) 0 (b) I
(b) calcium chlorohypochlorite (c) 2 (d) 3
(c) calcium chlorate 4. Which of the following statements is wrong for. inter-
(d) calcium perchlorate halogen?
(a) The value of n in AXn (interhalogen) can be 1,3,5 or 7
(b)-Thevalue~ofn~in-AXn-(interhalogen)l:anbe2;'4~or6-~··- ..
(c) A can never be fluorine as it is most electronegative
A salt (A) when heated with K2Cr20? and conc. H 2S04 liberates
halogen
a gas which is absorbed in NaOH solution. The NaOH solution
(d) X can never be iodine as it is least electronegative
turns yellow. When this solution is acidified with acetic acid and
halogen
lead acetate solution is added, a yellow precipitate (B) is formed.
(A) is mixed with Mn02 and heated with conc. H2S04 when a
THOUGHT 4
gas (C) is evolved which turns starch-iodide paper blue.
1. The acidic radical present in the salt (A) is : Fluorine, the first member of group 17, differs from the other
(a) N0 3 (b) a- members of the group in many respects due to following reasons:
(c) S2- (d) r (i) Its size is very small
2. The compound formed, which turns NaOH solution yellow, (li) It has very high electronegativity
is : (iii) It does not have vacant d-orbitals in the valence shell
(a) Na2Cr2~ (b) Na2S (iv) Its dissociation energy in the molecular form (X2) is the
(c) NaI (d) Na2Cr04 least
3. What is the colour of gas which is evolved when salt (A) is 1. Which member of the group 17 does not show positive
heated with Mn02 and H2S04 ? oxidation state? .
(a) violet (b) brown (a) Iodine (b) Bromine
(c) greenish yellow (d) colourless (c) Chlorine (d) Fluorine
2. Which has the maximum molar enthalpy of vaporisation?
THOUGHT 3 (a) HF (b) Ha
(c) HBr (d) HI
Halogens react with each other to form a number of compounds
3. Which of the following bonds is the strongest?
called interhalogen compounds. Their general formula is AXn;
(a) F-F (b) Cl-CI
where A is less electronegative halogen while X is a more
(c) Br-Br (d) I-I
electronegative halogen and n is its number. The interhalogen
4. Which halogen does not form any oxyacid?
compounds are essentially covalent and more reactive than the
(a) Iodine (b) Bromine
halogens since the bond A-X is weaker than A-A or X-X bond.
(c) Chlorine (d) Fluorine
The reactions of interhalogens are similar to those of halogens.
5. The most basic among the following is:
1. Which of the following interhiuogen compounds is not (a) Cl- (b) Br-
possible? (c) F- (d) r
L&{lkli
Thought 1 1. (d) 2. (d) 3. (a) 4. (c) 5. (b)
Thought 2 1. (b) 2. (d) 3. (c)
Thought 3 1. (d) 2. (a) 3. (c) 4. (b)
Thought 4 1. (d) 2. (a) 3. (b) 4. (d) 5. (c)
624 , GR.B. Inorganic Chemistry for Competitions
The answer to each of the following questions is a single 4. In a given sample of bleaching powder, the percentage
digit integer, ranging from 0 to 9. chlorine is 49. The volume in litres of chlorine obtained if
1. Sodium iodate is treated with calculated amount of sodium 20g of the sample is treated with HCI at NTP is :
bisulphite to prepare iodine. How many moles of sodium 5. What is the oxidation ~tate of iodine in HSI06?
bisulphite required to prepare one mole of iodine from sodium 6. How many orbitals are
involved in the hybridisation of iodine
iodate? in IPs?
2. In the molecule ICI 3 • how many lone pairs of electrons are> . 7. Chlorine water on cooling deposits greenish yellow crystals
associated with iodine? /' of formula CI2,XH20. What is the value of X?
3. In the known interhalogen compounds ABm what is maximum
"~vatiie--of-,£?~ --. ---~------.----------
49 22.4
1. (5) 2NaI03 + SNaHS0 3----7 3NaHS04 + 2Na2S04 + H20 + 12 4. (3) Vol.ofCI2 = 100 X20X TI '" 3 litre
5 mole one
mole 5. (7) 5 + x - 12 = 0, x =+ 7
6. (6) sld2
hybridisation.
7. (8)
2. (2) sld hyb,
3. (7)
Group 18
or Zero
2
He I
13
Helium
1s"
10 I CHAPTER
Ne
Neon "
2s"2p' !
Ar I
A~on
3s3" J
36
'
-The"Elemeftts"or18~~'ofZ-ero~Group ~
- ....J
jl{f
~
Krvoton
4i,'4p·
Xe
54 i
l
(Inert Gases or Noble Gases)
. .
"Xenon""!
5s"5p' J
Rnl
Radon !
13.1,~,j POSITION IN THE PERIODIC TABLE
6s"ep.
118
The zero or 18th group consists of seven dements; helium, neon, argon, krypton,
xenon, radon and ununoctium. The zero group was unknown when Mendeleev
iUUO presented the periodic table and has been inserted in the table only at a later
IUounoclium
I' 7s·7p· Contents: stage. The existence of such a group may be natlllially expected from the fact
13.1 Position in the Periodic Table that there must be art inert group as transition when we go from highly
13.2 ()ccurrence electronegative elements (halogens) to highly electropositive elements (alkali
13.3 History of the Discovery of Noble Gases metals). Thus, zero group occupies the intermediate position between the
13.4 Isolation of Noble Gases from the Atmosphere elements of VITA (17th) and IA (lst) g r o u p s . .
13.5 Separation of Noble Gases The members of zero group are the end members of respective peri4Kis of
13.6 Uses of Noble Gases the periodic table. Helium is the end member 'of ftrst period, neon the end
13.7 Compounds of Noble Gases member of second period, argon the end member of third period and s9 on. This
13.8 Importance of Noble Gases in Theoretical
is the only group of the periodic table, all members of which are gases and
Chemistry chemically inactive under ordinary conditions. On account of this, these are
13.9 Detennination of Atomic Mass of a Noble Gas collectively called as inactive gases or inert gases. However, these are now
called noble gases as some compounds of these gases have been obtained under
certain speciftc conditions, i.e., they do show some chemical activity under
~I VIlA Zero
special conditions. They are also termed as zerovalent elements because they
Period ' (17) (18) I show zero valency due to chemical inertness. On account of zerb valency, the
H He
1 group to which these elements belong is termed as zero group.
(1) (2) I
F Ne VIlA (Halogens) IA (Alkali metals)
2 Zero group
(9) (10) Electrouegative elements Electropositive metals
CI Ar H (1) He (2) li (3)
3
(17) (18) F (9) Ne (10) Na (11)
Br Kr Cl (17) Ar (18) K (19)
4 Br (35) Kr (36) Rb (37)
(35) (36)
I (53) Xe (54) Cs (55)
I Xe At (85) Rn (86) Fr (87)
5
I (53) (54)
Except last two members radon and ununoctium which are radioactive. all
At Rn
6
(85) (86) other members are present in atmosphere in very minute quantities. Thus, these
Uuo
are termed as rare gases of atmosphere.
7 -
I (1l8)
The chemical inertness of these elements is due to the following reasons:

(i) Stable electronic configuration: All of these, except helium, have the highly stable i p 6 configuration in the outer
(valency) shell. Helium has the stable Ii configuration.
On account of highly stable il
configuration in the valency shell, these elements have no tendency either to lose, gain or
share electrons with the atoms of other elements, i.e., their combining capacity or valency is zero. These elements are, thus,
chemically inert.
(ii) All the orbitals in the atoms of these elements are doubly occupied, i.e., electrons are not available for sharing. Hence,
these elements cannot form c'ovalent compounds.
(iii) The ionisation enthalpies of these elements are very high. Hence, the atoms of these elements have no tendency to lose
electron from the outermost shell as to form cation.
(iv) The electron gain enthalpy values of these elements are positive. Hence, the atoms of these elements have no tendency
to accept electrons, i.e., to form anions.
~-----j- ...... -~ 1::..onfiguratiQn of.~
Element At. No. outer-shell
He 2 2 Ii
Ne 10 2,8 Ii, 2s22i
·Ar 18 . . e2i·8i8 li,2i2p6,.3i3i
Kr 36 2, 8, 18, 8 Ii, 2iq}, 3i3i3d lO, 4i4p6 4i4p 6
Xe 54 2, 8, 18, 18,8 Ii, 2i2p6, 3s23p63dlO, 4i4p64d 1O, 5i5p6 5s25p6
Rn 86 2,8, 18,32, 18, 8 Ii, 2i2p6, 3i3p63d lO, 4i4p64d 104l4, .si5i5d IO, 6i6i 6s 26p 6
Uuo* I
118 2, 8, 18, 32, 32, 18, 8 Ii, 2i 2p6, 3i3i3d IO , 4i4p64d104l4, 5i5p65dJ05l4, 6i6p66d lO, 7i7i 7i7i
Besides similar electronic configuration and chemical inert- Amongst the known elements, helium has got the lowest
ness, the following points justify the inclusion of these elements melting and boiling points. The low melting and boiling points
in the same group of the periodic table. A gradation in the of these gases are due to weak inter-molecular forces of
propelties is also observed with the increase of atomic number. attraction in these cases. The weak intermolecular forces,
(i) They are all colourless, odourless and tasteless gases. however, increase with increase of atomic mass from He to Rn
(ii) These gases do not burn and also do not help in burning. and therefore, the melting and boiling points increase
(iii) All are mono-atomic in nature as they have no combining gradually.
C (v) In a period of representative elements, it is observed that
capacity. The specific heat ratio, i.e., / for all the inert gases atomic radius decreases as the atomic number increases from
v
has been found to be 1.66 (theoretical value for mono-atomic 1st group to 17th group. H9wever, the radii values of noble
character). gases which come after the elements of group 17th are
Mono-atomic character was also proved by bond order exceptionally high. This is due to the fact that in the case of
data, bond order of the molecules like Hel, Nel was calculated noble gases, the atomic radii correspond to van der Waals' radii
to be zero, e.g., which are always larger than covalent radii. van der Waals'
Hel : Four electron system; its molecular orbital configuration radii of noble gases increase gradually from He to Rn. This is
is due to addition of new energy shell from member to member.
1 Element He Ne Ar Kr Xe
Bond order = "2 [Number of bonding electrons Number of van der Waals' radius (pm) 120 160 191 200 220
antibonding electrons] (vi) All have high values of ionisation enthalpies. However,
1
= 2 [2 ~ 2] = 0 ; these values decrease from He to R.n. However, the ionisation
zero bond order proves mono-atomic character. enthalpy of the inert gas is highest amongst the members of the
(iv) All have low values of melting and boiling points. same period.
These values increase gradually as the atomic number increases. Element He Ne Ar Kr Xe Rn
Element He Ne Ar Kr Xe Rn First ionisation 2372 2080 1520 l351 1170 1037
Melting point (K) I 24.6 83.8 115.9 161.3 202 enthalpy (kJ mol-1)
Boiling point (K) 4.2 27.1 87.2 119.7 165 211
*Recently discovered. It is synthetic, radioactive and unstable element. Not much is known about its properties.
The Elements of 18 or Zero Group (Inert Gases or Noble Gases) 627
(vii) These gases are sparingly soluble in water (8 to 40 mL N2 + O2 Electric) 2NO
per litre at 25°C). The solubility, in general, increases with discharge "
increasing atomic number. 2NO + O2 ~ 2N02
(viii) Except helium, these gases can be adsorbed by coconut
The oxides of nitrogen and unused oxygen were removed
charcoal at suitable temperatures.
by the use of caustic potash and alkaline pyrogallol solutions,
(ix) These gases give a characteristic spectra by which they
respectively. Cavendish observed that a small volume of the
can be easily identified.
gas which was about 11120 part of the original air, was left.
(x) These gases have fairly high electrical conductivity.
It was neither nitrogen nor oxygen. Cavendish, however, could
They produce characteristic coloured lights when an electrical
not draw any conclusion regarding the nature of the residual
discharge is passed through them at low pressure.
gas. This experiment was not given any importance for about
(xi) These gases are relatively difficult to be liquefied as
109 years.
very weak van der Waals' forces of attraction exist in these
In the yearsJ §9~~94,_1Qrd~R1!yJ§gjLwhile working..-..on~
g<ls~i;,H~)\l~YeI,fue~ liquefaction becomes easier from He to
accurate detenllination of densities of gases obtained nitrogen
Xe as forces increase gradually.
from two sources. The nitrogen obtained from the atmosphere
13~2~ OCCURRENCE
.,yit~
was found to be heavier in comparison to the nitrogen obtained
by heating a mixtllre of ammonium compound (NH4CI) and
The noble gases (exceptradon) al\\laysoccurin thefreestat,e. sodium nitrite. The actual" values were' found .to ,- bel :25TZ,=-
ThechiefsQufcesare:- -"" ".- """ " gIL for atmospheric nitrogen and 1.2505 gIL for chemical
1. Air: It is the most important source for the first five nitrogen. Rayleigh repeated his experiments several times and
gases. They form about 1% by volume of the air. Argon is the each time he found the same difference. He, thus, concluded
principal constituent and others are present in minute quantities. that the nitrogen, obtained from the atmosphere must contain
The percentage by volume of various elements is as given: some gas or gases which are heavier than nitrogen.
Helium 5.24 x 10-4 Neon 1.82 x 10-3 Rayleigh discussed the problem with Ramsay. Both took up
Argon 9.34 x 10- 1
Krypton 1.45 x 10-3 the investigations to prove that a heavier gas was present in
Xenon 8.70 x 10-6 atmospheric nitrogen. Two methods were used for the pre-
paration of the new gas:
2. Natural gas: The natural gas found in certain parts of (i) Ramsay method: This consisted of passing air over
America and Canada contains 2 to 7% helium. At present, most hot copper and heated magnesium to remove oxygen and
of the helium is obtained from this source. nitrogen, "respectively.
3. Spring water: The water of certain springs has been
found to contain dissolved helium, argon and neon in very Air ~ heated copper ~ heated magnesium ~ residue
small amounts. 2Cu + O2 ~ 2CuO ; 3Mg + N2 ~ Mg3N2
4. Radioactive minerals: Radioactive minerals such as The vapour density of the residue was determined and found
monazite, clevite, pitchblende and uranite contain considerable to be 20.
amounts of helium. The gas is produced as the result of (ii) Rayleigh method: Cavendish experiment was repeat-
radioactive disintegration of uranium and thorium present in ed. A mixture of air and oxygen was taken and an electric
the minerals but instead of escaping, it is retained by minerals discharge of 6000-8000 "volts was passed. After the removal
probably in a state of solid solution. The gas is obtained when of oxides of nitrogen and unreacted oxygen, the vapour density
these minerals are either heated at 10000C in vacuum or heated of the residual gas was determined and it also came to 20.
with sulphuric acid. N2 + 02~2NO
2NO + O2 ~ 2N0 2
13.3" HISTORY OF THE DISCOVERY 2N0 2 + 2NaOH ~ NaN0 2 + NaN0 3 + H20
OF NOBLE GASES Oxygen + Alk. pyrogallol ~ Oxygen absorbed
The credit for the discovery of inert gases goes to William The gas was examined spectroscopically and the spectrum
Ramsay and his co-workers. ' proved that this was an unknown gas. The gas was found to
be chemically inert. The new gas was named argon (Greek:
m Discovery of argon argos, lazy or inert). Later on, it was found that it was not a
In 1785, the English chemist, Henry Cavendish performed single gas but a mixture of many gases.
an experiment by passing electric discharge through a mixture
~ Discovery of Helium
of purified air (dry) and excess of oxygen. Nitrogen was thus
converted into corresponding oxides. On August 18, 1868, there occurred a total solar eclipse in
India. The sun's chromosphere was studied for the first time The last member of the family, ununoctium (118) has been
spectroscopically. J.C. Jannsen observed a new bright line in recently discovered. Only three atoms of the new element with
the yellow region of the sun's spectrum which did not coincide an average lifetime of 0.9 milliseconds have been produced so
with the two known lines D 1 and D z due to sodium. He named far. Scientists bombarded californium with calcium ions beam
the new line D 3. Frankland and Lockyer pointed out that for many months.
new D3 line was due to a new element which did not occur
on earth but only existed in the sun's chromosphere. They, ISOLATION OF NOBLE GASES FROM
therefore, named it Helium (Greek; heUos means sun). THE ATMOSPHERE
Hillebrand, in 1888, observed that a uranium mineral, devite,
Two methods are used for the separation of noble gases from
on treatment with dilute sulphuric acid gave out a gas which
he thought to be nitrogen as it was chemically inert. Ramsay the atmosphere. These are:
repeated this experiment and examined the evolved gas spectro- (i) Chemico-physical method
s_copj~ally. Th~_sI'~c;trum()fth~g~_~~ taken and it was
(ii) Physical method.
analysed by Crookes. He confirmed that the spectrum-besides
other lines contained D3 line in the yellow region which was (i) Chemico-physical method
similar to D3 line observed in the sun's spectrum. Ramsay This involves the use of some chemical reagents for the
was, thus, first to find belium on the earth. Its vapour density removal of nitrogen and oxygen of the air and a physical
was determined and it was found to be 2. It was also completely method for the separation of individual noble gases from~e_=.
chemically inactive like argon. gaseous mixture of five noble gases He, Ne, Ar, Kr and Xe.
There are three chemical methods for the isolation of a mixture
l!il Discovery of other inert gases
of all the noble gases from the atmospheric air. These methods
A new group, i.e., zero group was introduced in the periodic are:
table to accommodate argon and helium. Argon was placed (a) Ramsay and Rayleigh's first method.
before potassililll and helium was given position before lithium. (b) Ramsay and Rayleigh's second method.
Ramsay and Travers, thus, predicted that there must be an (c) Modem method-Fisher and Ringe's method.
element before sodium also as to fill the position between The first two methods are of historical importance only and
helium and argon in the zero group. They further said that are not used these days (already dealt in the discovery of
atmosphere might be the place where the new element could argon).
be searched.
Ramsay and Travers isolated about 16 litres of argon from ~ Fisher and Ringe's method
atmosphere which now they began to suspect to be a mixture
of a number of gases and they liquefied it. The liquid was then This is the modem method for the large scale production of
subjected to careful fractional evaporation under different noble gases. Air free from moisture is circulated through an
reduced pressures. Each fraction was' examined spectros- iron retort containing 90 parts of calcium carbide (CaC2) and
copically. From the first fraction, they isolated a new element 10 parts of anhydrous calcium chloride (CaClz) kept at 800°C.
which gave a number of red lines in the spectrum. It was Both oxygen and nitrogen are removed according to the following
named neon (meaning new). From the final fraction they isolated equations.
two new elements krypton (meaning hidden one) and xenon CaC2 + N2 ~ CaCNz + C
(meaning stranger) which gave new spectral lines in the Calcium cyanamide
spectrum. 2C +.0 2 ~ 2CO
The sixth member of the family, radon, was discovered in 2CO + O 2 ~ 2C02
1902 amongst the radioactive disintegration products of radium
C+02~·C02
and other isotopes found in thorium and actinium radioactive
series. Some of the CO2 combines with calcium carbide.
2CaCz + 3COz ~ 2CaC03 + 5C
z~~Ra~ Z§gRn (Uranium series)
The mixture of gases containing CO, CO 2 and noble gases
z~~ Ra ~ 2~2Rn (Thorium series) is passed over heated cupric oxide (CuO) when CO is oxidised
to CO 2, The COz is absorbed by caustic potash solution when
2~§Ra~ 2§~Rn (Actinium series)
the gaseous mixture is passed through it.
[The isotope 2~~Rn is also called thoron and the isotope CO + CuO ~ CO 2 + Cu
2i~Rn, actinon.] This discovery was announced by Dom but 2KOH + CO 2 ~ K2C03 + H 20
Ramsay had also made similar observations simultaneously.
The Elements of 18 or Zero Group (Inert Gases or Noble Gases) 629.
The gaseous mixture which now contains only noble gases Noble gas mixture containing He, Ne, Ar, Kr
is dried by bubbling through conc. H 2S04 and is finally passed and Xe brought in contact with coconut
. .charcoal maintained at -1 QOGC
through tubes packed with phosphorus pentoxide and collected.
The purpose of addition of CaCl2 is to reduce the reaction
temperature from lOOO°C to 800°C. Ar, Kr and Unadsorbed
Xe adsorbed He andNe
13.1 SEPARATION OF NOBLE GASES Connect with another coconut Brought in contact
charcoal maintained at liquid with charcoal at
~ Dewar's charcoal adsorption method air temperature' -180°C
This method is based on the faCt that activated coconut charcoal Argon diffuses First coconut
adsorbs different gases at different temperatures. The mixture 'and adsorbed in charcoal,.kr and adsorbed Helium
of noble_gases~ obtaine<i from -atmosphere is-taken~in~ a~ bulb~~
filled with activated coconut charcoal and placed in a cold
bath. The gases are allowed to remain in the bulb for about half
~
1
--fres&cllafooal- -Xe-in-adserbed~te--1--~- - - - - -
Warm
Warm
Neon
an hour and unadsorbed gases are removed by a Toepler's """.~._......",,,.,,,,,,,,_~,,.,,,.,. evolved )
pump and kept separately.
At ...:.1 oeoC;coconu( ~charcoara.dsorbs'argori,ki'ypton and
xenon while helium and neon remain free. The unadsorbed
helium and neon are brought in contact with another charcoal
Xenon remains in
maintained at -180°C, when neon is adsorbed and helium is
adsorbed state
obtained in free state. Neon can be recovered from this charcoal
on warming. lwann
Gases
-"---If--~ir,::::--___-...::. To pump
~ Physical method
(Fractional distillation of liquid air) :
Various constituents of liquid air possess different boiling
Coconut points. These boiling points are:
charcoal
Helium Neon Nitrogen Argon Oxygen Krypton Xenon
-269°C -246"C -196°C -186°C -183°C -152°C -107°C
The sufficient difference in the boiling points of various
constituents helps in carrying the fractional distillation of liquid
air. This is done in Oaude's apparatus (Fig. 13.2), which is
~1;1~~L-cO'd bath
especially used for the manufacture of liquid oxygen and liquid
nitrogen but noble gases are also obtained as by-products.
C@ld, compressed air enters the plant at the bottom. It
ascends through the rectifier and through the tubes surrounded
by liquid oxygen. It gets partially condensed into liquid which
Fig. 13.1 collects at the bottom.
The more volatile gases, mainly nitrogen get condensed in
When the charcoal containing Ar, Kr and Xe at -lOOoe is the receivers at the side.
connected with another charcoal maintained at liquid air The liquid collected at the bottom is pumped up and opens
temperature, the argon diffuses into this charcoal from which at the middle of the top rectifier. As it flows down, it meets the .
it may be obtained by warming. After the separation of argon, ascending gases from liquid oxygen. The contact between the
the temperature of first charcoal is raised to -90°C when pure two currents makes the desc,ending liquid richer in oxygen
krypton is evolved. Xenon which remains behind is recovered which collects at the middle.
by further warming the charcoal. Liquid from the side tubes is pumped up to the top. Liquid
The whole process of separation can be summarised with is partially used for cooling purpose and partially for separation
the help of the flow sheet chart given ahead : of helium and neon from nitrogen. At the various openings as
shown in Fig. 13.2 (ahead), three fractions are obtained.
respiratory diseases. If nitrogen is used along with oxygen in

1--r.~~~2=====:=-- Nitrogen
the cylinders of sea divers then nitrogen dissolves in blood at
high pressure and create painful sensation called BENDS.
(iii) Helium is used in research work for maintaining very
low temperatures.
Rectifier
t __ Liquid nitrogen
(iv) It is used in producing inert atmosphere.
(v) It is filled in tubes of aeroplane tyres.
Pump (vi) It is used for food preservation.
Pump (vii) Nucleus of helium (a-particles) are used as bombarding
Argon and
=-- oxygen particles in artificial radioactivity. ~-particles are produced
Liquid from helium using cyclotron.
oxygen (viii) It is llsed as filler in electric transformer.
!i!1l Argon
Receiver Receiver (i) It is widely used for filling incandescent metal filament
electric bulbs.
Liquid
nitrogen -·-Pump- (ii) It is also used for filling,radio-v:alv:es,~rectifiers and~--~
fluorescent tubes. The neon-argon mixtures are used in
Rectifier
advertising signs for various colours.
(iii) It is used in producing inert atmosphere during welding
Cold air from
expansion and extraction of various metals.
50% N2 and
engine
50%0 2
Fig. 13.2 Separation of the noble gases by fractionation
1. Helium and neon mixed with gaseous nitrogen.

2. Argon and oxygen in gaseous state above liquid oxygen.
3. Krypton and xenon present in liquid oxygen. The various
noble gases are isolated from these fractions.
(i) The gaseous mixture of He, Ne and nitrogen is passed
through a spiral cooled by liquid nitrogen. Most of the nitrogen
present in the gaseous mixture condenses. Nitrogen is
completely removed by passing over CaC 2 at 1000°C. Helium Fig. 13.3 Noble gases in cathode ray discharge tubes
and neon are separated by passing the mixture through a spiral characteristic glows. Argon glows blue.
cooled by liquid hydrogen (-2S3°C) when the neon is condensed
leaving behind helium in free state. ~ Neon
(ii) The second fraction containing argon and oxygen is
(i) It is used in neon discharge lamps and signs which are
fractionated by passing it around coils containing liquid nitrogen
used for advertising purposes, since the neon lights (generally
when oxygen is condensed and argon obtained in gaseous
. orange red) are visible from long distances and even visible
state.
(iii) The liquid containing oxygen, krypton and xenon is
fractionally distilled as there is wide difference in their boiling
points.
13~1 USES OF NOBLE GASES
III Helium
(i) Since helium is light, non-inflammable, it is uS!;!d in filling
air-ships and balloons for weather study. . Fig. 13.4 Noble gases in cathode ray discharge tubes
(ii) Unlike nitrogen, helium is not soluble in blood even characteristic glows. Neon glows red.
under high pressure, a mixture of 80% helium and 20% oxygen
is used instead of ordinary air, by divers for respiration. The through fog and mist. If mercury vapours are mixed with
same mixture is used to' assist breathing in asthama and other neon, a glow of blue or green colour is obtained. Neon lamps
are used over telephone tower, helipad and in music beat strong dipole water when brought in contact with a noble gas
indicators of deck. under high pressure and low temperature is likely to cause
(ii) It is used in safety devices for protecting dectrical polarisation of the gas atom, i.e., making it as a dipole which
instruments as it has a property of carrying exceedingly high attracts the original dipole water.
currents under high voltages. Recent work of Wiberg and Karbe ha~ reiected the idea of
the formation of such hydrates.
II Krypton and xenon (iii) Clathrates: Noble gases form a number of combi-
These are used in filling incandescent metal filament electric nations in which gases are trapped into the cavities of crystal
bulbs. These gases are considered superior than argon for this lattices of certain organic and inorganic compounds. These
purpose. combinations are called enclosure or cage or clathrate
Krypton-85 is used to determine () thickness of metal sheet compounds. (Latin : clathrate = enclosed or protected by
Gross~ bars} Thee1athr-ates- are normal1y~non=stoichiometric
and plastic sheets.~Kr;:85isalsuusedtrrregu1ating tlH!voltage~ ~
in electronic tubes. compounds.
When quinol (o-dihydroxy benzene) is allowed to crystallise
1'1 Radon its solution in water in the presence of heavier noble gases
such as argon, krypton or xenon under a pressure of 10-40
(i) It 'is used in radiotherapy of cancer. atmosphere, the noble gases get trapped within the lattice ~of ~.".'.~~
(ii) It is used to check the defects in steel castings. quinol crystals. These crystals are quite stable. However, when
(iii) Photography of internal opaque materials is made with heated or dissolved in solvent, the gas escapes.
the help of radon. The crystal structure with cavities is called the 'host' and
the atom or molecule entrapped in it is called the 'guest'. The
13~ COMPOUNDS OF NOBLE GASES formation of a clathrate is only possible when the size of the
On account of stable electronic configuration, high ionisation cavity is such that it can fit in tightly the guest atom or molecule.
potential and positive electron affinity, the noble gases are not Thus, helium-and neon do not form clathrate compounds
expected to form chemical compounds with other elements. with quinol as the size of the cavity is more than the size
However, the recent researches have shown that under certain of helium or neon atom.
conditions these gases especially the higher ones are capable (iv) Compounds discovered from 1962 onwards:
to form a few compounds. The only compounds known before Bartlett, in 1962, prepared a compound by reacting oxygen
1962 were those observed in the discharge tubes or the hydrates with a powerful oxidising agent platinum hexafluoride. The
and clathrates. X-ray examination of the solid compound, 02PtF6, showed
First theoretical support about compounds of inert gases that it consisted of 01 and PtF6" ions. Bartlett thought that a
was given by Van Anthropove in 1957 by taking into considera- similar compound could also be prepared with xenon since the
tion of following compounds: ionisation potential of xenon is quite close to the ionisation
Molecule Number of valence e- potential of oxygen. When he reacted xenon with platinum
with central atom hexafluoride, a red solid compound of composition, XePtF6
We was obtained. Similarly, XeRuF6, XeRhF4 were also synthesized.
11£ XePtF 6 was first real compound of any of the noble
14e. gases. The excitement caused by this discovery led to active
search for other noble gas compounds and in a short time three
Central atom of above compounds have more than 8 electrons
fluorides of xenon, XeF2, XeF4 and XeF6 had been obtained
in valence shell (expanded octet). Thus, zero group elements
as white crystalline solids.
can also form compounds by expanding their already existing
Xenon difluoride, XeF 2, is formed by heating a mixture of
octet.
xenon and fluorine in molecular ratio 1 : 2 at 400°C in a nickel
(i) Compounds formed in the discharge tubes: Boomer
tube.
in 1925, reported the formation ofWHe2 by subjecting helium
400·C
to electron bombardment using tungsten filament. In 1927, Xe + Fz ~ XeF2
Manley reported that in presence of electric discharges mercury Dioxygen fluoride reacts with Xe at about 118°C to give
and helium combined to form combinations like HgHe2 or
XeF 2·
HgHelO. Recent researches have shown that these reported
compounds are not true chemical compounds. Xe + 02F2 ~ XeF2 + 02i
(ii) Hydrates: The hydrates of argon, krypton and xenon In presence of mercury arc light, Xe and fluorine combine.
have been reported in literature. These are Ar·6H20, Kr·6H20, Mercury
Xe + F2 --~) XeF 2
Xe·6H 20. The formation is due to dipole-dipole interaction. A arc light
It is a colourless, crystalline solid (m. pt. 140°C). XeF4 + SbFs ~ [XeF 3t[SbF 6r
It is decomposed by hydrogen and water. Lewis base Lewis acid Adduct
• XeF2 + H2 ~ Xe + H2F2 Other Lewis acids like PFs , AsFs , SbFs , NbFs , RuFs. OsFs
also undergo similar addition reactions.
2XeF2 + 2H20 ~ 2Xe + 2H2F2 + O2
Like XeF2, xenon tetrafluoride also acts as fluorinating
It acts ru; a strong Oxidising agent. agent, e.g.,
XeF2 + 12 ~ 2IP + Xe XeF4 + Pt ~ Xe + PtF4
XeF2 + 2HCI ~ Xe + H2F2 + Cl 2 4NO + XeF4 ~ Xe + 4NOF
XeF2 dissolves in HF but do not react with HFXeF2 forms 4N0 2 + XeF4 ~
Xe + 4N0 2F
addition compound with Lewis acids by itself acting as Lewis Xenon hexafluoride, XeF6, is formed by heating xenon
base, e.g., and fluorine in molecular ratio 1 : 20 under pressure in a nickel
Lewis ~base~+-l:;ewis-acid~ - ~ . ~ ~Adduct~- tube..-~ ___ .-------~--... .-----------~.-
XeF2 + 2SbF s ~ XeF2·2SbFs Xe + 3F 3000C ) XeF

2 50 atm. 6
or
It is a colourless crystalline solid (m. pt. 49.5°C).
[XeFt [Sb 2F l1 r It is reduced by H2, HCI and NH3 •
XeF2 +·IFs·~ [XeFt ·[IF6r
XeF6 + 3lIz ~Xe;-3H2F2
XeF2 undergoes hydrolysis in aqueous alkaline solution,
XeF6 + 6HCI ~ Xe + 3H2F 2 + 3Cl2
e.g.,
2XeF2 + 40H- ~ 2Xe + 4F + 2H20 + O2 XeF6 + SNH3 ~Xe + 6~ + N2
Lastly, XeF2 acts as fluorinating agent also. The hydrolysis of XeF6 with water yields new compounds.
o +xeF2~OF+HF+xe
XeF6 + H20 ~XeOF4 + H2F2
XeOF4 + H20 ~ Xe02F2 + H2F2
Xe02F2 + H 20 ~ xe0 3 + H2F2
2NO, + XeF2 ~ 2NOF + Xe
2N02 + XeF2 ~ Xe + 2N02F Like qther xenon fluorides, XeF6 is also stored in nickel
alloy (monel metal) vessel. It cannot be stored in glass vessel
Note: Vessels of monel metal (alloy of nickel) are used to store XeF2•
because silica in glass reacts with XeF6.
Xenon tetrafluoride, XeF4, is formed by heating a mixture 2XeF6 + Si02 ~ 2XeOF4 + Sif4
of xenon and fluorine in the molecular ratio I : 10 at 400°C in
2XeOF4 + Si02 ~ 2Xe02F2 + Sif4
a nickel tube.
2XeOF4 + 2Si02 ~ 2Xe03 + 2SiF4
400°C
Xe + 2F2 ~XeF4 XeF6 dissolves in HF according to the following reaction
It is never synthesized in pure form because its formation XeF6 + HF ~ [XeFst [HF2 r
is accompanied with the formation of XeF2 and XeF6' XeF6 undergoes thermaI decomposition
It is a colourless, crystalline solid (m. pt. 107°C). It 2XeF6 ~ XeF2 + XeF4 + 3F2
undergoes sublimation. ~t is reduced by hydrogen, mercury (Like XeF2 and XeF4, XeF6 also acts as fluorinating agent.
and boron trichloride. XeF6 has strongest fluorinating tendency. XeF6 undergoes
XeF4 + 2H2 ~ Xe + 2H2F2 addition reactions with Lewis acids, e.g.,
XeF4 + 2Hg ~ Xe + 2HgF2 XeF6 + AsFs ~ [XeFst [AsF6r.
3XeF4 + 4BCl3 ~ 4BF3 + 3Xe + 6Cl2 XeF6 + BF3 ~ [XeFst [BF4 r
It forms a highly explosive solid, xenon trioxide (Xe03) XeF6 + NaP ~ NaXeF7
when treated with water. 2NOF + XeF6 ~ [NO]~+ [XeFg]2-
2XeF4 + 3H20 ~ Xe + Xe03 + 3H2F2 + F2 Hexafluoride undergoes hydrolysis in strongly alkaline
It is soluble in fluoroacetic acid (CF3COOH). When it is medium.
heated with excess of Xe it changes to XeF2. 2XeF6 + 160H- ~ 8H20 + 12F- + XeO~- + Xe + O2
Warm
XeF4 + Xe(excess) ~ 2XeF2
~.i Structure of Xenon Fluorides
It undergoes addition reactions like XeF2• forming
The bonding in these compounds is covalent. The formation
adducts.
involves the unpairing of p-orbitals and promotion of electron
or electrons to the vacant d-orbitals in the outermost shell. In
the excited state, the xenon atom undergoes hybridization In the formation of XeF6, sl
d 3 hybridization occurs which
. fonning definite configurations. The unpaired electroI)s in the gives the molecule a pentagonal bipyrarnidal structure. Six
hybrid orbitals form covalent (sigma) bonds with fluorine atoms. positions are occupied by fluorine atoms and one position is
The hybridization of xenon atom and shapes of different occupied by a lone pair of electrons.
fluorides can be predicted' with the 'help of following Due to presence of lone pair, distortion in structure takes
generalisation: place: The actual structure is distorted octahedral.
Hybridization = 112 [No. of electrons in the valence HYBRID.IZAT!ON AND SHAPES OF XENON FLUORIDES
shell of central atom + No. of
I No ..of No. of Total I
monovalent atoms surrounding the Molecule' bonded lone electron Hybridi- Structure Actual
central atom-charge on the cation + i pairs of pairs of pairs zation shape
• charge on the anion] ;eiectrons electrons
Molecule Thtal number of orbitals Hybridi. _ Sha~

XeF2 2 3 I 5 s/" _I Trigonal Linear
- --~.bipyramidaJ---
---1ilidergoing jiYbridizatio~tion ---- -- - -----~
4 2
SI/ d . Octahedral; Square
XeF4 2 6
XeF2 112[8 + 2 - 0 + 0] =5 sp3 d Linear
XeF6 6 I 7 sld
3
i planar
pentagonalll Distorted
XeF4 112[8 + 4 - 0 + 0] =6 - s/d2 Square planar bipyramidal octahedral
XeF6 1/2[8 + 6 - 0 + 0] =7 sp 3d 3 Distorted octahedral
Krypton also forms krypton difluoride- (KrF2)candkrypton---.--.~~
XeF 2 tetrafluoride (KrF4) under suitable conditions, Rnf2 has also
5s 5p 5d
F been prepared. However, all attempts have failed to prepare
similar compounds in the case of He, Ne and Ar.
[1] IHIHI HII....-I ...l--.I---I---1.......J
Xenon oxides and xenon oxyfluorides: Xenon fonns
Xenon atom in ground state :~------~----~~
two oxides, xenon trioxide (Xe03) and xenon tetroxide «Xe04)'
Xenon trioxide is obtained by hydrolysis of XeF4 and XeF6
with water.
6XeF4 + 12H20 ~ 4Xe + 2Xe03 + 12H2F2 + 30z
Xenon atom in first excited state F XeF6 + 3H20 ~ Xe03 + 3H2F2
In the formation of XeFz, sp3 d hybridization occurs which Xenon tetroxide is obtained by the action of anhydrous
gives the molecule a trigonal bipyrarnidal structure. The xenon sulphuric acid on barium perxenate.
and two fluorine atoms lie in a straight line while the three equato- Ba2 [Xe06] + 2H2S04 ~ 2BaS04 + Xe04 + 2H20
rial positions are occupied by the three lone pairs of electrons... Xe03 is a colourless explosive solid. It is a powerful
- to Pu4+.In the presence 0 f H+
. agent. I t OXI'd'Ises Pu?+
OXI'd'lsmg
ions.
3Pu2+ + Xe03 + 6H+ ~ JPu4+ + Xe + 3H20
5s 5p 5d
Xe03 reacts with aqueous alkali to form the hydrogen xenate
[IT] IHit I t III....-t.J. . .t-,-:-I
;.I --1---1.--'
ion (HXe04) which slowly disproportionates to give xenon
,~----~~~------~/
Xenon atom in second excited state
and perxenate iQn (XeOt-) in which xenon is present in +8
F"'----..--- oxidation state. .
Xe03 + OH- ~ HXe04
In the formation of XeF4, sl 2
d hybridization occurs which 2HXe04 + 20H- ~ XeOt" + Xe + 2H20 + 02
gives the molecule an octahedral structure. The xenon and Perxenate solutions are yellow and powerful oxidising
four fluorine atoms are co-planar while the two equatorial agents. Xe04 is less stable than Xe03 and decomposes into
positions are occupied by the two lone pairs of electrons. xenon and oxygen.
F Xe04 ~ Xe + 202
XeF6
•x Xenon oxyfluorides: A number of oxyfluorides are
known.
5s 5p 5d
(i) Xenon oxydifluoride (XeOF2)
(ii) Xenon dioxydifluoride (Xe02F2)
[tl]ltltltlltltltl Ff---:':--- (iii) Xenon oxytetrafluoride (XeOF4)
, y---------/
Xenon atom in third excited state (iv) Xenon dioxytetrafluoride (Xe02F4)
(v) Xenon trioxydifluoride (Xe03F2).
Some of the oxyfluorides are obtained by partial hydrolysis
of XeF4 and XeF6<
F
XeF4 + H20 ~ XeOF2 + H2F2

XeF6 + H 20 ~ XeOF4 + H2F2
XeOF4 + H20 ~ Xe02F2 + H2F2
Shapes of xenon oxides and xenon oxyfluorides: The
shapes of oxygen containing compounds of xenon are correctly
predicted on the basis of Valence Bond Theory and Valence
Structure Total No. of orbitals Hybridization
Shell Electron Pair Repulsion Theory. undergoing hybridization
In this case 1t-electrons must be subtracted in counting the
Xe04 112[8 + 0 0 + 0] = 4 sp3
total number of electron pairs in the valence shell of central
(v) Xe02F2: 1t bonds 2
atom.
Total number of electron pairs = 7
(i) XeOF2 : 1t bond = 1
Number of lone pair = 1
.. --TotaLnumber-oLelectron pairs 6~ ~ ~~~-Shape -;; Trig<iiirufiipyramiutsp3{J-Y- ----.. . .
Number of lone pairs = 2
Shape --7 T-shape geometry (sp3 d) F
O~I
<:J()
F~Xe~F
II
)1"0 F
o Structure Total No. of orbitals Hybridization
Structure Total No. of orbitals Hybridization undergoing hybridization
mldergoing hybridization
1/2[8 + 2 0 + 0] 5
XeOF 2 112[8 + 2 - 0 + 0] =5
(ii) XeOF4 : 1t bond = 1 13.8:; IMPORTANCE OF NOBLE GASES IN
Total number of electron pairs 7 -- ..;...~
THEORETICAL CHEMISTRY
Number of lone pair = 1
2
Shape --7 Square pyramidal geometry (sl d ) Noble gases have played an important role in the development
o of various subjects of theoretical chemistry.
F.,..----I+----:>I (i) Improvement in periodic table: Insertion of zero
group between highly electronegative halogens and highly
electropositive alkali metals improved the periodic table. Zero
group occupies the intermediate position between two extreme
groups of elements.
(ii) In establishing the scheme for the arrar.gement of
electrons in atoms: All noble gases except helium have 8
Structure Total No. of orbitals Hybridization
electrons in the outermost energy shell. This configuration
undergoing hybridization
accounts for the inertness of these elements. It led Bohr and
XeOF4 112[8 + 4 - 0 + 0] = 6 Bury to assume that the outermost energy shell of any stable
(iii) Xe03 : 1t bonds = 3 atom cannot have more than 8 electrons.
Total number of electron pairs 7 = (iii) In the development of electronic theory of valency:
Number of lone pair = 1 All elements tend to acquire stable configuration during chemical
Shape --7 Pyramidal geometry (sp3) union. This is possible when they acquire noble gas configura-
tion, i.e., 8, electrons in the outermost energy shell. This occurs
V either by transference of electrons from one atom to another
/xe, (electrovalency) or by sharing of electrons (covalency) or by
o II
o
0 contributing both electrons to be shared by only one atom
(coordinate valency).
Pyramidal (iv) Group displacement law in radioactivity: (X-particles
Structure Total No. of orbitals Hybridization are emitted by the disintegration of radioactive elements. Alpha-
undergoing hybridization particles are actually helium nuclei. It has proved useful in
112[8 + 0 - 0 + 0] = 4
formulating the theory of radioactive disintegration and the
group displacement law.
1t bonds = 4
(v) In the discovery of isotopes: Neon was the first
Total number of electron pairs =8 non-radioactive element whose isotopes were first of all
Shape --7 Tetrahedral (sp3) separated. On this basis, it was concluded that other elements
may also consist of a mixture of two or more isotopes. This' Atomic mass = Equivalent mass x valency
has helped in the discovery of many new isotopes. The molecular mass of any gaseous element is related
with its atomic mass by the following relationship:
13.9 DETERMINA1"ION .OF ATOMIC MASS Molecular mass :::; Atomicity x Atomic mass
OF A NOBLE GAS The atomicity of noble gases is unity.
Chemical equivalent masses of noble gases cannot be determined
Thus, =
Molecular mass Atomic mass
Molecular mass can easily be calculated if vapour density
by usual methods as these are chemically inert. Thus; the
is determined experimentally.
following relationship cannot be used for the determ~l}atiori of
atomic masses of noble gases. Mol. mass = 2 x vapour density
or At. mass = 2 x vapour density
b 5UMMAR¥-AND-lMPQR-l"ANf-POfN-TS-ta-REMEMBER b-~.-
.
1. The zero or 18th group consists of seven elements-helium, 12. Noble gases always occur in the free state. The chief sources
neon, argon, krypton, xenon, radon and ununoctium. 'Ibis are:
group was unknown when Mendeleev presented the periodic . (a) Air .
table and hastieen Inserted -onlyata-later-stage.Ttoccupies (b) Natural gas : contains up to 7% helium.
an intermediate position between electronegative elements of (c) Radioactive minerals: only He .
. VIlA (l7th) and electropositive elements of IA (Ist) groups. (d) Spring water-dissolved He, Ne and Ar.
2. . The members of zero group are the end members of respective (e) Radon-radioactive decay 2~~Ra ---7 2~~Rn + iHe.
periods of periodic table. This is the only .group of the 13. Argon--Greek word-argos meaning lazy or inert.
periodic table, all members of which are gases and chemically lIelium--Greek word-helios meaning sun. First reported on
inactive under ordinary conditions. These are collectively the surface of sun.
called as inactive or inert gases. However, these are now Neon-Meaning new.
called noble gases as some compounds of these gases have Krypton-Meaning hidden one.
been obtained under specific conditions. They are also Xenon-Meaning stranger.
termed zerovalent elements because they show zero valency. The credit for the discovery of above gases goes to Ramsay
3. Except radon which is radioactive, all other members' are and Travers. Radon was discovered by Dorn.
present in atmosphere in minute quantities. Thus, they' are 14. Two methods are used for the separation of noble gases from
termed rare gases of atmosphere. • h,~ y form about 1% by the atmosphere.
volume of the air. Argon is the i '·'.Hl constituent. (i) Chcmico-physical method: It involves the use of some
4. All the noble gases have stable configuration. Except helium chemical reagents for the removal of nitrogen and oxygen
which has Is2 configuration, rest has 8 electrons, Le., s2p 6 of the air and a physical method for the separation of
configuration' in the outer shell. They have no tendency indiyidual noble gases from the gaseous mixture. The
either to lose, gain or share electrons with the atoms of other modem method for isolation of gaseous mixture of noble
elements. gases from air is : .
5. Ionisation potential values are high. However, decreases on Fisher"Ringe~s method: Air free from moisture and
moving down the group. CO 2 is passed over a mixture in an iron retort containing
6. Electron afflnity values are positive. 90% CaC2 and 10% Ca02 anhydrous kept at 800°C. Both
7. They all are colourless, odourless and tasteless gases. All 02 and N2 are removed.
are mono-atomic in nature as CpfCv value for every gas is CaC 2 + N2 ---7 CaCN2 + C
1.66. All have low values of melting and boiling points. The 2C + O2 ---72CO 1 or C + O2---7 CO 2
values increase as the atomic number increases. 2CO + O2 ---7 2C~ J
Among the known elements~ helium has got the lowest The mixture of gases containing CO, CO 2 and noble gases
melting and boiling points. is passed over heated CuO when CO is oxidised to CO 2,
8. These gases have fairly high electrical conducti.vity. They The CO 2 is absorbed in caustic potash solution and the
produce characteristic coloured lights whert an electrical unabsorbed gases are dried over P20S'
discharge is passed through at low temperature. Noble ga~es mixture is separated into individual gases
9. These gases are relatively difficult to be liquefied. by Dewar's charcoal adsorption method. At -IOO"C,
Liquefaction becomes easier from He to Xe. coconut charcoal adsorbs argon, krypton and xenon. The
10. Thes~ gases are sparingly soluble in water. The solubility unadsorbed He and Ne are separated at -I80a C, when
increases with increasing atomic number. neon is adsorbed and helium is left free. Neon is
.11. Except He, these gases can be adsorbed by coconut charcoal recovered by warming the charcoal. When the charcoal
at suitable temperatures. containing Ar, Kr and Xe is connected with another
charcoal at liquid air temperature, the argon diffuses to XeF6 + 3H2 ~ Xe + 3H2F2;
new charcoal from which it can be obtained by warming. XeF6 + H20 ~ XeOF4 + H2F 2;
When the temperature of first charcoal is raised to -90"C,
XeF2 -I' IPs ~ [XeFt [IP6f;
krypton is set free and on further warming, xenon is
recovered. XeOF4 + H20 ~ Xe02F2 + H2F 2;
(il) Physical method of separation, i.e., distillation of liquid XeF4 + SbFs ~ [XeF3t [SbF6L
air. For fractional distillation of liquid air claude's Xe02F2 + H 20 ~ Xe03 + H2F2;
apparatus is used. Three fractions are obtained :
XeF6 + AsFs ~ [XeFst [AsF6r
(a) Helium and neon mixed with gaseous nitrogen.
(b) Argon and oxygen in gaseous state. 17. Xenon forms two oxides xenon trioxide (Xe03) and xenon
(c) Krypton and xenon present in liquid oxygen. tetroxide (Xe04)' Xenon trioxide is a colourless explosive
These mixtures are further fractionally separated into solid. It is a powerful oxidising agent. Xenon tetroxide is less
-i----1ndividualmemher&. ____. . .____ ... _________ _ stable than Xe03 and decomposes into Xe and 02'
IS. (a) Since helium is light and non-inflammable, it is filled in 18. A number of oxyfluorides of xenon are known:
filling airships and balloons. (i) Xenon oxydifluoride, XeOF2
(b) A mixture of 80% helium and 20% oxygen is used instead (li) Xenon dioxydifluoride, Xe02F2
of ordinary air for respiration by sea divers and asthama (iii) Xenon oxytetrafluoride, XeOF4
patients. (iv) Xenondioxytetrafluoride! XeQZE4
(c) Helium is used for inflating the tyres of big aeroplanes (v) Xenon trioxydifluoride, XeO)f2
in place of air being lighter.
(d) Argon is used in creating inert atmosphere during I Hybridization No. of lone
extraction of various metals and welding. 19. Molecule. of central pair(s) around Shape
(e) Argon is used for filling incandescent metal fIlament atom central atom
electric bulbs, radio-valves and fluorescent tubes. XeF2 sp3 d 3 Linear,
(f) Liquid helium is used as cryogenic. Two cr bonds
2
(g) Neon signs for advertising contain neon gas. XeF4 sld 2 Square planar,
(h) Radon is used in radiotherapy of cancer. Four cr bonds
XeF6 sp3 d 3 Distorted octahedral,
16. Until 1962, no real compound of noble gases was known. In
Six crbonds
1962, it was observed that oxygen reacts with PtF6 to form a Pyramidal, Three cr
Xe03 sl
compound oi [PtF6f. and three 11: bonds
Since O 2 molecule has ionisation energy [02 ~
. 1
oi + e; Xe04 sp 3 Tetrahedral, Four cr
1166 kJmol-] almost same as that ofXe [Xe~ Xe+ + e; and four 11: bonds
1170 kJmor1], Neil Bartlett suggested that PtF6 should show XeOF2 sld 2 T-shaped, Three cr
a similar reaction with xenon. He then tried to react these two and one 11: bond
XeOF4 sp3 d 2 Square pyramidal, Five
at 298 K. He actually obtained the compound, XePtF6.
XePtF6 was first real compound of any of the noble gases cr and one 1i bond
Xe02F2 sp3d See-Saw, Four cr
and in a short time three fluorides of xenon, XeF2, XeF4 and
and two 11: bonds
XeF6 has been obtained as crystalline solids. i
20. No compound of He and Ne is known so far. Heliumand neon

1 : 2 400'C XeF
Ni
2 do not form any clathrate due to small size. Ar, Kr and Xe
1 : 10 400"C XeF4 form clathrates.
Ni 21. Noble gases have played an important role in the
1 : 20 300"C XeF6 development of various subjects of theoretical chemistry
50 aim.
such as :
Xenon fluorides react with hydrogen. water and fluoride ion
(a) Improvement in periodic table by introducing zero group.
acceptors like, PF5, SbF5 and AsF5, etc.
(b) In establishing the scheme for the arrangement of
XeF2 + H2 ~ Xe + H2F2; electrons in various energy shells of atoms.
2XeF2 + 2H20 ~ 2Xe + 2H2F2 + 02; (c) In the development of electronic theory of valency.
XeF4 + 2H2 ~ Xe + 2H2F2; (d) Group displacement law in radioactivity.
(e) In the discovery of isotopes.
2XeF4 + 3H20 ~ Xe + Xe03 + 3H2F 2 + F2;
• Subjective Type Questions (iv) Helium and neon do not form compounds with fluorine.
[Hint: He and Ne are smaller atoms and possess very high
1. Name the noble gas whjch: ionisation potential. Both do not have d-orbitals in
(i) is abundant in atmosphere their valency shells. Thus, the paired orbitals of
(ii) is found in natural gas valency shell cannot be unpaired. In absence of singly
(iii) is radioactive occupied orbitals, no sharing is possible with other
(iv) is not adsorbed in coconut charcoal atoms. Hence, no compounds are formed by He and
Ne.]
(v) highest boiling point. '
2. (a) Which was the first noble gas compound synthesized? (v) The boiling points of noble gases' increase with increase
Who prepared it? " _" in atomic number.
(0) Whlch-6ne-6ftlie-fc)llowmgdoes not exist? [Hliif: - van-aeiWaaEnorcesofittractlonamong molecUles
increase with the increase of atomic masses. Thus,
(i)XeOF4 (ii)NeF2 (iii)XeF2 (iv)XeF6
higher energy is required to separate these molecules
(c) Name the chemical compound which can remove both as to get gaseous state. Hence, the boiling points
nitrogen and oxygen from pure and dry air. increase with increase of atomic masses.]
, 3. (a) Whatwere the reasons forlatediscoveryof.noble gases? (vi) Why neon is usoomwarn.irig signal illiii:nlriations;rc~--'
(b) What made Rayleigh suspect that there may be an [Hint: Neon lights are visible from long distances. The lights
additional element in air? are even visible during fog and mist cOf,lditions.]
(c) Why noble gas compounds are formed only with 02 and (vii) A mixture of He and O 2 is used for respiration by sea
F2? divers.
4. Complete the following reactions: [Hint : Unlike nitrogen, helium is not soluble in blood even
(i) XeF4 + H20 ~ under high pressure.]
(ii) XeF2 + H2 ~ (viii) Why helium and neon do not form clathrate compounds
with quinol?
(iii) XeF6 + Si02 ~
[Hint: The size of the cavities formed during crystallisation
(iv) XeF6 + NH3 ~
of quinol is more than the size of helium and neon
(v) XeF6 + H 20 ~ atoms.]
(vi) XeF6 + SbFs ~ (ix) Why xenon does not form fluorides such as XeF, XeF3
orXeFs?
5. Answer the following with relevant reason.
[Hint: By unpairing of one paired orbital, two singly
(i) Why the group in which inert gases are accommodated occupied orbitals come into existence. Thus, either two
was called zero groupZ or four or six singly occupied orbitals can be formed
[Hint: Inert gases do not show chemical activity under instead of one or three or five singly occupied orbitals.
ordinary conditions due to possession of completed Hence, XeF or XeF3 or XeF5 are not formed.]
outermost shell, i.e., they show zero valency. On
account of zero valency, the group in which inert gases 6. Draw the molecular structures of XeF2, XeF4 and Xe02F2
were placed was called zero group.] indicating the location of lone pair(s) of electrons.
[I.I.T.2000]
(ii) Why the zero group elements do not form compounds
7. What is the hybridization of xenon in, geometry and shape of
under ordinary conditions?
the following molecules?
[Hint! Zero group elements have complete electronic confi-
guration of their outermost shells, i.e., s2l (except XeOF2, XeOF4, Xe02F2 and XeF6.
helium which has ll), hence they do not have any [Hint :
tendency either to lose or accept electron/electrons Molecule Hybridization Geometry Sbape'
of xenon
or share electrons with other atoms.]
XeOF z sp3 d Trigonal T-shaped
(iii) Xenon has closed shell configuration but is known to bipyramidal
give compounds with fluorine. XeOF 4 sp3 d Z Octahedral Square
[Hint: Xenon atom has large size and lower ionisation pyramidal
potential in comparison to He, Ne, AI and Kr. The sp3 d .
XeOZF2 Trigonal Distorted
outermost energy shell has d-orbitals. The paired
bipyrarnidal trigonal
electrons of valency shell can be unpaired and the
bipyrarnidal
electrons are shifted to d-orbitals under suitable
XeF6 sp3 d 3 Pentagonal Distorted
conditions. The unpaired electrons are shared by
fluorine atoms and covalent bonds are formed. In this bipyramidal octahedral
way, xenon forms compounds with fluorine.]
638 O.R.B. Inorganic Ch~.mistry for Competitions
8. Does the hydrolysis of XeF6 lead to a redox reaction? • Matching Type Questions
[Hint: When XeF6 undergoes hydrolysis, it forms XeOF4 , Xe02F2
and Xe03 as products. In these compounds, there is no Match the following:
change in oxidation state of Xe. Thus, the hydrolysis of (i) Helium (a) Lazy
XeF6 is not a redox reaction.] (ii) Neon (b) Hidden one
(iii) Argon (c) Stranger
(iv) Krypton (d) li,2i2p6
(v) Xenon (e) Sun's element
(vi) Radon (f) Radioactive
Answers : Subjective Type Questions 6.
(iv) Helium (v) Xenon F

2. (a) XePtF6, Bartlett . (b) NeF2 (c) CaC 2 (Calcium Carbide) ~-+--/IF
3. (a) Chemical inertness and rare abundance
O~~-----------r--~
(b){)t:nsi~ of~n!n:oge!1cis~!~!~d}'I'<;!flair ",as_al\Va)'s }1i.gher !han
the nitrogen obtained chemically.
(c) Because noble gases have extremely low reactivity, they need
FtL-----+_~
strongest oxidising agents to form compounds. o
4. (i) 2XeF4 + 3H20 ~ Xe + Xe03 + 6HF + F2 (It undergoes dis-
proportionation. ) F -
(ii) XeF2 + H2 ~ Xe + 2HF
Trigonal bipyramid
(iii) 2XeF6 + Si02 ~ 2XeOF4 + SiF4
2XeOF4 + Si02 ~ 2Xe02F2 + SiF4 XeF2 :
F
2Xe02F2 + Si02 ~ 2Xe03 + Sif4
Explosive
(iv) XeF6 + 8NH3 ~ Xe + 6NH4F + N2
(v) XeF6 +' 3H20 ~ Xe03 + 6HF
(vi), XeF6 + SbF3 ~ [XeFst [SbF6r
[Addition ionic product is formed.]
F
Answers : Matching Type Questions
(i--e); (ii-d); (iii-a); (iv-b); (v-c); (vi-f).
... -
1. The credit for the discovery of noble gases is given to: 16. The formation of XeF4 is due to ....... hybridization of
(a) Cavendish 0 excited xenon.
(b) Ramsay 0 (a) sp2 (b) sp3 0
(c) Rayleigh 0 (c) sid 0 (d) sid2 0
(d) Frankland and Lockyer 0 17. Xenon difluoride is:
2 Noble gases are chemic.ally inactive because of: (a) linear 0 (b) angular 0
(a) mono-atomic nature 0 (b) low boiling points 0 (c) trigonal 0 (d) pyramidal
(c) closed valency shell 0 (d) rare occurrence 0 18. The mixture which is used by sea divers for respiration is of:
-3. Which-of-the·following-is-mostabul1danhn air? (a}Niantl-02 . ----D-(bfIieliumanaO;'
(a) Ar 0 (b) He 0 (c) argon and 02 0 (d) neon and O 2 0
(<?) Ne 0 (d) CO2 0 19. The gas which is fIlled in tungsten lamp is:
4. The lightest gas which is non-inflammable: (a) H2 0 (b) He 0
(a) H2 0 (b)N2 0 (c) Ar 0 (d)O;z " _D __
---,c-{c}Ar "'[J'(d}He 0 20. Aradioactiveelement which can decay to give two noble
5. If one litre of air is passed repeatedly on hot copper and hot gases, is:
magnesium till no further decrease in volume takes place, the (a) U 238 0 (b) Th232 0
239
volume of residual gas would be about: (c) Ac 0 Cd) Ra226 0
(a) 200mL 0 (b) lOOmL 0 21. A noble gas which is not adsorbed by coconut charcoal is:
(c) lOmL 0 (d) zero 0 (a) He 0 (b) Ne 0
6. Radon is a: (c) Ar 0 Cd) Ra 0
(a) drug 0 (b) explosive 0 22. The coloured discharge tube for advertisement mainly
(c) trade name of nylon 0 (d) noble gas 0 contains:
7. ........ is the compound which can remove both oxygen (a) xenon 0 (b) helium 0
and nitrogen of the air when it is passed over it at lOOO°C. (c) neon 0 (d) argon 0
(a) Cac2 0 (b) CaQ2 0 23. Maximum number of compounds are known in the case of:
(c) CaCN2 0 (d) Ca(CN)z 0 (a) neon 0 (b) xenon 0
8. The CJCv ratio for noble gases is: (c) krypton 0 (d) argon 0
(a) 1.99 0 (b) 1.66 0 24. XeF6 on complete hydrolysis gives:
(c) 1.33 0 (d) 1.0 0 (a) Xe 0 (b) XeOz 0
9. The inert gas obtained from monazite sand is: (c) Xe03 0 (d) xe04 0
(a) He 0 (b) Ne 0 25. XeF4 exists as ...... under ordinary atmospheric conditions.
(c) Ar 0 (d) Kr 0 (a) solid 0 (b) liquid 0
10: Which of the following does not react with fluorine? (c) gas 0 (d) none 0
(a) Kr 0 (b) Xe 0 26. In solid argon, the atoms are held together by:
(c) Ar 0 (d) all of these 0 (a) ionic bonds 0 (b) hydrogen bonds 0
11. The gas with lowest boiling point is: (c) van der Waals' forces 0 (d) none of these 0
(a) hydrogen 0 (b) helium 0 27. The oxidation state of xenon atom in XeF4, HXe04' and
(c) nitrogen 0 (d) argon 0 Na4Xe06 are respectively:
12. The element having highest ionisation potential is:
(a) hydrogen 0 (b) .oxygen 0 (a) + 4, + 6, + 6 0 (b) +4,+6,+7 0
(c) nitrogen 0 (d) helium 0 (c) + 4, + 6, + 8 0 (d) +4,+5,+8 0
13. Claude's apparatus is used for the isolation of ....... from 28. Which of the following is u·sed to attain very low temperature
liquid air. during cryoscopic studies ?
(a) liquid oxygen only 0 (b) liquid nitrogen only 0 (a) Ar 0 (b) He 0
(c) noble gases only p (d) all of these 0 (c) Ne 0 (d) Kr 0
14. The valency of inert gasei' is: 29. The source of me:.t of the ncble gases is:
(a) 0 0 (b) 1 0 Ca) decay of radio;;;,tive minerals 0
(c) 2 0 (d) 3 0 (b) the atmospheric "ir 0
15. Of the following species, one which is non-existent: (c) the natural gases coming out of the earth 0
(a) XeF6 0 (b) XeF5 0 (d) the decay of rocks 0
(e) XeF4 0 (d) XeF2 0
30. The elements with atomic numbers 10, 18, 36, 54 and 86 are (a) sl o
all:
(a) light metals 0 . (b) inert gases 0
(c) sld o
(c) halogens 0 (d) rare-earths 0
(e) sp3d 2 o
45. Bond angle in Xe03 is: (J.E.E. (Orissa) 2006}
31. Which of. the outer electronic configuration represents
argon?
(a) 101' 0 (b) 103° o (c) 119" 0 (d) 9'l' 0
46. Select the correct matching:
(a) ni 0 (b) nini o List I List II
(c) ninp4 0 (d) nini o A: XeF4 1. Pyramidal
32. Which one of the following fluorides does not exist?
(a) HeF4 0 (b) XeF4 [J B: XeF6 2. T-Shape
(c) CF4 0 (d) SF6 o C: xe03 3. Distorted octahedral
33. Electron affinity of noble gas element is: D: XeOF2 4. Square planar
(a) very high 0 (b) high 0 A B C D
(c) low ·0 (d) zero 0 (a) 4. 3 .. J.2~
34. In Kroll and I.C.I. process of the production of titanium, the (b) 1 2 3 4 o
inert gas used is: (c) 2 1 3 4 o
(a) Ne 0 (b)'Ar o (d) 4 1 3 2 o
(c) Kr 0 (d) Xe o 47. Which one of the following is a correct pair with respect to
35. the~spectrum of helium is simllarto: molecular formula of xenoncompoundandhybridizationstate=·c.~
(a) H 0 (b) Na 0 of xenon in it? (E.AJ\-I.C.E.T.2002]
(c) U+ 0 (d) He+ 0 (a) XeF4 sl 0 (b) XeF2 sp 0
36. Which of the following gaseous molecules is monoatomic? (c) XeF2 sld 0 (d) XeF4 sp2 0
(a) chlorine 0 (b) helium 0 48. First compound of inert gases was prepared by Bartlett, in
(c) oxygen· 0 (d) nitrogen 0 1962, this compound is:
37. Which one of the following noble gas is not found in (a) Xe03 o (b) XeOF4 o
atmosphere? (c) XePtF6 o (d) XeF6 o
(a) Rn 0 (b) Kr 0 49. What is formed when xenon combines with fluorine in the
(c) Ne [] (d) Ar 0 presence of mercury vapour? [PJ\-1.E.T.2003]
38. Helium is added to oxygen used by deep sea divers because: (a) XeF 0 (b) X~F 0 (c) XeF2 0 (d) XeF4 0
(a) it is. less soluble in blood than nitrogen under high SO. In Xe03 and XeF6 the oxidation state of Xe is:
pressure o [P.E:f. (M.P.) 2003]
(b) it is lighter than nitrogen o (a) +4 0 (b)+6 0 (c) +1 0 (d) +3 0
(c) it is readily miscible with oxygen o 51. In Fischer-Ringe's method of separation of noble gas mixture
(d) it is less· poisonous than nitrogen o from air . . . . . .. is used. [E.A.M.C.E. T. (F.ngg.) 2005}
39. Which of th~ following statements is not correct? (a) 90% CaC2 and 10% CaCl2 0
(a) Argon is used in electric bulbs 0 (b) coconut charcoal 0
(b) Krypton is obtained during radioactive disintegration 0 (c) sodalirne + potash solution 0
(c) Half life of radon is only 3.8 days 0 (d) 90% CaC03 + 10% urea 0
(d) Helium is used in producing very low temperatures 0 52. Which of the following is not correct?
40. The siructure of XeF6 is: [E.AM.C.E.T. (Medical) 2005]
(a) distorted octahedral 0 (b) pyramidal 0 (a) Xe03 has four (J and four 1t bonds. 0
(c) tetrahedral. 0 (d) none of these 0 (b) The hybridization of Xe in XeF4 is sld •
2
0
41. Which of the following exhibits the weakest inter molecular (c) Among noble gases, the occurrence of argon is highest
forces? in~ 0
(a) He 0 (b) HO 0 (d) Liquid helium is used as cryogenic liquid. 0
(c) NH3 0 (d) H20 0 53. Xenon hexafluoride reacts with silica to form a xenon
42. The percentage (by volume) of argon in the atmosphere is compound X. The oxidation state of Xe in X is:
about: .
[E.A.M.C.E.T. (Medi~n 2004; D.C.E. 20(8)
(a) 1 % 0 (b) 2 % 0
(a) +2 0 (b) +4 0 (c) +6 0 (d) 0 0
(c) 10% 0 (d) 0.2% 0
[Hint: Si02 + 2XeIt---t 2XeOF4+ SiF4
43. Which of the following is planar? rC.B.S.E., P.M.T. 2000} (X)
(a) XeF4 0 (b) xe04 0 Oxidation state of Xe in (X) is +6.]
(c) ~F2 0 (d) XeOF4 0 54. In the Dewar's method of separation of noble gases, the
44. The hybridization of Xe in XeF2 is: [M.E.E. (Kerala) 2000) mixture of noble gases is kept in contact with coconut
charcoal at 173 K. Which one of the following gaseous 60. What is the correct order of occurrence (% by weight) in air
mixture is not adsorbed on the charcoal? of Ne, AI and Kr? [A.F.M.C. 2008J
[E.A.M.C.E.T. (Engg.) 2004] (a) Ne>AI>Kr 0 (b) Ne>Kr>AI 0
(a) Ar, Kr 0 (b) He, Ne 0 (c) AI>Kr>Ne 0 (d) AI>Ne>Kr 0
(c) Xe,Ar 0 (d) Xe, Kr 0 61. The compound in which the number of d1t-pTC bonds are
55. Among the following molecules, equal to those present in Cl04: [E.A.M.C.E.T.(Engg.) 2008]
(i) Xe03 (li) XeOF4 (iii) XeF6 (a) XeF4 0 (b) Xe03 0
Those having same number of lone pairs on Xe are: (c) xe04 0 (d) XeF6 0
[A.I.I.M.S, 2005] r
62. The formation of 01 [PtF6 is the basis for the formation of
(a) (i) and (ii) only o· (b) (i) and (iii) only 0 xenon fluorides. This is because: [J.M.I. (Engg.) 2008]
(c) (ii) and (iii) only 0 (d) (i). (ii) and (iii) 0 (a) 02 and Xe have comparable sizes 0
56. The xenon compound(s) that are isostructural with IBri (b) Both O2 and Xe are gases 0
and BrOi respectively are: (c) O2 and Xe have comparable ionisation energies 0
(a) linear XeF2 and pyramidal Xe03 _ _. _ _. . __I:J_, __~(d2 Both_~ an4.J9~m_m_. . _ _. _ _. ._mm_. . ~...m. .m
(b) bentXeF2 and pYra:mldal Xe03 - - 0 63. Which of the following reactions of xenon compounds is not
(c) bent XeF2 and planar Xe03 0 feasible? [A.I.E.E.E.2009]
(d) linear XeF2 and tetrahedral Xe03 0 (a) Xe03 + 6HF~ XeF6 + 3H20 0
[Hint: ffiri is linear like XeF2 while Br03 is pyramidal like (b) 3XeF4 + 6H20~ 2Xe + Xe03 + 12 HF + 1.5 O2 0
Xe03'] . (c) 2XeFz + 2H20---4-2Xe+4HF+-02~m ·~El-
57. Number oflone pairs of electrons on Xe atoms in XeF2 • XeF4 (d) XeF6 + RbF ----+ Rb[XeF71 0
and XeF6 molecules are respectively: [A.LE.E.E.2OO2] [Hint: The reaction (a) is not feasible because XeF6 fonned at
(a) 3, 2 and I 0 (b) 4, 3 and 2 0 once reacts with water producing again the reactants.]
(c) 2. 3 and 1 0 (d) 3, 2 and 0 0 64. Argon is used: [C.E.T. (Karnataka) 2009]
58. Which is the most easily liquefiable rare gas? (a) to obtain low temperature 0
[C.E.T. (Karnataka) 2008] (b) in high temperature welding 0
(a) AI o (b) Ne 0 (c) in the radiotherapy for treatment of cancer 0
(c) Xe o (d) Kr 0 (d) in filling airships 0
59. In the separation of noble gas mixture from air by Ramsay 65. Which of the following noble gas has its ionization potential
Rayleigh's first method, the substances used for the removal closest to oxygen? [C.E.C.E. (Bihar) 2010]
of N2 and O 2 respectively, are: [p.M.E.T.2008] (a) He 0 (b) Ne 0
(a) Cu and Mg 0 (b) Mg and Cu 0 (c) Xe 0 (d) AI 0
(c) C and CaC 2 0 (d) KOH solution 0
Set IT : This set contains the questions with two or more correct answers.
66. XeF6 on reaction with H2 gives: (a) Rare gases of atmosphere 0
(a) Xe 0 (b) HF 0 (b) Noble gases 0
(c) XeF2 0 (d) XeF4 0 (c) Inert gases 0
67. Which of the following compounds cannot be prepared by (d) Rare-earths 0
direct reaction between the constituent elements? 70. XeF6 on hydrolysis gives:
(a) XeF2 0 (b) XeF4 0 (a) XeOF4 0 (b) Xe02F2 0
(c) XeOF4 0 (d) Xe03 0 (c) Xe03 0 (d) xe04 0
68. Which of the following noble gases do not form any 71. Which among the following statements is/are correct?
compound? (a) XeF4 and SbFs combine to form salt. 0
(a) He 0 (b) Kr 0 (b) He and Ne do not form clathrates. 0
(c) Ne 0 (d) Xe 0 (c) He has lowest b.pt. in its group. 0
69. Which of the following names are used for group zero (d) He diffuses through rubber and polyvinyl chloride. 0
elements?
1. (b) 2. (c) 3. (a) 4. (d) 5. (c) 6. (d) 7. (a) 8. (b) 9. (a) 10. (c)
11. (b) 12. (d) 13. (d) 14. (a) 15. (b) 16. (d) 17. (a) 18. (b) 19. (c) 20. (d)
21. (a) 22. (c) 23. (b) 24. (c) 25. (a) 26. (c) 27. (c) 28. (b) 29. (b) 30. (b)
31. (d) 32. (a) 33. (d) 34. (b) 35. (c) 36. (b) 37. (a) 38. (a) 39. (b) 40. (a)
41. (a) 42. (a) 43. (a) 44. (c) 45. (b) 46. (a) 47. (c) 48. (c) 49. (c) 50. (b)
51. (a) 52. (a) 53. (c) 54. (b) 55. (d) 56. (a) 57. (a) 58. (c) 59. (b) 60. Cd)
61. (c) 62. Cd) 63. (a) 64. (b) 65. (c) 66. (a, b) 67. (c,d) 68. (a,c) 69. (a,b,c) 70. (a,b,c)
71. (a,b,c,d)
".~-=objective Questions for liT ASPIRANTS .;~>

1. What are the products formed in the reaction of xenon 4. The noble gas which shows abnormal behaviour in liquid
hexafluoride with silica? state and behaves as a superfluid is:
(a) XeSi04 + HF (b) XeF2 + SiF4 (a) neon (b) helium
(c) XeOF4 + SiF4 (d) Xe0 3 + SiF4 (c) argon (d) xenon.
[Hint: 2XeF~+Si62~·2Xe6F4· +SiF41 5. XeF2 reacts with SbF5 to form:
2. Which of the following two are isostructural? (a) [XeF] [SbF6] (b) [XeF3][SbF4]
(a) XeF2, IFi (b) NH3, BF3 (c) XeSbF6 (d) XeF4
(c) CO~-, SO~- (d) PCIs,ICls 6. Which of the following compounds is explosive?
[Hint: XeF2 is a linear molecule (Xe is sp3d hybridized with (a) XeF2 (b) XeF4
three equatorial positions occupied by lone pairs). (c) Xe03 (d) XeF3
is a linear molecule (I is sp 3d hybridized, with three 7. XeF6 on reaction with CsF gives:
positions occupied by lone pairs).] (a) [XeFs][CsF2] (b) XeFg
3. Number of atoms of He in 100 amu of He (atomic mass of (c) [XeF4][CsF3] (d) Cs[XeF7]
He is 4) are: 8. Which of the following is/are solid at room temperature?
(a) 100 x 6 X 1023 (b) 100 (a) XeF2 (b) XeF4
(c) 50 (d) 25 (c) XeF6 (d) All of these
Mass of substance - 100_ 25 ]
[Hint : No. 0 f atoms = - - -
mass 4
1. (c) 2. (a) 3. (d) 4. (b) 5. (a) 6. (c) 7. (d) 8. (d)

On p-block elements 2. Match List-I with List-II:
List·} List·II
1. Match the elements of List-I with their uses in List·II: (a) XeF 2 (p) Square pyramidal
Ust·} List·II (b) pels (q) Linear shape
(Element) (Uses) (c) XeOF4 (r) sp 3d hybridization
(a) He (p) Treatment of cancer (d) XeF4 (s) sp 3d 2
(b) Rn (q) Used in caution lamp 3. Match List-I with List-II:
(c) Ne (r) Filled in the oxygen cylinders List·} List-II
(a) He (p) London dispersion force
of sea divers
(b) Xe (q) Lowest boiling noble gas
(d) Ar (s) Filled in electric bulbs
(c) XeF 6 (r) sp 3d 3 hybridization
(t) Used in airship balloons
Cd) IF7 (s) Distorted octahedral
4. Match the process in List-I with compounds in List-TI and the 8. Match List-I with List-TI:
catalyst used in List-ill: List-} List-n
List-I List-n List-ill (a) Pnicogens (p) Geoup-17-elements
(a) Haber's process (p) Manufacture of (u) Iron powder (b) Halogens (q) Group-IS-elements
chlorine (c) Chalcogens (r) Group-16-elements
(b) Deacon's process (q) Manufacture of (v) Pt gauge (d) Group with eight atoms (s) Group with solid, liquid
,I nitric acid in the molecular form of and gaseous elements in free
(c) o.stwald's process (r) Manufacture of (w) Copper(II) element state
vanaspati ghee chloride 9. Match List-I with List-TI:
(d) Hydrogenation of (s) Manufacture of (x) Finely divided List-} List-n
vegetable oils ammonia nickel (a) S-S linkage (p) Dithionic acid
5. Match List-I with List-TI: (b) -0-0- linkage (q) Thio-sulphuric acid
List-I List-n (c) H 2S20 g (c) Caro's acid
(C:IDI!PQ!\P1D _____ ~(Hybrid stateoshape)__ (d)-H2SOs· . (s}MarshaH'sacid-···----··-
(a) BC13 (p) sp2 10. Match List-I with List-TI:
(b) H3Bo.3 (q) sp3 List·} List-n
(c) B2H6 (r) Bridge structure (a) Be(OHh (p) o.xidising agent
(d) Hybrid state of B and N (s) Triangular planar shape (b) HN0 3 (q) Amphoteric
in (HjNBF3) ... (c)HNOi- c ····(rr-·Ge1ani:ious-wtiiteppt:-=~~--··
6. Match the halides of List-I with their properties in List-II: (d) AI(OHh (s) Reducing agent
List-} List-n 11. Match each of the reactions given in column-I with corresponding
(a) BeC12 (p) Dirneric product(s) given in column-TI: [I.I.T. 2009]
(b) AIC1 3 (q) Lewis Acid Column-I Columo-n
(c) CC14 (r) Tetrahedral (a) Cu + di1. HN0 3 (p) NO.
(d) SiCl4 (s) Pyrene (b) Cu + cone. HN03 (q) NO. 2
(t) Polymeric (c) Zn + di1. HN03 (e) N2o.
7. Match the elements in List-I with their properties in List-TI: (d) Zn + conc. HN0 3 (s) Cu(N0 3h
List-} List-n (t) Zn(N0 3 h
(a) o.2(g) (p) Paramagnetic
(b) S2(g) (q) Two unpaired electrons
(c) Po (r) Radioactive
(d) Rn (s) Formed by a-decay of radium
1. (a-r, t) (b-p) (c-q) (d-s) 7. (a-p, q) (b-p, q) (c-r) (d-r, s)

2. (a-q, r) (b-r) (c-p, s) (d-s) 8. (a-q) (b-p, s) (c-r) (d-c)
3. (a-p. q) (b-p) (e-r, s) (d-r) 9. (a-p, q) (b-r, s) (e-s) (d-c)
4. (a-s:-u) (b-p-w) (c-q-v) (d-r-x) 10: (a-q) (b-p) , (c-p, s) (d-q, r)
5. (a-p. s) (b-p) (c-q, r) (d-q) 11. (a-p, s) (b-q, s) (c-r, t) (d-q, t)
6. (a-t) (b-p, q) (c-r, s) (d-r)

The following questions consist of two statements as 1. (A) Helium and neon do not form c1athrates.
Assertion (A) and Reason (R). While answering these questions, (R) Both have smallest atomic size among all the elements
you are required to choose anyone of the following responses. of group 18.
(a) If both (A) and (R) are true and (R) is the correct 2. (A) The elements of group 18 are called inert gases.
explanation of (A). (R) The elements of group 18 are mono-atomic in nature.
(b) If both (A) and (R) are true but (R) is not the correct 3. (A) Noble gases have highest ionisation energies in their
explanation of (A). respective periods.
(c) If (A) is true but (R) is false. (R) The outermost ~shell of the noble gases is completely
(d) If both (A) and (R) are false. filled.
4. (A) Noble gases can combine with fluorine to fonn (R) The atomic numbers of noble gases are even and all the
respective fluorides under specific conditions. orbitals are doubly occupied by the electrons.
(R) Fluorides of He, Ar and Ne are unstable in nature. 6. (A) Hez does not exist.
S. (A) Noble gases are diamagnetic atoms. (R) Bond order of Hez is zero. [BHU 2005]
1. (a) 2. (b) 3. (c) 4. (d) 5. (a) 6. (a)
11111111 11111111
... 1.~-A.rgQn~is~used~in~arcwelding-because .. ofits:-~-~.
(a) low reactivity with metal
The noble gases have closed shell electronic configuration and (b) ability to lower the melting point of metal
are mono atomic gases under nonnal conditions. The low boiling (c) flammability
points of lighter noble gases are due to weak dispersion forces (d) high calorific value
between-the7-atoms.~and .... the ... absence .of otheJ'~interatomic.
2. The structure ofXe03 is:
interactions. (a) linear (b) planar
The direct reaction of xenon and fluorine leads to a series of (c) pyramidal (d) T-shaped
compounds with oxidation numbers +2, +4 and +6. XeF4 reacts 3. XeF4 and XeF6 are expected to be:
violently with water to give Xe03' The compounds of xenon exhibit (a) oxidising (b) reducing
rich stereochemistry and their geometries can be deduced (c) unreactive (d) strongly basic
considering the total number of electron pairs in the valence shell.
[I.I. T. 2007]
Thought 1 1. (a) 2. (c) 3. (a)
The answer to each of the following questions is a single 4. How many lone pairs of electrons are present on xenon atom
digit integer, ranging from 0 to 9. in XeF4?
1. How many noble gases are radioactive in nature? S. Xenon hexafluoride reacts with silica. What is the oxidation
2. What is the bond order of Nez? state of xenon in the xenon compound fonned?
3. What is the percentage by volume of inert gases in the
atmosphere?
cr:WHifii ,<~.<-~"----------------------
..
1. (2) Radon and ununoctium. +6

2. (0) Number of bonding and antibonding electrons are equaL 5. (6) 2XeF6 + Si0 2 ~ 2XeOF4 +SiF4
3. (1)
..
4. (2) F~F
F~F
RE!vi§ion Exerci!il!
[l:lJap1:er -.
/ ~ ,
1:0 13)
--- - .
a
SINGLE CORRECT ANSWER TYPE 9. The ease of liquefaction of noble gases decreases the order:
(a) He> Ne > Ar > Kr > Xe D
L Which of the following oxides of nitrogen is paramagnetic?
(b) Xe > Kr > Ar > Ne > He D
(a) N 20 D (b) N 20 S D
(c) Kr> Xe > He >Ar >Ne D
(c) N~ D (d) N20 3 D
(d) Ar> Kr> Xe > He> Ne D.
2. The major role of fluorspar (CaF2) which is added in small
10. Al and Ga have nearly same covalent radius because of :
quantity in the electrolytic reduction of alumina dissolved in
(a) ..pooLshlelding_effecLofs"electronsjn..Ga.atom- --.....Q--
-eryolite{Na3AlFo) is-:
(b) poor shielding effect of d-electrons of Ga-atom D
(i) as a catalyst
ec) poor shielding effect of J-electrons of Ga-atom D
(Ii) to make the mixture very conducting
(d) none of the above D
(ill) to lower the temperature of the melt
11. Ge(II) compounds are powerful reducing agents whereas
(iv) to decrease the mte of oxidation of carbon at anode
CorrectoptIoiiis:- . Pb{IV) cmnpolinos-ate stfOifgoxidisiilgageiils.Tfdiii beaue~ ..
to:
(a) (i), (ii) D (b) (ii), (iii) D
(a) Pb is more electropositive than Ge D
(c) (i), (ii), (iii) D (d) (i), (iv) D
(b) ionisation potential of lead is less than that of Ge D
3. Which one of the following compounds has the smallest
(c) ionic radii of Pbz+ and Pb 4+ are larger than those of Ge2+
bond angle in the molecule?
and Ge4+ D
Ca) S02 D (b) H20 D
(d) more pronounced inert pair effect in lead than in Ge D
(c) H2S D (d) NH3 D
12. Which of the following statements is incorrect?
4. Thallium shows different oxidation states because :
(a) ICI is a good conductor of electricity in fused state. D
(a) of its reactivity D
(b) Clz0 7 is an anhydride of perchloric acid. D
(b) of its amphoteric nature D
(c) Melting and boiling points of HBr are more than HCl.D
(c) it is a transition metal D
Cd) F z forms only one oxoacid. D
(d) of inert pair effect of electrons D
13. Amorphous boron is extracted from borax by following steps:
5. Match list-I with list-II and select the correct answer:
List-} List·II CA) (B) (el
Bomx ---7 H3B03 ---7 B Z0 3 ---7 Boron
(p) XeF4 1. Distorted octahedral
(A,) and (C) are :
(q) XeF6 2. Tetrahedral
(r) Xe03 3. Square planar ' (a) H2S04,AI D (b) HCl,C D
i, (c) HCl, Fe D (d) H 2S04,Na D
(s) XeO.. 4. Pyramidal
(a) p-3, q-l, r-4, s-2 D (b) p-2, q-3, r-l, s-4 D 14. In the process XH3 + H+ ---7 XH! (X being N, P, As or
(c) p-4, q-l, r-3, s-2, D (d) p-l, q-4, r':"2, s-3 D Sb), the maximum increase in the bond angle will be in the
6. Which of the following represents the correct order of case of:
decreasing number of S = 0 or S ---7 0 bonds? (a) NH3 D (b) PH3 D
(a) H2S20 g > H2S04 > H2S03 D (c) AsH3 D (d) SbH3 D
(b) H2S03 > H2S20 s > H2S04 D 15. When Cl2 water is added to an aqueous solution of
(c) H2S20 g > H2S03 > H2S04 D potassium iodide in presence of chloroform, a violet colour
(d) H2S04 > H ZS03 > HzS 20 s D is obtained. On adding more of Cl2 water, the violet colour
7. The heavier elements of group 15 do not form pre-pre bonds disappears. This is due to formation of :
because: (a) KI03 D (b) KIO D
(a) their atomic orbitals are large and diffused D (c) HI03 D Cd) HI D
(b) their atomic orbitals do not overlap effectively D 16. Hydrolysis of PI 3 yields:
(c) both (a) and (b) D (d) none of these D (a) monobasic acid and a salt D
8. Bones glow in dark. This is due to : (b) monobasic acid and a dibasic acid D
(a) conversion of white P into red P D (c) dibasic acid an tribasic acid D
(b) conversion of red P into white P D (d) monobasic acid and tribasic acid D
(c) slow combustion of white P in contact with air D 17. In [B 40 S (OH)4]2-, the number of boron atoms having an octet
(d) none of the above D of electrons is :
(a) 0 o (b) I o ONE OR MORE THAN ONE CORRECT

(c) 2 o (d) 4 IJ ANSWERS TYPE
excess NH3 .
18. B2H{j h'19h temp. ) A, A IS : 31. Which of the following statements are correct?
(a) (BN)x 0 (b) B2H{j·2NH3 0 (a) Conc. HN03 attacks Alliberating N0 2. 0
(c) B3N3H{j 0 (d) all of these 0 (b) Al dissolves in HCl and not in conc. NaOH. 0
19.. CO is stable oxide of carbon while SiO.is unstable because: (c) The corrosion of Al is prevented by the formation of a
(a) carbon can form coordinate bond 0 coating of its oxide on its surface.
(b) p1t-p7t bond is present between C and 0 which is not (d) Dilute H2S04 attacksAl very slowly evolving hydrogen.
possible in SiO 0 o
(c) carbon is smaller in size than silicon 0 32. Mark the correct statements :
(d) none of the above· 0
(a) Alumina is used as a refractory material. IJ
(b) Boron carbide is used as an abrasive for polishing. 0
. 20. Ihe~hain.buildingJ!.nitin SilicQ.I1~J)Qlymeri~:
. (crBotax iSUstXnrf];lazing:-u~-n--~~-~Df-----
(a) Me3SiCl 0 (b) MeSiCl3 0
(d) Alum is used for ftre-prooftng fabrics. 0
(1::) MezSiCl2 0 (d) none of these IJ
33. Graphite:
21. Equimolar mixture of PCls and water gives:
(a) is paramagnetic 0 (b) has unpaired electrons 0
(a) PCX.13 0 (b) H~3 0
(c) has .mobile electrons 0 ~(d) is diamagnetic 0
(1::)cM3PO;:f~~-~c-~~·~nid)~both·(a~"and(c) .... ~ ... 0
34. Mark the incorrect statements : ~===
22. The hybridisation of P in pot is same as in : (a) Silicon hydrides are known as silicones. 0
(a) I in IC14 0 (b) Sin S03 0 (b) Liquid silicones act as lubricants. 0
(e) N in NO) 0 (d) Sin soi- 0 (c) Sheet silicates are formed from [Si04]4- tetrahedral units
23. An oxide of lead which is used in lead storage batteries, in by sharing three oxygen atoms. 0
safety matches and as a powerful oxidising agent, is : (d) Buckminsterfullerene is paramagnetic as it has unpaired
(a) PbOz 0 (b) Pb30 4 0 electrons. 0
(c) PbO 0 (d) 2PbO·Pb02 0 35. (NH4hCr2~ on heating gives:
24. z
The order of bond length in NO, NO). NO and N20 4 is : (a) Cr203 0 (b) N2 IJ
(a) NO)" > N02: > N204 > NO 0 (c) NO 0 (d) NH3 0
(b) NO>N 20 4 >N02:>NO)" 0 36. Which acids are formed by the action of water on phos-
phorus pentoxide ?
(c) NO> NO)" > N204 > N02: 0
(a) ~ 0 (b) ~P2~ 0
(d) N204 > N02" > NO) > NO 0
(c) H3P04 0 (d) H3P03 0
25. Oxygen is more electronegative than sulphur. Yet H2S is acidic 37. HI can not be prepared by heating Kl with conc. H 2S04
while H20 is neutral. This is due to : because:
(a) H2S is a gas while H 20 is a liquid 0 (a) H2S04 is stronger than HI 0
(b) H-S bond is weaker than H-O bond 0 (b) HI is stronger than H2S04 0
(c) H20 is highly associated compound 0 (c) H2S04 is an oxidising agent 0
(d) molecular mass of H2S is more than that of H20 0 (d) HI is a reducing agent 0
26. In ozone, there are : 38. Mark out the incorrect match of shape :
(a) 20' and I1t bonds 0 (b) 10' and 21t bonds 0 (a) ICl4:Squareplanar 0 (b) XeOF2:TrigonaLplanarCJ
(c) 20' and 21t bonds 0 (c) [SbFs]2-: Square bipyramidal b
(d) 20' and 11t bonds and one lone pair of electrons 0 (d) NH2: Pyramidal 0
Zl. Which of the following halogens is called super halogen? 39. Select the correct order of reactivity :
(a) Fluorine 0 (b) Chlorine 0 (a) HI>HBr>HCI>HF 0 (b) HCI04>HBr04>HI04 0
(c) Bromine 0 (d) Iodine 0 (c) HCIO<HBrO<HIO 0
28. Swimming pools are disinfected by bubbling through water (d) HCI04>HCI03>HCI0 2 >HCIO 0
a controlled quantity of : 40. Which of the following statements are correct ?
(a) Br2 0 (b) N2 0 (a) Cl2 reacts with aqueous Na2S203 to form HCI and
(c) Cl2 0 (d) Oz 0 NaHS04. 0
29. Diamagnetic oxide of chlorine is : (b) Cl2 reacts with aqueous Na2S203 to give Na2S406 and
.N~ . 0
(a) ClOz 0 (b) Cl~ 0
(c) Cl206 0 (d) none of these 0 (c) A white precipitate of silverthiosulphate is formed which
30. The reaction of XeF6 with silica gives: changes to yellow, brown and finally black when silver
(a) XeF4 and Sif4 0 (b) XeOF2 and Sif4 0 nitrate is added to Na2S203' 0
(c) XeOF4 and SiF4 0 (d) none of these 0 (d) Sodium thiosulphate is quantitatively oxidised by iodine.
o
ASSER~ION-REASON TYPE QUES,.IONS 52. Match Column-I with Column-II:
The questions given below consist of an Assertion (A) and Column-I Column-II
Reason (R). Use the following key for the appropriate answer of (a) H3P02 (p) Reducing
each. question. (b) H2S (q) Monobasic
(a) Both (A) and (R) are correct and (R) is the correct (c) HN02 (r) Dibasic
explanation of (A). (d) HI (s) Oxidising
(b) Both (A) and (R) are correct but (R) is not the correct
explanation of (A).
Column-I Column-II
(c) (A) is correct but (R) is incorrect.
(d) (A) is incorrect but (R) is correct. (a) Zn + V. diL HN03 (p) l\T{)
(e) Both (A) and (R) are incorrect. (b) Sn + diL HN0 3 (q) N02
41. (A) Lead exhibits oxidation states of +2 and +4. (c) Ag + diL HN0 3 \' (r) NH4N03
. (R) Lead_exhibitsinerLpaiLeffect. (d)Pb+conc.HN03 (s)Sn(N03J2
42. (A) Al forms [AIF6]3- but B does not form [BF6]3-. (t) Zn(N03h
(R) B does not react with fluorine. 54. Match Column-I with Column-II:
43. (A) PF5 and IF5 have similar shapes. Column-I Column-II
(R) PF5 has two types of P-F bond lengths. (a) NH4N03 (P) Laboratory reagent
44 •. {A)--Xenorc f()oos -tl:iree-flUoodes-Witli-mb1eclilar forijrlliae (b) (NHJ2S04 (q) In malcingoryceUs
XeF2, XeF4 and XeF6· (c) Nl40 (r) Fertiliser
(R) The formation of xenon fluorides involves the unpairing (d) NH40H (s) Explosive
of p-orbitals and promotion of electron or electrons to 55. Match Column-I with Column-II:
the vacant d-orbitals in the outermost shell. The number Column-I Column-II
of unpaired orbitals under the excited states are either 2 (a) P40\O (p) Ionic
or4 or 6. (b) Si02 (q) Covalent
45. (A) Halogens combine with each other and form binary (c) Al20 3 (r) Acidic
covalent compounds of ABn type which are called (d) SnO (s) Amphoteric
interhalogen compounds. B is always smaller atom and 56. Match Column-I with Column-II:
n may have values I to 7. Column-I Column-II
(R) Interhalogen compounds are less reactive than A2 or B2 (a) HF (p) Reducing agent
molecules. (b) HI (q) Oxidising agent
46. (A) Sulphuric acid has great affinity for water. It acts as a (c) O2 (r) Precipitate with AgN0 3 solution
powerful dehydrating agent. (d) (CN)2 (s) Attacks glass
(R) Sulphuric acid has corrosive action on skin also. (t) Pseudo halogen
47. (A) Boron, aluminium and gallium form complex anionic hy-
dridesofthetypeNaB~,LiAlH4andLiGaH4,respectively. LINKED COMPREHENSION TYPE
(R) These complex hydrides are powerful reducing agents.
48. (A) The abundance of carbon is more than silicon in earth's Passage 1
crust. Silicates are minerals containing tetrahedral SiOt structural
(R) Carbon has the maximum property of catenation. units. A variety of silicate structures occur in nature, ranging from
49. (A) All the oxidation states of nitrogen from + 1 to +4 show single tetrahedra to pairs, rings, chains, sheets and three-
disproportionation in acidic medium. dimensional networks of linked tetrahedra with cations to balance
(R) Aqueous nitric acid undergoes disproportionation. the total charge in the crystaL In aluminosilicates, aluminium
50. (A) All the halogens are paramagnetic in atomic forms. atoms substitute for some of tetrahedrally bonded silicon atoms
(R) Halogens have seven electrons in their outermost shell and additional cations are present in order to maintain a net charge
. thh
z.e., ey ave ns2np5 conf i'
IguratlOn. of zero. Zeolites are network aluminosilicates having pores on a
molecular scale. They are useful for exchanging ions, for separa-
MATRIX MATCHING QUESTIONS ting mixtures of gases and as catalysts.
51. Match Column-l with Column-II and Column-III: Answer the following questions :
Column-I Column-II Column-ID
57. Silicates which contain two units of SiOt joined along a
(a) XeF2 (p) 9(J' (i) Tetrahedral
comer containing oxygen are called :
(b) XeF4 (q) 109.so (ii) Pyramidal (a) orthosilicates (b) pyrosilicates
(c) Xe04 (r) 103° (iii) Linear (c) cyclic silicates (d) chain silicates
(d) Xe03 (s) 18Ct' (iv) Square planar
58. The general fonnula of cyclic or ring silicates is : same elements yield volatile fluorides with significant covalent
(a) (Si20s);n- (b) (Si0 3);"- character.
(c) (SiO~l" Cd) both (b) and (c) Compounds of fluorine with the non-metals possess a wide
59. Mark the incorrect statement : range of reactivities and molecular geometries. SF6 is an inert
(a) Zeolites are a class of three dimensional aluminosilicates compound while BF3 is a strong lewis acid. SbFs is a strong
which can accommodate water molecules in their cavities. fluorinating agent. PtF6, a strong fluorinating agent has opened
(b) Quartz, tridymite, feldspar, etc. are three dimensional up modern research on the compounds of the noble gases.
silicates. Answer the following questions :
(c) Zeolites can be used to soften hard water. 63. Which can bring the highest oxidation state in the transition
(d) Three dimensional silicates involve three oxygen atoms metal?
of each tetrahedra for sharing with adjacent tetrahedra. (a) (b) O 2
(c) Br2 (d) 12
···Pjssage2~~~~ . ·6<J.Amongffii~IIuonaesgivenoelow whiCJlwilnuitilerreactwl\:lf~-
~:
All the elements of group 13 fonn trihalides. The boron halides
(a) NaF (b) CaF2
are covalent. The trifluorides of AI, Ga, In and TI are ionic while
(c) SF6 (d) IFs
chlorides, bromides and iodides are largely covalent when
6~. Wlri~h .ollecoftheJollowingte.actigus ~does_no.LQccur.J7 ~~~
aIihyarous~However~~ffieif~cova1erit·· rianiii~ decreasei(oniliOvirig
from Ga to Tl. Trihalides fume in aif and undergo hydrolysis. They (a) ~ +2CI- ---,t2F +C12
act as Lewis acids. They fonn complex halides. (b) Cl 2 +2F- ---,t2Cl- +~
. Answer the following questions : (c) Cl2 + 2Br- ---,t 2CI- + Br2
60. Which of the halides does not undergo hydrolysis? (d) ~ +2Br- ---,t2F- +Br2
(a) BF3 (b) B03
(c) AlP3 (d) AlCl3 INTEGER ANSWER TYPE
61. Which of the following statements about anhydrous
66. How many 1t-bonds are present in the molecule of borazine?
aluminium chloride is, correct?
67. The number of'isomers possible for disubstituted borazine,
(a) It exists as AICl3 molecule.
B3N3.fJ4X2 is :
(b) It is not easily hydrolysed.
68. Red lead reacts with conc. HCI according to following
(c) It sublimes at lOO°C under vacuum. reaction, . .
(d) It is a strong Lewis base.
Pb304 + HCI---,t XPbCl2 + Cl2 + H20
62. Which of the following statements is correct?
Balance this reaction and find the value of X.
(a) Both AlCl 3 and BCl3 are not Lewis acids.
69. What is the basicity of phosphorus acid?
(b) Both AICl 3 and BCl3 are equally strong Lewis acids.
70. How many sigma bonds are present in the molecule of caro's
(c) AI0 3 is stronger Lewis acid than B03'
acid?
(d) BCl3 is stronger Lewis acid than Al0 3 .
71. What is the oxidation state of:> in H2S04?
Passage 3 72. How many lone pairs of electroJls are present in central atom
ofClF3?
The chemistry of fluorine differs sharply from the other
halogens. Fluorine atoms fo,m weak bonds to other fluorine atoms
but particularly strong bonds to most other kinds of atoms .
.Fluorine displaces other halogens from their compounds and
oxidises elements in compounds exposed to it. The compounds
of fluorine with metals in their lower oxidation states are salts with
strong ionic character. The higher oxidation states of many of the
1. (c) NOz is paramagnetic due to the presence of unpaired electron. 15. (c) 2KI + Cl 2 --? 2KCl + 12
2. (b) CaF2 in the system acts as a thinner. It lowers the temperature
12 + CHCl3 --? Violet layer
of the melt and makes it more conducting.
3. (c) S02 H20 H2S NH3 Cl2 + H 20 --? 2HCl + [0]
~2 ~3 ~3 ~3 12 or H 20+5[0) --? 2Hl03
0 Colourless
119.so 104.5 92.so 107.50
4. (d) 16. (b) PI3+3H20--? 3Hl +H3P03
2
5. (a) XeF4 sp3 d Square planar (Monobasic)' (DiOOsic)
3 17. (c) Borax ion can be represented as :
XeF6 sp3 d Distorted octahedral
Xe03 sp3 Pyramidal
---Xe04 '-~Sj53--~-letrahearaI~-" 2-
6. (a) H 2S 2 0S
o 0
~s S/
O/o~O~O~~'()
(4S=O)
bonds
H 2S0 4
Thus, borax contains two B-atoms having an octet of electrons.
O"S/O I
Low temp.
)B 2 H 6 · 2NH 3
18. (a) B2H6 + NH3 - l .
HO/ "'OH . I HIgh temp.) (BN) x
(2S=O)
High
bonds B2H6 . 2NH3 ~ B3N 3H6
Temp.
19. (b)
20. (c)
/s, 21. (a) PCl s +H 20--?POCI 3 +2HCl
HO j 0
OH (1 : \)
(One S=O bond) PCIs +4H 20 --? H 3P0 4 +5HCl

(1 4)
7. (c).
8. (c) 4P + 502 --? P40 lO + light
22. (d) ICl 4 SO~- . PO~-
The phenomenon of emitting light as a result of chemical change
sp 3d 2 Sp3 sj,3
is called chemiluminescence.
9. (b) Ease of liquefaction increases in the group from top to bottom 23. (a)
as van der Waals' forces increase with increase of atomiC size. 24. (a) NO NO:i N02
10. (b) Due to poor shielding effect of d-electrons the outer electrons Bond length 115 pm 122 pm 121 pm
in Ga experience more attraction by the nucleus. 25. (b)
)'
~
11. (d) Ge(IV) is more stable than Ge(II) while Pb(II) is more stable o
than Pb(IV). ~~ ~.>
'0 " '<9
12. (d) Fluorine does not form oxoacid. 26. (d) ,rO- . 116.80,o~.
13. (d) Na2B407 H 2S0 4--? Na2S04 + H 2 B40 7
(A) ..
:0 .0'
.. ....
H 2B40 7 +5H20 ---7 4H 3B0 3 27. (a) 28. (c) 29. (c)
30. (c) 2XeIt; +Si02--? 2XeOF4 + SiF4
Heat
2H3B03 ~ B203 + 3H 20 31. (c, d)
B203 + 6Na --? 2B + 3Na20 32. (a, b, c)
(C) 33. (c, d) Graphite has sigma and It-bonds. The 1t-electrons are free to
14. (d) The bond angle in the hydrides vary in the order: move throughout the entire layers.
NH3 > PH3 > AsH3 > SbH3 34. (a, d) Silicon hydrides are known as siJanes. Buckminsterfullerene
4,
In the formation of XH the bond angle becomes 109°28' . is diamagnetic as it does not have unpaired electrons.
Hence maximum increase will occur in SbH3. 35. (a, b) (NH4hCr207 heat)Nz+Cr203+4H20
50. (a)
36. (a, b, c) P40 lO 2H 20) 4HP0 3 2H 20) 2H 4P20 7 51. (a-s-iii); (b-p-iv); (c-q-i); (d-r-ii)
Metaphosphoric Pyrophosphoric 52. (a-p. q); (b-P. r); (c-P. q, s); (d-p, q)
acid acid
53. (a-r, t); (b-r. s); (c-p); (d-q)
2H 2 0 I 54. (a-r, s); (b-p, r); (c-p, q); (d-p)
4H 3P0 4 ~ 55. (a-q, r); (b-q, r); (c-P. s); (d-p, s)
Orthophosphoric
acid 56. (a-s); (b-p, r); (c-q); (d-q, t)
57. (b)
37. (c, d) 2HI + H2S04~I2 +S02 +2H 20 58. (d)
Reducing Oxidising
agent agent 59. (d)
60. (a) BF3 forms an addition product with water as B-F bond is
38. (b, d)XeOF2 - sp3 d ~ T-shaped
very strong.
NH z- sl
~ V-shaped
J!),-_(l!,J6~L _ _ _ _
. _ _ _ _ _ _ _ ~ _ _ _ _ _ __ _ + - - -
40. (a, c, d) Na2S203 +4C12 +5H 20 ~ 2NaHS0 4 +8HCI 61. (c)
62. (d)
2AgN0 3 + Na2S203~ Ag 2S20 3 + 2NaN0 3
63. (a)
Ag2S203 + H 20 ~ Ag 2S + H 2S04 64. (d) IFs + F2 ~ IF7
65. (b)-
2Na2SZ03 + I2~ 2NaI+ Na 2S40 6
66. Three: Borazine has structure similar to benzene.
41. (a)
67. Four: See objective question 15 on Page 407.
42. (c) B does not have d-orbitals.
68. Three: Pb304 +8HCI ~ 3PbCl2 +C12 +4H 20
43. (d) PFs has trigonal bipyramidal shape having two types of P-F
bond lengths. 69. Two: H3P03 is a dibasic acid. It forms two series of salts.
IFs has square pyramidal shape. 70. Seven: H2SOS is represented as :
44. (a)
45. (e) Assertion is wrong as n may have values 1, 3, 5 and 7.
o
all
Reason is also wrong as interhalogen compounds are more H~O~S~O~O~H
reactive than A2 or B2 molecules as A-B bond is weaker than all
A-A and B-B bonds. o
46. (b) 71. Six
47. (b) 72. Two: CI in first excited state
48. (d) Carbon is less abundant than silicon in the earth's crust, 3s 3p 3d
however, compounds of carbon are very large due to catenation
property.
Ilil IHI t -,----I--'----'--'------'
i i i I L!...I
49. (c) (A) is correct while (R) is incorrect. In RN0 3• the oxidation
state of nitrogen is +5.
'~.
CHAPTER
14
2 13
Transition Elements
-
F 3 4 5 6 7 8 9 10 11 12
-
or tl-blockElements and
~.-
Transition Elements
~
f=bloC1iElements
*
**
1~Y:~
, ~.,,~;:~,d
INTRODUCTION
In the extended form of the periodic table, the elements have been grouped
Contents: into four blocks namely s, p, d and f-blocks. The elements belonging to
14.1 Introduction groups 3 to 12 are called d-block or transition elements. These are
14.2 Electronic Configuration present between s-block and p-block elements. The properties of these
14.3 General Characteristics of Transition Elements elements are intermediate between the properties of s-block and p-block
14.4 Chemistry of Chromium elements, i.e., d-block elements represent change or transition in properties
14.5 Potassium Dichromate (KZCrZ07) from most electropositive s-block elements to least electropositive p-block
14.6 Chemistry of Manganese elements. Therefore, these elements are called transition elements.
14.7 Potassium Permanganate (KMn04) Previously the transition elements were regarded as those elements which
14.8 Position of Iron in Periodic Table possessed partially filled penultimate d-subshells in their ground state or in
14.9 Extraction of Iron one of their commonly occurring oxidation states. This definition included
14.10 Types of Iron coinage metals (Cu, Ag and Au) in the transition elements as their ions have
14.11 Passivity of Iron partially filled (n -l)d-subshells although their atoms have filled (n -1 )d-
14.12 Compounds of Iron subshells in the ground state.
14.13 Corrosion of Iron
Cu 3io4s1
14.14 Position of Coinage Metals in Periodic Table
Ag 4dI05s1
14.15 Copper
14.16 Compounds of Copper Au 5d106s1
14.17 Silver However, the above definition does not cover the elements of group 12,
14.18 Compounds of Silver i.e., zinc metals (Zn, Cd and Hg) as these elements do not have partially
14.19 Gold filled (n l)d-subshells either in the ground state or in ions.
14.20 Position of Zinc Family in Periodic Table
14.21 Zinc Zn 3io4i
14.22 Compounds of Zinc Cd 4io5i
14.23 Mercury Hg 5d106i
14.24 Compounds of Mercury
However, zinc metals showing similarities in some of chemical properties
14.25 Photography
with transition metals are also included in this block. These are considered
14.26 f-Block Elements
as end members of the transition series in order to maintain a rational
14.27 General Characteristics of Lanthanides classification of elements.
14.28 General Characteristics of Actinides Forty elements belong to d-block. Fourth, fifth, sixth and seventh periods
14.29 Comparison of Lanthanides and Actinides consist of ten elements each.
I d-block
Transition elements
I
vm
llB !VB VB VIB VllB IB lIB
3 4 5 6 7 8 9 10 11 12
21 22 23 24 25 26 27 28 29 30
Sc Ti V Cr Mn Fe Co I Ni Cu Zn-
s-block. 39 40 41 42 43 44 45 46 47 48 p-block
y Zr Nb Mo Tc Ru Rh Pd Ag Cd
,
57 72 73 74 75 76 77 78 79 80
La Hf Ta W Re Os Ir Pt Au Hg
89 104 105 106 107 108 109 110 111 112 .
Ac Ku Ha Sg Bh -Hs Mt Uun Uuu Uub
I i i
The d-block elements include the most common metal used There are four complete rows (called series) of ten elemel11L
in constrilCfi6n aridinariufacfUririi(irori),metals that are valued each corresponding to filling of 3d, 4d, 3[and 6d-orbii:ars-c~
for their beauty (gold, silver and platinum), metals used in respectively. Each series starts with a member of group third
coins (nickel, copper) and metals used in modern technology (IIIB) and ends with a member of group twelve (IIB).
(titanium). Copper, silver, gold and iron were known and used First transition or 3d-Sl 'les: This series consists of
in early civilization. This group contains the densest elements elements from Sc(21) to Zn(30). 3d-orbitals are gradually filled
(osmium, d = 22.59 g cm-3 and iridium, d = 22.61 g cm-3), up.
the metals with the highest and lowest melting points (tungsten,
=
m.p. ;;; 3410"C and mercury, m.p. -38.9°C) and radioactive Element Symbol At. No. Electronic configuration
elements such as technetium and ten members of seventh Scandium Sc 21 Ii, 2i2p6, 3i3p63d\4i
period. or [Ar] 3d 14i
p..
Certain d-block elements are particularly important in living Titanium Ti 22 ::: [Ar] 3d 24i
organisms. Iron, the transition element, is present in the largest Vanadium V 23 ~ [Ar] 3d 34i
qbantity in the human body. The best known biological iron- Chromium Cr* 24 -= [Ar] 3d 54s 1
containing compound is the protein haemoglobin, the red Manganese Mn 25 ~ [Ar] 3d 54i
In
component of blood that is responsible for the transport of Iron Fe 26 '5 - . [Ar] 3d 64s2
oxygen. Cobalt is the crncial element in vitamin B l2, a compound Cobalt Co 27 0 :e [Ar] 3d 74s2
that acts as a catalyst in the metabolism of carbohydrates, fats Nickel Ni ~
28 ("i [Ar] 3d 84}
Copper Cu* 29 [Ar] 3d 104&1
and proteins. Molybdenum and iron together with sulphur form
Zinc Zn 30 [Ar] 3d lO4i
the reactive portion of nitrogenase, a biological catalyst used
by nitrogen fixing organisms to convert atmospheric nitrogen The configuration of Cr and Cu are different than expected.
into ammonia. Copper and zinc are important in other biological The actua:l configurations are explained on the basis of stability
catalysts. Iron, zinc, copper, cobalt, nickel, manganese and concept of half-filled or completely filled (n-l)d-orbitals.
molybdenum are known to be essential components of enzymes. (n l)d-subshell is more stable when 5 or 10 electrons are
Vanadium and chromium are also essential for life. Some bad present, i.e., every d-orbital is either singly occupied or doubly
elements are also present in this block. For example, mercury occupied.
is toxic and is threat to the environment.
i (3d 54sl) instead of (3d 44s2)
14.?Jl ELECTRONIC CONFIGURATION 4s
In the transition elements, the last differentiating electron is Cu lit lit lit I it I it I i (3d 4s
I0 l
)
9
instead of (3d 4s
2
)
accommodated on penultimate d-orbitals,_ i.e., d-orbita:ls are 4&
successively filled. The genera:l electronic configuration of
transition elements is : Second transition or 4d-series: This series consists of
(n l)i- lO ni· 1 or 2 elements from Y(39) to Cd(48). 4d-orbitals are gradually filled
up.
Transition Elements or d-block Elements and f-block Elements 653
Electronic The elements from atomic numbers 106 to 112 have recently
Element Symbol At. No. configuration been reported but these heavy elements are very unstable.
1 It is evident from the above electronic configurations that
yttrium Y 39 [Kr] 4d si
in transition elements ns-orbital is filled before (n - 1)d-orbitals.
Zirconium Zr 40 [Kr] 4d
2
si
Fig. 14.1 tells that near about atomic number 20, 4s-subshell
[Kr] 4d 4 Ssl
0..
Niobium Nb' 41 ::I
"0 has somewhat lower energy than 3d-subshell. Due to this, in
Molybdenum Mo' 42 ~ [Kr] 4d 5 Ssl
ta potassium (Z = 19) and calcium (Z = 20), 4s-subshell is filled
Technetium Tc' 43 [Kr] 4d 6 si
~
Ruthenium Ru' 44 .,C<l [Kr] 4d 7 Ssl
Rhodium Rh' 4S 3 [Kr] 4d 8 Ssl
Palladium Pd' 46
:e
0 [Kr] 4d JO Sso
~
Silver Ag • 47 "'" [Kr] 4d 10 Ssl
Cadmium Cd 48 [Kr] 4d JO si
Elements marked with asterisk have anomalous configura-

tions. These are attributed to factors like nuclear-electron and
electron-electron forces.
Third transition or Sd-series: ThIS senes conSIsts of
elements from La(S7) to Hg(80) except 14 elements oflanthanide
series from Ce(S8) to Lu(71). Sd-orbitals are gradually filled
up.
Electronic
Element Symbol At. No. confjgurati.on. _
~
Lanthanum La S7 [Xe] Sd 1 6i 25
4 2 50 75 100
Hafnium Hf 72 0.. [Xe] 4/ Sd 6i Atomic number
::I
Tantalum Ta 73 "0 [Xe] 4/ 4 Sd 3 6i
Tungsten W ~
74 t;::: [Xe] 4f14 Sd 4 6i Fig. 14.1 The relative energies of the atomic orbitals
Rhenium - Re 7S 0.... [Xe] 4f14 Sd 5 6i as a function of atomic number
76 .,
C<l
4
Osmium Os [Xe] 4/ Sd 6 6i
77 3 4/ 4 Sd 7 6i before 3d-subshell. Therefore, the electronic configurations of
Iridium Ir
:e [Xe]
Platinum
Gold
Pt'
Au
. 78 0
~
79 V)
[Xe]
[Xe]
4f14
4/ 4
Sd 9 6sl
Sd JO 6sl
potassium and calcium are:
Potassium 19 ls22s22p63s23p64s1
Mercury Hg 80 [Xe] 4i4 Sd JO 6i
Calcium 20 ls22s22p63s23p64s2
Fourth transition or 6d-series: This series consists of
Beyond calcium, the energy of 3d-subshell is less than the
elements from Ac(89) to Uub(112) except 14 elements of
energy of 4s and 4p-orbitals. Thus, 3d-orbitals are filled from
actinide series from Th(90) to Lr'(103). 6d-orbitals are gradually
scandium (Z = 21) to zinc (Z = 30). The filling of the
filled up.
3d-orbitals proceeds one at a time. The d-orbitals are first
Electronic occupied singly and then. pairing starts. However, in two cases,
-Element Symbol At. No. configuration chromium (Z = 24) and copper (Z = 29), one electron IS
1
[Rn] 6d 7i
Actinium Ac 89 present on 4s-orbital.
Rutherfordium Rf 104 [Rn] S/4 6d 2 7i
3d
Hahnium Ha lOS .[Rn] S/4 6d 3 7i
Seaborgium Sgt 106 [Rn] S/4 6d 4 7i
5
Cr 24 I iii I iii I i I [!] 5
3d 4s
1
Bohrium Bht 107 [Rn] S/4 6d 7i

Hassium Hst 108 [Rn] S/4 6d 6 7s2 Cu 29 I it I it I i J, I i J, I it I IT] 3io4s1
Meitnerium
Ununnilium
i:'::
Mtt
Uun
. 109
110
[Rn] S/4 6d 7i
[Rn] S/4 6d 8 7i
7
The unusual filling patterns in chromium and copper lead us
to conclude that half filled and fully filled subshells are
(Darmstadtium) (Ds)t unexpectedly stable.
Unununium Uuu • 111 [Rn] S/4 6d JO 7s 1
In the first series, 3d-electrons become more effective in
(Rontgenium) (Rg)t
shielding 4s-electrons from the nucleus, i. e., 3d-electrons suffer
Ununbium Uub* 112 [Rn] S/4 6d 10 7i
more attraction than 4s-electrons from nucleus. This is apparent
*lUPAC names t American names from the fact that when atoms of the elements from atomic
number 21 to 30 change into cations, the 4s-electrons are lost transition series, there is no change in the number of electrons
fIrst before 3d-electrons, although 4s-subshell was filled earlier. of outennost shell and only change occurs in the (n l)d
Mn 25 (3d 54i) Mn 2+ 3d 5 electrons from member to member in a period. These elements
Fe 26 (3tf4s2) 2
Fe + 3d 6 show horizontal and vertical relationships or they show
Ni 28 8
(3d 4i) 2
Ni + 3d 8 a
similarities in period as well as in group. The general trends
The same thing is repeated in second transition series, i.e., of some of the important properties are discussed here fIrst in
in the 5th period, the 5s-subshell is filled before 4d-subshell. In the respective periods and then in groups.
=
rubidium (2 37) and strontium (2 = 38), 5s-subshell is filled. til 1. Metallic Character
4d-subshell is gradually filled from yttrium (2 = 39) to cadmium
All the transition elements are metals. They exhibit most of
(2 = 48). In 6th period, 6s-subshell is filled first before any
the properties of metals. They possess metallic lustre, high
electron is accommodated on 5d or 4f-orbitals. In lanthanum.
density, high melting and boiling points, malleability, ductility,
(2 = 57), the energies of 4f, 5d and 6s are very close to one
high tensile strength, hardness, brittleness, etc. They are good
another and after filling 6s-orbital in caesium (2 = 55) and
conductors of heat and electricity. They exhibit all the three
barium (2 = 56), the next electron in lanthanum is acco-
types of structures: face centred cubic (fcc), hexagonal closed
mmodated on 5d-orbitals. In the subsequent elements from
packed (hcp) and body centred cubic (bcc). These properties
=
~_ _~ce=n::::'u=m=-(2 58) to lutetium (2 = 71)4f-orbitals are gradually
re'v'eaHftat:-betb:-metallie--and-e6Valem-~preseftt:-in-····-···
filled. Fro~ hafnium (2 = 72), the 5d-orbitals are filled. This
the atoms of transition elements.
process is completed in mercury.
The metallic bonding is due to possession of one or two
Hf 72 4i 4sd26s2 electrons in the outennost energy shell like alkali and alkaline
Hg 80 4i45d106i earth metals and relatively low ionisation energies. Copper,
Similar pattern in fourth transition series is observed. silver and gold are outstanding in their thennal and electrical
The fourteen elements following lanthanum (2 = 57) from conductivities. The properties of hardness and brittleness are
cerium (58) to lutetium (2 = 71) constitute the first inner associated with covalent bonding. The presence of unpaired
transition series. These are also called lanthanides. In these and unfilled d-orbitals favours covalent bonding. Greater the
elements 4f-orbitals are being filled successively. Similarly, the number of unpaired d electrons, greater the number of covalent
fourteen elements following actinium (2 = 89) from thorium bonds and therefore, greater is the strength of these bonds. Cr,
(2 = 90) to lawrencium (2 = 103) constitute the second inner Mo and W are very hard metals as they have maximum number
transition series. These are also called actinides. In these of unpaired d-orbitals while Zn, Cd and Hg are softer in nature
elements 5j-orbitals are successively fllied. as they do not have any unpaired d-orbitals.
• Conclusions If:j 2. Atomic Radii
(i) An inner core of electrons with noble gas configuration The atomic radii for transition metals are smaller than their
is present. corresponding s-block elements.
Series Inner core with noble gas s-block elements Transition metals
3d [Ar] I I I i
4d [Kr]
4th period K Ca Sc Cu
5d [Xe] At. radius (pm) 203 174 144 117
6d [Rn] The atomic radii * of the elements of a given series decrease
(ii) (n l)d orbitals are filled up gradually with electrons, with increase in atomic number but this decrease becomes
i.e., configuration varies from (n ~l)i to (n ~l)dlO. Each small after midway. In the first transition series, the atomic
series accommodates ten elements each. radius gradually decreases from scandium to chromium but
(iii) Most of the elements possess two electrons in the from chromium to copper, it is nearly the same. Similar behavi-
outennost orbital, i.e., ni. However, some of the elements our has been observed in the second and third transition series.
such as Cr; Cu, Nb, Mo, Tc, Ru, Rh, Ag, Pt, Au and Uuu have·
1 3d-series At. radii 4d-series At. radii Sd-series At. radii
one electron in the outermost orbital, i.e., ns while one element
(pm) (pm) (pm)
palladium has no electron on ns orbital.
Sc 144 Y 162 La 168
14.31~ GENERAL CHARACTERISTICS OF Ti 132 Zr 145 Hf 144
V 122 Nb 134 Ta 134
TRANSITION ELEMENTS Cr 117 Mo 130 W 130
The members belonging to a given transition series do not Mn 117 Tc - Re 128
Fe 117 Ru 125 Os 126
differ so much from one another as those of representative
Co 116 Rh 125 Ir 126
elements of the same period. It is due to the fact that in a Ni 115 Pd 128 Pt 129
'" Covalent radii
Cu 117 Ag 134 Au 134
Zn 125 Cd 141 Hg 144
Transition Elements or d-block Elements andf-blockElements
The decrease in atomic radii in each series, in the beginning, still higher. The two elements osmium and iridium have high-
is due to an increase in nuclear charge from member to member est densities 22.59 g mL-1 and 22.61 g mL-1 respectively.
which tends to pull the ns electrons inward, i.e., it tends to Practically all the transition elements except scandium, yttrium
reduce the size. At the same time, the addition of extra electrons and titanium possess density higher than 5 g mL-1.
to (n - I )d-orbitals also provides the screening effect. As the
number of d electrons increases, the screening effect increases. 11 5. Melting and Boiling Points
Thus, there are operating two effects namely screening effect The transition metals have very high melting and boiling
and nuclear charge effect which oppose each other. In the points. In each series, the melting points of these metals rise
midway onwards of the series both these effects become to a maximum value and then decrease with increase in atomic
nearly equal and thus, there is no change in atomic radii inspite number. However, manganese and technetium have abnormally
of the fact that atomic number increases gradually. low melting points. The melting points of most of the transition
The values of atomic radii at the end of each series are bit elements except Zn, Cd and Hg are above 900"C. Tungsten
higher. This is due to electron-electron repulsions among has the highest melting point (341O°C) amongst trarisi?on
(n - l)d electrons. These repulsions become predominant at elements.
the end of each series and thus size increases. It is evident
The high melting and boiling points of transition metals ar~_~_~.~
from the atomic radii values of coinage and zinc metals. "itttributed-to-the-strorrgerfurc-esttra:rOiIlotlleirafomStogether.
----~~avertica1 row, the atomic radii is expected to increase
The presence of one or more unpaired d electrons contributes=--=
from top to bottom. Therefore, the atomic radii of transition to higher interatomic forces on account of covalent bonding
metals of second series have larger values than those of the and therefore, to high melting points. [However, this concept
fIrst transition series. However, the transition metals of third does not explain why manganese having five unpaired
series except the fIrst member, lanthanum, have nearly the d electrons possesses lower melting point than that of vanadium
same radii as metals of second transition series above them. or cobalt which have only three unpaired d electrons. The
This is due to Lanthanide contraction. Due to inclusion of complex structure is responsible for this abnormal behaviour.]
fourteen lanthanides between lanthanum and hafnium, [there is When no unpaired electrons are present, the melting points
continuous decrease in size from Ce(58) to Lu(7l)] hafnium are low as in the case of Zn, Cd and Hg.
size becomes nearly equal to the size of zirconium.
3d-Series Sc Ti V Cr Mn Fe Co Ni Cu Zn
!,:! 3. Ionic Radii M.pt. COC) 1539 1668 1900 1875 1245 1536-1495 1453 1083 419.5
B.pt. COC) 2730 3260 3450 2665 2150 3000 2900 2730 2595 906
The ionic radii follow the same trend as the atomic radii. For
the same oxidation state, the ionic radii generally decreases as m 6. Ionisation Energies
the atomic number increases in a particular transition series.
The ionisation energy values of majority of d-block elements
Ion Sc2+ Ti 2+ V2+ Cr2+ Mn2+ Fe2+ Co 2+ Ni 2+ Cu2+
lie in between those of s- and p-block elements. The d-block
Ionic radii (A) 0.95 0.90 0.88 0.84 0.80 0.76 0.74 0.72 0.69
elements are less electropositive than s-block elements and
The ionic radii decreases with increase of charge on the ion. more electropositive than p-block elements. The transition
Fe3+CO.64) < Fe2+(O.76) elements do not form ionic compounds so readily as s-block
Ni3+(O.62) < Ni 2+(O.72) elements do. Unlike s-block metals, transition elements form
Mn3+(O.66) < Mn2+(O.80) covalent compounds as well. Generally, lower valencies are
ionic and higher valencies are covalent in nature. The first
The ionic radii of the transition metals are smaller than those ionisation potential values are tabulated below in kJ morl.
of representative elements belonging to same period.
Sc TI V 0 ~ ~ ~ m Cu ~
. 631 656 650 652 717 762 758 737 745 906
rm 4. Atomic Volumes and Det:lsities Y b m ~ Th ~ ~ N ~ rn
The atomic volumes of the transition elements are low as 616 674 664 685 703 711 720 804 731 876
compared with elements in neighbouring groups I and II. This La Hf Ta W Re Os Ir Pt Au Hg
541 760 760 770 759 840 900· 870 889 1007
is because the nuclear charge is poorly screened and so attracts
all the electrons more strongly. Ionisation potential values increase in a period from left to
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
right. The increase, however, is not regular. For example, in
At. volume (mL) 15.0 10.6 8.3 7.23 7.39 7.10 6.70 6.60 7.109.20 the case of first transition series, the ionisation potential values
Density (gmL-1) 3.0 4.5 6.1 7.20 7.40 7.t6g.;~ 8.90 8.967.14 of Sc, Ti, V and Cr are fairly close to one another. Similarly,
values of Fe, Co, Ni and Cu are almost similar,
Consequently, the densities of transition metals are high.
The increase in the ionisation potential values in a given
The densities of second row are high and third row values are
transition series is explained on the basis of increasing nuclear
656 QR,B, Inorganic. Chemistry for Competitions
charge and~screening effect of (n l)d electrons on ns This process involves three steps:
electrons. With the increase of electrons in (n-l)d-subshell, First step
the outer ns electrons are shielded more and more. Thus, the M(s) ~ M(g) !1Hsub (Energy of sublimation)
effect of increasing nuclear charge is somewhat neutralised by
Second step
the additional screening effect and consequently, ionisation
potential increases but quite slowly among a period of d-block M(g) ~ M\g) + e I.E. (Ionisation energy)
elemen~. The value of zinc is appreciably higher due to Third step
additional stability associated with completely filled 3d-level in M+(g) + aq ~ M\aq) !1Hhyd (Hydration energy)
zinc. Slight variations that occur in ionisation potential values
Thus, !1HT =: !1Hsub + I.E. + !1Hhyd
are mainly due to the slight changes in atomic radii.
!1HT is the total energy change when solid metal, M is
Second and third ionisation energies, in general, also increase
brought in the aqueous medium in the form of monovalent ion,
in a series. However, exceptions are observed. M+(aq).
. lInd ionisation IIIrd ionisation The smaller the value of total energy change for a particular
3d series
energy (kJ morl ) energy (kJ morl ) oxidation state in aqueous solution, greater will
be the stability
.&: 1245 2451 of that oxidation state. The electrode potentials are the-measure
Ti 1320 2721 .. -~--~
_----.illtotal.en~~hange.Henc~tJl'lantitatively'_ the stability of_~_
V 1376 2874 the transition metal ions in different oxidation states in solution
Cr 1635 2995 can be deterriiined on the basis of the electrode potentialdatff.
Mn 1513 3258
Fe 1564 2964
The lower the electrode potential, i.e., more negative the
Co 1648 3238 standard reduction potential of the electrode, more
Ni 1757 3401 stable is the oxidation state of the transition metal in the
Cu. 1962 3561 aqueous medinm. The standard reduction potential values,
Zn 1736 3839 2 3 2
EO (M +IM) and (M +IM +) of the rriembers of first transliion
Third ionisation energy of manganese is very high. This is series are given below:
because the third electron is to be removed from a stable Element Ti V Cr Mn Fe Co Ni Cu Zn
configuration, (Mn 2+ 3et), i.e;, half-filled 3d-subshell. E' (M 2+IM)V -1.63 -1.18 -0.91 -US -0.44 -0.28 -0.25 +0.34 -0.76
The second ionisation potential values of Cu and Cr are E' (M 3+IM 2+)V 0.37 0.26 -0.41 +1.57 +0.77 +1.97
sufficiently higher than those of neighbouring elements. This
is because of the electronic configuration of Cu+ which is 3dlO • Trends in /tA2+1I'A
(completely filled) and of Cr+ which is 3et (half-filled), i.e., . Standard Electrode Potentials
for the second ionisation potential, the electron is to be removed
(i) It is evident that there is no regular trend in the
from very stable configurations.
£O(M2+1M) values. This is due to irregular variation of ionisation
In vertical columns, i.e., groups, the ionisation potential
energies and sublimation energies of the atoms of the members
decreases from first member to second member in most of the
of the transition series.
cases as expected, however, the third member has higher value
(ii) Except copper, all other elements have negative reduction
than second member. This is due to lanthanide contraction,
potential values, i.e., these elements except copper should
i.e., the atomic radii of the elements of the same group of the
have the capacity to liberate hydrogen from dilute acids.
second and third transition series are nearly the same but
atomic numbers differ by 32. Thus, the outer electrons are M + 2H+ (from acid)'~ M2+ + H21
held very firmly and the ionisation potential values are very
high. On account of this, the members of 5d are inert under In actual practice, the rate of liberation of hydrogen is very
ordinary conditions, i.e., Pt, Au, Hg, etc., are noble metals. slow. Some of the metals, in fact, get protected by the formation
of a thin film of an inert oxide on the surface. Chromium, for
7. Standard Reduction Potentials example, in spite of its high negative reduction potential value
is an unreactive metal as it does not liberate hydrogen due to
In solution; the stability of the compounds depends upon a thin coating of Cr203 on its surface.
electrode potentials. Electrode potential value depends upon Copper having positive £0 value, does not liberate hydrogen
enthalpy of sublimation of the metal, the ionisation enthalpy from acids. It reacts only with oxidising acids such as HN0 3
and hydration enthalpy, i.e., and cone. H2S04 ,
M(s) ~ M+(aq) + e !1HT (Total energy change)
THERMOCHEMICAL DATA (kJ mol-1) FOR • Trends in (fiJ+Iu'l+) Standard
FIRST SERIES OF TRANSITION METALS Electrode Potentials
Element IlHsub
LE'(i) LE'(iI)
IlHbyd (i) IS' value for Sc 3+/Sc 2+ is very low. Hence, Sc3+ is stable.
(M) (M) (M 2+) This is due to its noble gas configuration.
2
Ti 469 661 1310 -1866 (ii) IS' value for Mn3+/Mn2+ is high. This reflects that Mn +
V 515 648 1370 -1895 state is stable due to d' configuration.
Cr 398 653 1590 -1925 (iii) IS' values for the redox couple M3+/M 2+ indicate that
Mn 279 716 -1510 -1862 Mn3+ and C03+ ions are strong oxidising agents.
Fe 418 762 1560 -1998
Co 427 757 1640 -2079
Ni 431 736 1750 -2121 ~~ 8. Oxidation States
Cu 339 745 1960 -2121 The transition elements with the exception of a few show
Zn 130 I 908 1730 -2059
a large number of oxidation states. The various oxidation states
(iii) Less negative of IS' values along the series is due to are related to the electronic configuration of their atoms. The
increase in the fIrst and second ionisation energies. oxidation states of the members of fIrst transition series are
(iv) The values of EO for Mn, Zn and Ni are more negative tabulated below. The oxidation states within brackets are not
- - - - - than-expected. Tins is-due-m-extra-stability--of--half~ftHed-----stabte;4'he-highesroxidatiotrstates-are-found-in-componnds---
2
d-subshell (d') in (Mn 2+) and completely filled (dlO) in Zn +. with fluorine and oxygen because fluorine and oxygen arec -
The high value in Ni can be attributed due to high hydration -most electronegative in nature.
energy. The variable oxidation states of a transition metal is due to
(v) In spite of the fact that all the metals except copper have the involvement of (n l)d and,outer ns electrons in bonding
negative E' values, but are not good reducing agents in as the energies of ns and (n - l)d subshells are nearly equal.
comparison to s-block elements. This is on account of high The lower oxidation state is generally shown by when ns-
enthalpy of sublimation, high enthalpy of ionisation and poor electrons participate in bonding and higher oxidation states are
enthalpy of hydration. exhibited when ns and (n l)d-electrons take part in bonding.
Element Outer electronic cOilltgnration Oxidation states
Sc 3d1,4i (+2), +3
4s
Ti 3d2,4s2 (+2), +3, +4
V 3i,4i Ii Ii Ii +2, +3, +4, +5
Cr 3d5,4s1 Ii Ii Ii Ii Ii I (+1), +2, +3, (+4), (+5), +6
Mn 3d5,4i Ii Ii Ii Ii Ii I +2, +3, +4, (+5), +6, +7
Fe 3tf,4i @] +2, +3, (+4), (+5), (+6)
Co 3d7 ,4i 1iJ, 1iJ, Ii Ii Ii I +2, +3, (+4)
Ni 3d 8 ,4s2 I it I it I it I i i +2, +3, +4

I I
Cu 3dlO,4s1 +1, +2
Zn 3d lO ,4i +2
658 G.RB. Inorganic Chemistry for Competitions
From the survey of the oxidation states of transition elements, Ti4+ (3do4s0) is more stable than Ti 3+ (3i4so);
the following conclusions are drawn: Mn2+(3~4s0) is more stable than Mn3+ (3d 44s0); Fe3+
(i) Generally, within the transition series, the highest (3~4i) is more stable than Fe2+(3d64i), etc.
oxidation state increases with increase of atomic The relative stabilities of various oxidation states of a
number, reaching to a maximum in the middle and given element can also be explained on the basis of
then starts decreasing. For example, in the fIrst standard electrode potential data. For example, in case
transition series manganese shows the maximum of copper we have
oxidation state of +7. The highest oxidation state shown
Cu+(aq) + e- - - 7 Cu(s); E' 0.52 V
by any transition metal is +8. Ruthenium in second
Cu +(aq) + 2e- - - 7 Cu(s); E~ = 0.34V
2
transition series and osmium in the third transition
series show +8 oxidation state. Thus, Cu+ is reduced easily and hence is less stable
(ii) In general, the minimum oxidation state sown h by a than eu2+.
transition metal is equal to the number of ns-electrons. (vii) In a group of d-block elements, the higher oxidation
Except scandium, (which has +3 oxidation state) for states are more stable for heavier elements. For
the elements of fIrst transition series +2 oxidation example, in group 6, Mo(vi) and W(vi) are more stable
state is the most common. This state arises due to than Cr(vi). For example, dichromate having Cr(vi) is
loss of 4s-electrons. However, for chromium and. a strong.9xidising agent in acid.ic medium whil.~Mo..Q3-~ _ _
~~·---~··copper,- the lowest oxidation state is + 1. Thisis~-·--~ ·-and W0 3 are stable. oxides. .
. due to their electronic confIgurations, Cr(3d 54s 1) and (viii) In transition elements the successive oxidation states
Cu(3i04s\ Thus, it is evident that after scandium differ by unity.
d-orbitals are more stable than 4s-orbital, i.e., the
energy associated with 3d-subshell is less than that of
4s-subshell. A substance appears coloured because it absorbs light at--
(iii) In the fIrst fIve elements of the first transition series, specific wavelengths in the visible part of the electromagnetic
i.e., upto manganese (3d-subshell is no more than spectrum i4000 to 7000A) and transmits or .reflects the rest
half-fIlled), the maximum oxidation state is equal to of the wa~lengths. Each wavelength of visible light represents
the sum of the 4s and 3d-electrons. For example, a different colour. White light is a combination of all colours.
2
maximum oxidation state for titanium is +4 (3d 4l), The table given shows the relationship of wavelength absorbed
for vanadium +5(3~4;), for chromium +6(3ds4s 1) to the observed colour.
and for manganese, it is +7 (3~ 4i).
For the remaining fIve elements the maximum oxidation Wavelength absorbed (A.) Colour observed
state is not related to their electronic configurations. 4000 (Violet) Greenish yellow
The common oxidation states for the elements from 4500 (Blue) Yellow.
Fe to Ni are +2 or +3. The oxidation state higher than 4900 (Blue-green) Red
+3 is rarely shown.
5700 (Yellowish green) Violet
(iv) Some of the transition metals form compounds in
5800 (Yellow) Dark blue
zero oxidation state. The common examples are
Ni(CO)4 and Fe(CO)s in which nickel and iron are in 6000 (Orange) Blue
zerovalent state. 6500 (Red) Blue-green
(v) In +2 and +3 oxidation states, the bonds formed are Most of the compounds of transition metals are coloured in
mostly ionic. On the other hand, in higher oxidation the solid or in solution states. The colour of transition metal
states, the bonds formed are essentially covalent. ions arises from the excitation of electrons from the d-orbitals
Higher states are usually attained with elements of of lower energy to the d-orbitals of higher energy. The energy
high electronegativity such as fluorine and oxygen. required for d--d electron excitations is available in the visible
For example, in the ions such as CrO~-, Mn04, the range. It is for this reason that transition metal ions have the
bonds formed are covalent: property to absorb certain radiations from the visible region
(vi} The relative stability of various oxidation states of a and exhibit the complementary colour. The colours and outer
given element can be explained on the basis of stability electronic confIgurations of important ions of the elements of
of dO, d 5 and iO configurations. For example, fIrst transition series are tabulated ahead:
.Tra.nsition EleIIlents of d-blockElementSaild [-block Elements
COLOURS AND MAGNETIC MOMENTS OF IONS OF tm 10. MagnetiC Properties

THE FIRST TRANSITION SERIES
Majority of substances show magnetic nature. These are
Outer
Number of Magnetic
Colour of the moment
either paramagnetic or diamagnetic. A paramagnetic sub-
Ion unpaired stance is one which is weakly attracted into a magnetic field
configuration electrons ion (B.M.)
and a diamagnetic substance is one which is repelled by a
Sc3+ 3do 0 Colourless 0 magnetic field. The paramagnetic behaviour arises due to the
Ti4+ 3d o 0 Colourless 0 presence of one or more singly occupied atomic orbitals, while
Ti 3+ 3d l I Purple 1.75
diamagnetic behaviour is due to presence of paired electrons
V3+ 3d 2 2 Green 2.76
in the atomic orbitals. .
Cr3+ 3d 3 3 Violet 3.86
Most of the compounds of transition elements are para-
Mn 3+ 3d4 4 Violet 5.0
magnetic in nature as unpaired electrons in d-subshell are present.
Mn 2 + 3d 5 5 Light pink 5.96
The magnetic character is expressed in terns of magnetic
Fe 2+ 3d6 4 Green 5.10
Fe 3+ 3d5 5 Yellow 5.96
moment. The magnetic moments arise only from the spin of
Co2+ 3d 7 3 Pink 4.4 - 5.2 electrons. The effective total magnetic moment, ~ff' is given
Ni 2+
the "'VT'rp,,,,,r,...
3d 8 L-._ Gr.eelL.. 2.9. - 34
Cu 2+ 3d9 I Blue 1.8 - 2.2 . ~ff = .In(n + 2) B.M.
Cit 3d 1O 0 Colourless 0 where n is the number of unpaired electrons. Larger the humber
Zn 2+ 3d 1O 0 Colourless 0 of unpaired electrons in a substance, the greater is its magnetic
Complementary colours can be identified using Munshel moment in Bohr-magneton and larger shall be its paramag-
colour wheel. netism. The magnetic moments of some important ions of the
elements of first transition series are given in the table.
V :::: Violet It is evident from the values that the magnetic moments or
B = Blue paramagnetic behaviour increases as the number of unpaired
G :::: Green electrons increases from I to 5. After d5 configuration, there
Y Yellow is decrease in magnetic moment as the number of unpaired
o : : Orange electrons decreases.
R = Red
In the case of iron, cobalt and nickel the unpaired electron
Y spins are much more pronounced. As a result, these elements
Opposite colours are complementary. are much more paramagnetic than the rest of the elements.
The transition metal ions which have completely filled These elements are termed ferromagnetic and can be
d-orbitals (3dlO, 4io or 5io) such as Zn2+, Cd2+, Hg2+, eu+, magnetised.
Ag+ and Au+ ions are colourless as the excitation of electron
or electron.s is not possible within d-orbitals. The transition 11. Tendency to form Complexes
metal ions which have completely empty d-orbitals such as d-block elements have a marked ability to form complex
Sc3+, Ti4+, etc., are also colourless. . compounds. This ability is on account of following three
[Note : fu the ox;ysalts of transition elements like KMn04, K2Cr207, reasons:
there are no unpaired electrons at the central atom but they are
deep in colour. The colour of these compounds is due to charge
(i) Small size (ii) high nuclear charge (iii) a number of
transfer spectrum. vacant orbitals of equivalent energy where, the electrons donated
Observe the colour of following compounds of silver by ligands can be accommodated. Ligands are species with
AgCl AgBr AgI Ag2S lone pair of electronS which they can readily donate. These
Colour White Pale Yellow Yellow Black species can be neutral molecules such as NH 3, H20, NO, CO,
% Ionic character 80% 24% 15% 4% etc., or ions such as CC CN-, etc.
Ag+ == 4d105sO
The number of attachment with ligands are usually either
There is no unpaired electron with Ag+. Thus, colour of these
compounds can be explained on the basis of percentage ionic
four or six, i.e., the coordination number of metal ion is usually
character. four or si~: The compounds containing complex ions are termed
If the ionic character of these ionic compounds is less than 20% as coordination compounds. Na3[Fe(CN)6], [CU(NH3)4]S04,
then the compound will be coloured.] [Cr(NH 3)6]CI3 and Ni(CO)4 are some of the examples of
* This expression is applicable mainly to 3d elements.
eh
1 B.M.=: 4nmc B.M.:::: Bohr-magneton
e Charge of electron; h:::: Planck constant; m Mass of electron; c = Velocity of light
660 G.R.B. Inorganic Chemistry for Competitiona
coordination compounds. Coordination compounds are II 15. Some Important Compounds

discussed in detail in chapter 15.
The transition metals combine with a number of non-metals
~ 12. Formation of Interstitial Compounds .such as oxygen, nitrogen, carbQn, halogens, sulphur and
phosphorus, etc., to form useful binary compounds. General
Small non-metallic atoms such as H, B, C, N, etc., are able trends in oxides, halides and sulphides are discussed.
to occupy interstitial spaces of the lattices of the d-block (a) Oxides: The elements of first transition series form
elements to form combinations which are termed interstitial a number of oxides having general formulae MO, M 20 3, M 30 4,
compounds. These are non-stoichiometric in nature and do not M0 2, M 20 S, M03' The oxides are generally formed when the
follow the common rules of valency. The bonds present are metals are strongly heated at high temperature in the atmosphere
neither typically ionic nor covalent. The formulae do not of oxygen. These oxides exhibit acidic, basic and amphoteric
correspond to any normal oxidation state of the metal. behaviour. The important and common oxides of the elements
Some of the characteristics of interstitial compounds are: of first transition series are listed in the following table :
(i) The interstitial compounds have similar chemical
properties as the parent metals but differ appreciably OXIDES OF THE METALS OF FIRST
in their physical properties such as density, conductivity, TRANSITION SERIES
Sc
(ii) As a result of filling up of the interstitial spaces, the Ti TiO(b) Ti 20 3(b) Ti0 2(c)
metals become rigid and hard. Steel is quite hard as it VVD(6) .. V2olbr-"Vt:>i(c}-ViOslaj
is interstitial compound of Fe and C. Some of the Cr CrO(b} Cr03(a)
borides are as hard as diamond. [Mn03(a) ]Mn2~( a)
(iii) Interstitial compounds possess high melting points Fe
which are higher than those of pure metals. Co
Ni Mixed
~ 13. Catalytic Properties Cu
Many of the d-block elements and their compounds act as Zn
catalysts in various reactions. Some common examples are : where a = acidic; b == basic; c = amphoteric; h hydrated
(i) Pt-used as a catalyst in the manufacture of H 2S04 . [Note: Stable oxides have been indicated by bold letters. Unstable are
(ii) Fe-used as a catalyst in the manufacture of NH3 by in parentheses.]
Haber process. A small amount of molybdenum is
(i) The oxides in lower oxidation states are basic in nature.
added as a promoter.
(ii) The oxides in intermediate oxidation states are
(iii) Ni.-used as a catalyst in the hydrogenation of oils.
amphoteric.
(iv) V20S-used as a catalyst for the oxidation of S02
(iii) The oxides of higher oxidation states are acidic in nature.
into S03 for the manufacture of H2S04 in the contact
process. Examples:
Oxides of chromium :
(v) Mn02-used as a catalyst in the decomposition of
KCI03 for preparation of oxygen. CrO Cr02 Cr03
(vi) Cobalt salts catalyse the decomposition of bleaching O.N. +2 +4 +6
powder. Basic Amphoteric Acidic
Catalytic property is probably due to the utilisation of ----------------7 Acidic character
increases
(n 1)d-orbitals or formation of interstitial compounds.
Oxides of manganese :
g;'i 14. Alloy Formation MnO
Transition metals form a large number of alloys. Since d- O.N. +2
block elements are quite similar in atomic size, the atoms of Basic Amphoteric Acidic
one metal can substitute the atoms of other metal in its crystal -----------~)Acidic character
lattice. Thus, on cooling a mixture solution of two or more increases
transition metals, smooth solid alloys are formed. It can also be said that if a metal forms a number of oxides,
Alloys containing mercury as one of the constituent elements the acidic nature of the oxides increases as the percentage of
are called amalgams. The pUi-pose of making alloys is to oxygen increases.
develop some useful properties which are absent in the (iv) The basic and amphoteric oxides generally dissolve in
constituent elements. non-oxidising acids like HCI to form hexaaquo ions,
[M(H 20)6]n+. .~
Transition Elements or d-block Elements and I-block Elements 661
(v) Some of the oxides dissolve in acids or bases to form The concentrated ore is mixed with excess of sodium
oxometallic salts such as chromates, dichromates, perman- carbonate and roasted in a reverberatory furnace in a free
ganates, etc. supply of air. CrZ03 present in the ore is converted into sodium
(b) Halides: Transition metals combine with halogens at chromate.
high temperatures to form compounds called halides. On 4FeO·CrZ03+8NazC03+70 z---7 8NazCr04+2Fez03+ 8C02
account of high activation energies of these reactions, high Chromite ore (from air)
temperature is usually needed to start the reaction, but once the
The roasted mass is extracted with water when NaZCr04
reaction starts, the heat of reaction is sufficient to maintain the
goes into solution leaving behind insoluble FeZ03 and
continuity of the reaction (Reactions are exothermic in nature).
unconverted ore. The solution is treated with calculated amount
The order of the reactivity of halogens is :
of sulphuric acid to convert sodium chromate into dichromate.
F > Cl > Br > I
Metals in higher oxidation states only form fluorides as it is 2NazCr04+HzS04 ---7 Na2CrZ07+NazS04+H20
the most electronegative and reactive element. The following The solution is concentrated when less soluble NaZS04
are some of the general characteristics of halides. crystallises. out. The solution is further concentrated when
(i) Fluorides are mainly ionic in nature. The chlorides, crystals ofNa2Cr207are obtained. Na2Cr207 isheate~ wit~_ _
-----ljromides and iodides have-ionic as welCascovalen.t character.-- carbon ancftllecmomitethus-formed is extracted with water
The covalent character increases as atomic mass ofthe halogen when Cr203· is· precipitated;
increases. For example, CuF2 is ionic compound while CuCl 2 Na2CrZ07 + 3C ---7 NaZCrZ04 + 3CO
and CuBr2 are covalent forming infInite chains. The coordination Sodium chromite
number of the copper in these compounds is six. The structure NaZCr204 + HzO ---7 2NaOH + CrZ03
of CuCl2 is given below: Reduction of Cr203 is done by Goldsmith alumino-thermic
CI~~.<Cl>~<Cl>Ju<
u
process.
Cr203 + 2Al---7 2Cr + Al 20 3
CI/: CI : CI : The mixture is taken in the ratio of 3 : 1 in a refractory
>~<Cl>~u<Cl>~/I>~<
crucible and the mixture is ignited with burning magnesium
:~l:
ribbon. The metal obtained is about 92% pure. It is further
: Cl: CI purifIed electrolytically using mercury as cathode and chromic
(ii) Halides of metals in higher oxidation states are relatively chloride solution as electrolyte. The amalgam is finally heated
unstable and undergo hydrolysis very easily. in vacuum to get 99.7% pure metal.
TiCl4 + 2H20 ---7 Ti0 2 + 4HCl Ferrochrome : An alloy of Cr and Fe containing about
The solutions of several halides are acidic in nature due to 75% Cr is obtained when chromite oreis reduced with carbon
hydrolysis. These solutions can be stabilised by addition of in an electric furnace.
acids in order to prevent hydrolysis. FeO·Cr203 + 4C ---7 Fe + 2Cr + 4CO
FeCl3 + 3HzO ~ Fe(OHh + 3HCI Alloy
CuClz + 2H 20 ~ Cu(OHh + 2HCI Ferrochrome is extensively used for alloying with iron to
(c) Sulpbides: Sulphides of transition metals can be make special steels.
formed either by direct combination of the metals with sulphur
or by action of H 2S or Na2S on the salts of these metals. • Uses
Fe + S ---7 FeS (i) Chromium is used in making alloys such as chrome
CUS04 + HzS ---7 CuS + HZS04 steels, stainless steel (18% Cr) and nichrome (Ni 60%, Fe
2AgN03 + Na2S ---7 AgzS + 2NaN03 25%, Cr 15%).
Sulphides of transition metals are coloured usually black (ii) It is extensively used for plating metals because it is very
and are insoluble in water. resistant to corrosion.
(iii) Its compounds [md wide applications.
14?~1
.:'~
CHEMISTRY OF CHROMIUM The.outer electronic configuration of chromium is 3d 54s •
1
Chromium belongs to group 6 (VI B) of the extended form of It exhibits a large number of oxidation states varying from 0
periodic table. The other members of the group are molybdenum to +6. The stable and important oxidation states of Cr are +2,
(Mo) and tungsten (W). The most abundant element of this +3 and +6. Chromium (II) compounds are reducing agents as
group is chromium. The most important ore of chromium is they are readily converted into chromium (ill) compounds
chromite or chrome-iron stone, FeO·Cr203' even by the oxygen of the air. +3 oxidation state is highly stable
in acid solutions but it gets oxidised readily to +6 oxidation
state in alkali solutions. Chromium compounds in +6 oxidation Some typical oxidation reactions are given below :
states are strong oxidising agents. (i) Iodine is liberated from potassium iodide.
14.5/ POTASSIUM DICHROMATE, K2Cr207 K2Cr207+4H2S04 ---? K2S04+Cr2(S04h+4H20+3[0]
[2KI + H2S04 + [0] ---? K2S04 + 12 + H20] X 3
It is the most important compound of Cr (VI). I~ is manufactured
from chromite ore. Chromite ore is first converted into sodium K2Cr207+6KI+7H2S04 ---? 4K2S04+Cr2(S04h+7H20+3I2
dichromate as described in section 14.4. The hot saturated The equation in terms of electron method may also be
solution of sodium dichromate is mixed with KCl. Sodium written as
chloride precipitates out from the hot solution which is filtered Cr2~-+ 14Ir+6e- ---? 2Cr3++7H20
off. On cooling the mother liquor, crystals of potassium
6r ---?3I2 + 6e-
. dichromate separate out.
•
Na2Cr207 + 2KCI ---? K2Cr2~ + 2NaCI
. oxygen.
3
+ 7H20 + K2S04
2K2Cr20 7 ---? 2K2Cr04 + Cr203 + 2: O2 2
or 6Fe + + Cr20~-+ 14H+ ---? 6Fe + + 2Cr3+ + 7H20
3
On heating with alkalies, it is converted to chromate, i.e.,
(iii) Sulphites are oxidised to sulphates.
the colour changes from orange to yellow. On acidifying,
yellow colour again changes to orange. K2Cr20 7 + 4H2S04 ---? K2S04 + Cr2(S04h + 4H20 + 3[0]
K2Cr207 + 2KOH ---? 2K2Cr04 + H20 [Na2S03 + [0] ---? Na2S04]x3
Cr2~- + 2oH----?2CrO~-+H20 K2Cr20 7 + 3Na2S03 + 4H2S04 ---? 3Na2S04 + K2S04 +
Orange Yellow Cr2(S04h + 4H20
2CrO~- + 2Ul- ---? Cr20~- + H20
Yellow Orange
or Cr2~- + 3S0~- +SH+ ---? 3S0~- + 2Cr3+ + 4H20
In alkaline solution, chromate ions are present while in acidic (iv) H2S is oxidised to sulphur.
solution, dichromate ions are present. Both the ions are in K2Cr207+4H2S04+3H2S ---? K2S04+Cr2(S04h+7H20+3S
eqUilibrium at pH = 4.
or Cr209- + 3H2S + SH+ ---? 2Cr3+ + 7H20 + 3S
pH=4
Cr20t + H 20 ~ 2CrO~- + 2H+ (v) S02 is oxidised to H2S04.
Potassium dichromate reacts with hydrochloric acid and K2Cr207 + 4H2S04 ---? K2S04 + Cr2(S04h + 4H20 + 3[0]
evolves chlorine. [S02+ [O~ + H20 ~ H2S04]x3
K2Cr207 + 14HCI---? 2KCI + 2CrCl3 + 7H20 + 3Cl2
K2Cr207 + H2S04 + 3S02 ---? K2S04 + Cr2(S04h + H20
It acts as a powerful (,xidising agent in acidic medium
(dilute H2S04). or Cr20~-+3S0 2+2H+ ---? 2Cr3++3S0~-+H20
Cr20~- + 14H+ + 6e- ---? 2Cr3+ + 7H20 When the solution is evaporated, chrome-alum is obtained.
(vi) It oxidises ethyl alcohol to acetaldehyde and acetaldehyde
Cold concentrated solution of K2Cr2~' on treatment with to acetic acid.
concentrated H2S04 forms chromic anhydride (Cr03)'
C2HSOH ~ CH3CHO ~CH3COOH
K2Cr207 + H2S04 ---? 2Cr03 + K2S04 + H20 Ethyl alcohol Acetaldehyde Acetic acid
Red crystals
It also oxidises nitrites to nitrates, arsenites to arsenates,
The oxidation state of Cr changes from +6 to +3.
thiosulphate to sulphate and sulphur (S20~- + 0 ---? SO~
The potential equation in terms of available oxygen can be
given as: . + S), RBr to Br2, HI to 12, etc.
K2Cr207 + 4H2S04 ---? K2S04 + Cr2(S04h + 4H20 + 3[0] Cr20~- + SH+ + 3NO:Z ---? 2Cr3+ + 3N0 + 4H20 3
I mole 6x8 Cr20~- + sIr + 3S20~- ---? 2Cr3+ + 3S0~- + 3S + 4H20
Thus, the equivalent mass of K2Cr207 in acidic medium is K2Cr207 + 14HBr ---? 2KBr + 2CrBr3 + 7H20 + 3Br2
Mol. mass i.e., 294 =49.
6 6 K2Cr207 + 14HI ---? 2KI + 2Cd3 + 7H20 + 312
(vii) Chromyl chloride test: This is a test of chloride. (c) Potassium dichromate on heating with carbon is reduced
When a mixture of a metal chloride and potassium dichromate to potassium chromite which on treatment with water gives
is heated with conc. H2S04, orange-red vapours of chromyl chromium sesquioxide.
chloride are evolved. K2Cr207 + 3C ---t K2Cr204 + 3CO
K2Cr2Oy + 2H2S04 ---t 2KHS0 4 + 2Cr03 + H 20
K2Cr204 + H 20 ---t 2KOH + Cr203
[N:;tCI + H2S04 ---t NaHS04 + HCI] x 4
(d) When potassium dichromate and ammonium chloride
[cr0 3 + 2HCI---t Cr0 2Cl2 + H20] x 2 mixture is heated, nitrogen is evolved.
K2Cr207 + 6H2S04 + 4NaCI ---t 2KHS0 4 + 4NaHS04 Heat
+ 2Cr02Cl2 + 3H20 K2Cr207 + 2~CI ---t 2KCI + Cr203 + N2 + 4H20
Chromyl chloride
(e) K2Cr207, on fusion with ~Fe(CN)6, potassium cyanate
When chromyl chloride vapours are passed through NaOH is formed.
solution, yellow coloured solution is obtained.
2K2Cr207 + 2~Fe(CN)6 ---t 6KCNO + 2Cr203 + 2K~0~_._
.. - --~--~-~4NaQH-+-bfOzGl·"...z-~)NazerO.r-+-~NaC+-+-2Hzo-- ~ - . ----~-~-~~.-~--.----.-- ...-~--~-~- ... ---~~.~~~----. ~--.
Yellow soln. + KzFe[Fe(CN)~
The yellow coloured solution on acidification with acetic Structure of chromate and dichromate : ~.ns : The
acid followed by addition of lead acetate gives thick yellow chromate ion has a tetrahedral structure. In dichromate, two
precipitate of lead chromate. tetrahedral sharing one oxygen atom at one comer are present.
Na2Cr04 + (CH3COOhPb ---t PbCr0 4 + 2CH3COONa
Lead chromate
(yellow ppt.)
or
[Note: This test is not positive with the chlorides of Hg. Ag. Pb and Sn.]
(viii) Acidified KZCr207 solution reacts with hydrogen
peroxide to give a deep blue solution due to formation of crOs.
It is unstable and blue colour fades away gradually due to
formation of chromic sulphate.
KZCr207 + H2S04 ---t K2S04 + H2Cr207
(cone.)
[H202 ---t H20 + 0] X 4

H2Cr2Oy + 4[0] ---t 2Cr05 + H20 • Uses
K2Cr207 + H2S04. + 4H20 2 ---t 2Cr05 + K2S04 + 5H20 Potassium dichromate is used (i) as a volumetric reagent in
4Cr05 + 6H2S04 ---t 2Cr2(S04h + 6H20 + 702 the estimation of reducing agents such as oxalic acid, ferrous
cr05 (peroxide of chromium) is represented as ions, iodide ions, etc. It is used as a primary standard. (ii) for
the preparation of several chromium compounds such as
o . 0
6)~r<6
chrome alum, chrome yellow, chrome red, zinc yellow, etc.
(iii) in dyeing, chrome tanning, calico printing, photography,
etc. (iv) chromic acid as a cleansing agent for glassware.
o (v) in organic chemistry as an oxidising agent (vi) as laboratory
(Butterfly shape)
reagent. (vii) Acidified solution of K2Cr2Oy provides a test to
find out whether a person is drunken or not. A person is asked
• Some Miscellaneous Reactions
to breathe into a solution of K2Cr207 (acidified). If the colour
(a) Powdered K2Cr207 on treatment with warm concentrated of the solution turns green, it confirms that the person is in
HCI forms petigot's salt. drunken state.
K2Cr2Oy + 2HCI ---t 2KCr03Cl + H20
Potassium 14.6 CHEMISTRY OF MANGANESE
chlorochromate
(Petigot's salt) Manganese is a member of group 7 (VIIB). The other members
of the group are technetium (Tc) and rhenium (Re). Of these
(b) With K2C03, K2Cr207 forms potassium chromate.
elements, only manganese is important. It is twelfth most
K2Cr207 + K2C03 ---t 2K2Cr04 + CO2 abundant element by mass in earth's crust. Technetium is not
found in nature and was the fITst man-made element. Rhenium 2K2Mn04 + H20 + 0 3 ---7 2KMn04 + 2KOH + O2
is a very rare element. The important ores of manganese are: 3K2Mn04 + 2C02 ---7 2KMn04 + Mn02 + 2K2C03
(i) Pyrolusite, Mn02 Now-a-days, the conversion is done electrolytically.
(ii) Braunite, Mn203 and . It is electrolysed between iron cathode and nickel anode.
(iii) Hausmannite, Mn304' Dilute alkali solution is taken in the cathodic compartment and
Manganese is obtained from its oxide ore generally pyrolusite potassium manganate solution is taken in the' anodic
or hausmannite by reduction with carbon or aluminium. compartment. B?th the compartments are sepai-ated by a
Since Mn02 gives an explosive reaction with aluminium, it diaphragm. On plt\ssing current, the oxygen evolved at anode
is first converted into Inanganomanganic oxide, Mn304, by oxidises manganate into permanganate.
heating to redness. This is then reduced with aluminium in fire- At,anode:
clay crucible embedded in sand. 2K2Mn04 + H20 + 0 ---7 2KMn04 + 2KOH
3Mn0 2 ---7 Mn30 4 + O2 MnO~- ---7 Mn04 + e
3Mn30 4 + 8AI ---7 9Mn + 4A1203 Green Purple
Manganese is purified by distillation in vacuum. At cathode :
---~--~chiefuse_ofmanganes~is_inmsteeLproduction. 95% ofm~ ___~ . . ----2H±-~e~1I2----~~~----m-____~ _ _ _ _. ._
the manganese ores mined are used in steel industry to produce Th di 1 ti" trat d d lIed di-~.- ~
all Th' d 'd C d ed d e ano c so u on IS concen e un er contro con ..
oys. . e ffilxe oX! es 0 Iron an manganese are r uce tions. when crystals of potassium permanganate are obtained.
by heating in a blast furnace along with carbon. Two important
alloys are ferromanganese (80% Mn and 20% Fe) and • Properties
spiegeleisen (20 30% Mn, 5% C and rest Fe).
It is purple coloured crystalline compound. It is fairly soluble
The outer electronic configuration of manganese is 3d 54i.
in water. When heated alone or with an alkali, it decomposes
It exhibits a large number of oxidation states varying from
evolving oxygen.
o to +7. The zero oxidation state is observed in carbonyls. The
+2 state is the most stable and most common. Manganese 2KMn04 ---7 K2Mn04 + Mn02 + 02
exhibits +3, +4, +6 and +7 oxidation states. In +7 state the 4KMn0 4 + 4KOH ---7 4K2Mn04 + 2H20 + O2
permanganates are strong oxidising agent. +4 and +7 states are On treatment with conc. H2S04, it forms manganese
also stable. Manganese forms a number of oxides. The basic heptoxide via permanganyl sulphate which decomposes
nature decreases while acidic nature increases as the oxidation explosively on heating.
state increases. 2KMn04+3H2S04 ---7 2KHS04 + (Mn03hS04 + 2H20
Oxide MnO Mn03 (Mn03hS04 + H20 ---7 Mn2~ + H2S04
(unstable) 3
Mn20 7 ---7 2Mn02 + 2: ~
Oxid. state +2 +3 +6 +7
'---v-------'
Basic
Potassium permanganate is a powerful oxidising agent. A
Nature Amphoteric Acidic Strongly
acidic mixture of sulphur, charcoal and KMn04 forms an explosive
Manganous Manganic Manganites Manganates Permanga- powder. A mixture of oxalic acid and KMn04 catches fire
. salts . salts nates spontane.ous after a few seconds. The same thing happens
Manganese also forms a mixed oxide, Mn304, which is a when glycerine is poured over powder~d KMn04'
combination of MnO and Mn203' It is known as mangano- Potassium permanganate acts as an oxidising agent in
manganic oxide. alkaline, neutral or acidic solutions.
'.'''r1l! (a) In alkaline solution: KMn04 is first reduced to
14~. POTASSIUM PERMANGANATE, KMn04
-·.'.1,'," manganate and then to insoluble manganese dioxide. Colour
This is the most important and well known salt of permanganic changes first from purple to green and fmally becomes
acid. It is prepared from the pyrolusite ore. It is prepared by colourless. However, brownish precipitate is formed.
fusing pyrolusite ore either with KOH or K2C03 in presence 2KMn04 + 2KOH ---7 2K2Mn0 4 + H20 + 0
of atmospheric oxygen or any other oxidising agent such as 2K2Mn04 + 2H20---7 2Mn02 + 4KOH + 20
KN0 3. The mass turns green with the formation of potassium 2KMn04 +H20 Alkaline) 2Mn02 + 2KOH + 3[0]
manganate, K2Mn04. or 2Mn04 + H20 ---7 2Mn02 + 20Ir + 3[0]
2Mn02 + 4KOH + O2 ---7 2K2Mn04 + 2H20 (h) In neutral solution: Mn02 is formed. Brownish
2Mn02 + 2K2C03 + 02 ---7 2K2Mn04 + 2C02 ppt. is present.
The fused mass is extracted with water. The solution is 2KMn04 + H20 ---7 2Mn02 + 2KOH + 3[0]
now treated with a current of chlorine or ozone or carbon
dioxide to convert manganate into permanganate. or 2Mn04 + H20 ---7 2Mn02 + 20Ir + 3[0]
2K2Mn04 + Cl2 ---7 2KMn04 + 2KCI or Mn04 + 2H20 + 3e- ---7 Mn02 + 40H-
(c) In acidic solution (in presence of dilute H2S04): 2KMn04 + 3H2S04 + SH202 -----7 K2S04 + 2MnS04
Manganous sulphate is formed. The solution becomes . + SH20 + S02
colourless. or 2Mn04 + SH20 2 + 6H+ -----7 2Mn2+ + SH20 + S02
2KMn04 + 3H2S04 -----7 K2S04 + 2MnS0 4 + 3H20 + S[O] (x) Ethyl alcohol is oxidised to acetaldehyde.
or 2Mn04 + 6H+ -----7 2Mn2+ + 3H20 + S[O] 2KMn04 + 3H2S04 -----7 K2S04 + 2MnS04 + 3H20 + S[O]
[C 2HsOH + [0] -----7 CH3CHO + H20] x S
or Mn04 + SH+ + Se- -----7 Mn 2+ + 4H20
2KMn04 + 3H2S04 + SC2HsOH -----7 SCH3CHO + K ZS04 +
This medium is used in quantitative (volumetric) estimations.
2MnS04 + SH20
The equivalent mass of KMn04 in acidic medium is
=Mol.Smass . The OX}'danon
. reactIons
. 0 f'difi
act ed KMnO4 are • In Neutral Med'lum
catalysed by Mn (ii) ion. (i) H2S is oxidised to sulphur.
The important oxidation reactions are : 2KMn04 + H 20 -----7 2Mn02 + 2KOH + 3[0]
(i) Ferrous salts are oxidised to ferric salts. [H2S+[0] -----7 H 20 + S] x 3
_ 2KMn0<L:t 3HzS04 -----7_K2~04 + 2Mn~Q4.±:3HZO + S[0]_ _._2KMnO-4-=1-_3H~_==::::7.2KO.H_+_2MnO~±2H2-Q.t3S
[2FeS04 + H2S04 + [0] -----7 Fe2(S04h + H20] x S, (ii) Manganese sulphate is oxidised to Mn02.
2KMn04 + H 20 -----7 2Mn02 + 2KOH + 3[0]
2KMn0 4 + lOFeS04 + SH2S04 -----7 SFez(S04h + K2S04
+ 2MnS04 + SH20 [MnS04 + H20 + [0] -----7 Mn02 + H2S04] x 3
2KOH + H 2S04 -----7 K2S04 + 2H20
or 2Mn04+lOFe2++16W -----7 lOFe3++2Mn2++SH20
(ii) Iodine is evolved from potassium iodide. 2KMn0 4 + 3MnS04 + 2H z0-----7 K2S04 + SMnO z + 2H zS04
(iii) 'Sodium thiosulphate is oxidised to sulphate and
2KMn04 + 3H2S04 -----7K2S04 + 2MnS04 + 3H20 + S[O]
sulphur.
[2KI + H2S04 + [0] -----7 K2S04 + 12 + H20] x S 2KMn04 + 3Na2S203 + H20 -----7 2KOH + 2Mn02 +
2KMn04+ lOKI+SH2S04 -----7 6K2S04+2MnS04+S12+SHzO 3Na2S04 + 3S
or 2Mn04 + lOr + 16H+ -----7 2Mnz+ + SI2 + SHzO • In Alkaline Medium
(iii) H 2S is oxidised to sulphur.
(i) It oxidises iodide to iodate.
2KMn04 + 3H2S04 + SH2S -----7 K2S04 + 2MnS04 +
2KMn04 + H20 -----7 2KOH + 2Mn02 + 3[0]
SS + SH20
KI + 3[0] -----7 KI03
(iv) SOz is oxidised to H ZS04.
2KMn04 + KI + H20 -----7 2KOH + 2MnOz + KI03
2KMn04 + SS02 + 2H20 -----7 K2S04 + 2MnS04 + 2HzS04
(li) It oxidises ethylene to ethylene glycoL
(v) Nitrites are oxidised to nitrates.
2KMn04 + SKN02 + 3H2S04 -----7 K2S04 + 2MnS04 CH2 CH20H
+ SKN03 + 3H zO II +H20 + [0] -----7 I
(vi) Oxalic acid is oxidised to CO2. CH2 CH20H
COOH In alkaline medium it is called Baeyer's reagent.
SI + 2KMn04 + 3H2S04 -----7 K2S04 + 2MnS04 Structure: In permanganate ion, manganese undergoes
COOH + lOCOz + SHzO sp3 -hybridisation i.e., tetrahedral configuration results. Four
(vii) It oxidises hydrogen halides (HCI, HBr or HI) into oxygen atoms are present on the four apices of the tetrahedron.
X2(halogen). o
2KMn04 + 3H2S04 + lOHX -----7 K2S04 + 2MnS04 + II
(viii) Arsenites are oxidised to arsenates.

SH20 + SXz
~~n""o_
2KMn04 + 3H2S04 -----7 K2S04 + 2MnS04 + 3H20 + S[O] o
• Uses
[Na3As03 + [0] -----7 Na3As04] x S
2KMn04 + 3H2S04 + SNa3As03 -----7 K2S04 + 2MnS04 + (i) KMn04 is used as an oxidising agent in laboratory and
SNa3As04 + 3H zO industry. In volumetric estimations, the solution is ftrst
(ix) Hydrogen peroxide is oxidised to HzO and Oz. standardised before use. In volumetric estimations, acidifted
2KMn04 + 3H2S04 -----7 K2S04 + 2MnS04 + 3HzO + S[O] standardised KMn04 solution is used. For maintaining acidic
[H202 + [0] -----7 H 20 + O 2] x S medium only dilute H 2S04 is used. HCI or RN03 are not used
because HCl reacts with KMn04 and produce C12 gas while Thus, in ous-series, nickelous compounds are most stable
HN0 3 , itself reacts as an oxidising agent. while in ic-series, ferric compounds are most stable.
(li) Alkaline potassium permanganate is called Baeyer's 3. Occurrence: All the three are relatively abundant.
reagent. This reagent is used in organic che~stry for the test However, iron is more abundant than nickel and cobalt.
of un saturation. KMn04 is used in the manufacture of saccharin,
benzoic acid, acetaldehyde, etc. • Physical Characteristics
(iii) KMn04 is used in qualitative analysis for detecting (a) Physical state: These are all greyish white hard metals
halides, sulphites, oxalates, etc. of high densities. The hardness and density increases from Fe
(iv) It is widely used as a disinfectant and germicide. A very to Ni.
dilute solution of KMn04 is employed for washing wounds
and gargling of mouth sores. It is also used for purifying well Element Fe Co Ni
water. Density 7.86 8.9 8.9
(b) Melting and boiling points: They have high melting
14.8" POSITION OF IRON IN PERIODIC TABLE and boiling points. This shows that covalent bonding is also
. __ .lton..belongs~to.iourth..perio£Land-\rnL.group-oUhe..extended . ._. pre~eE-t inv~lving~_electr'()ns betw(!en atom~~-,-.~.~._. . . _ __
form of periodic table. vrn group consists of nine elements Element Fe Co Ni
arranged in three triads. Iron is a member of flrst triad and M:pt.·COC) 1536 1495 1453
other two members of this triad are cobalt and nickel. These B.pt. eC) 3000 2900 2730
three metals are called ferrous metals and belong to flrst (c) Ionisation energy: Ionisation energies are about the
transition series (3d series) of the periodic table. The members same. Hence, they have same tendency to form ions.
of second and third triads are collectively known as platinnm (d) Oxidation potential: The values of oxidation potentials
metals or noble metals. are fairly close to each other. The values are positive and hence
Three elements iron, cobalt and nickel possess nearly the they can liberate hydrogen from dilute acids.
same atomic masses and resemble each other closely in their
Element Fe Co Ni
properties. The following discussion shows similarities and
First I.E. (eV) 7.90 7.86 7.63
gradation in the properties of Fe, Co and Ni.
Oxidation potential (Volt) +0.44 +0.28 +0.25·
1. Electronic configuration: Two electrons are present
in outermost shell while the penultimate shell is incomplete. (e) Magnetic property: All the three elements are ferro-
The number of electrons on 3d-shell varies from 6 to 8. magnetic, i.e., these are strongly attracted by a magnet and
Fe 26 2,8, 14, 2 ls2,2i2p6,3s23p63t/',4i [Ar](3d 64s2) remain magnetised even after the removal of the magnetic
Co 27 2,8, 15,2 1i,2i2p6,3i3l3d ,4i7 7
[Ar](3d 4i) fleld. The ferromagnetic property decreases from iron to nickel.
Ni 28 2, 8, 16, 2 6
li,2i2p6,3hp 3ti,4i 8
[Ar](3d 4i) (f) Catalytic property: All the three elements are used
Thus, the last differentiating electron is accommodated on as catalysts especially in the reactions involving the addition of
3d-shell. Hence, these elements are called transition elements hydrogen as they occlude or adsorb hydrogen.
or d-block elements.
2. Valency: They form 'ous' and 'ie' salts showing
• Cherrilcal Properties
di- and trivalencies. The stability of M2+ cations increases The metals are reactive and their reactivity decreases from
from Fe2+ to Ni2+ ion. Thus, the reducing property of these Fe to Ni.
is in the order Fe2+> C02+ > Ni2+. The removal of a (a) Action of air:. Cobalt and nickel are not affected by
3d electron from M2+ cations to oxidise them into M3+ cations air under ordinary conditions. However, iron is affected by
becomes more and more difficult as we move from Fe2+ to moist air. The oxidation of iron into hydrated iron oxide,
NP+. Thus, the tendency to show trivalency decreases sharply 2Fe203·3H20, is termed rusting of iron.
from Fe to Ni, i.e., stability of M3+ cations is in the order When iron is strongly heated in air or oxygen, it forms
Fe3+ > C03+ > Ni 3+. The reason for more stability of Fe3+ ferroso-ferric oxide, Fe304 (upto 500°C) and Fe203 above
cations is that it has a half-fllled 3d-orbitals. 500"C. Cobalt when strongly heated also forms C0304 while
3d nickel forms NiO.
5
Fe3+ 2, 8, 8 +5 3d i 3Fe + 202 - - 7 Fe304
C0 + and Ni3+ have relatively unstable 3d 6 and 3d 7
3 2Ni + O2 - - 7 2NiO
configurations respectively. (b) Action of water: The metals are not affected by
Co3+ 2,8,8 +6 3d 6 water under. ordinary conditions but when steam is passed
over hot metals, these get oxidised with evolution of hydrogen.
2,8,8+7 3d
7
I jJ, IjJ, I i i i I i I
3Fe + 4H20 (steam) ~ Fe304 + 4H2 (i) Alloy formation: All the three elements have great
Co + H20 (steam) ~ CoO + H2 tendency to form allDYs with each other an~ with other metals.
Ni + H 20 (steam) ~ NiO + H2 (j) Colour of the compounds: The cDmpDunds of iron,
(c) Action of acids: Non-oxidising acids (dilute HCI and cobalt and nickel are cDloured as 3d-energy shell is incomplete
dilute H 2S04) evolve hydrogen with irDn, cobalt and nickel. in M2+ and M3+ cations.
Iron reacts readily while cobalt and nickel react slowly. Ferrous cDmpDunds are usually green while ferric CDm-
M + 2HCI~ MC1 2 + H2 pounds are yell .ow. The cDIDur .of nickel cDmpounds is green
while .of cobalt cDmpounds is pink.
M + H 2S04 ~ MS04 + H2
All the three metals, dissolve in concentrated sulphuric acid
14~~~ EXTRACTION OF IRON
evolving sulphur dioxide.
2Fe + 6H2S04 ~ Fe2(S04h + 3S02 + 6H20 Occurrence: IrDn is the fDurth mDst abundant element and
Co + 2H2S04 ~ CoS04 + S02 + 2H20 the secDnd mDst abundant metal in nature. It occurs in cDmbined
Ni + 2H2S04 ~ NiS04 + S02 + 2H20 state. Th: main ores of iron are:
These meta1s dissoIve m . d'l
1 ute RNO I'
3 evo vmg. NO 1.• OXide ores: • .
__ .__ ~~__ ._~~M-+-~---+ME~)z-+-2H}X--3-- ..~..- - __-:_(!LMI!g!!e~lte.,.]"hQ....-.l:~usuallyJllackjIl...colol.lL..ll1S---.
nchest ore of tron and contams upto 70% of the metal.
[3H + lINQ3~NO + 2H20 1 x 2 Eii) Haematite, Fe20j. It is usually red in colour.
3M + 8RN03 ~ 3M(N03h + 2NO + 4H20 (iii) Limonite or hydrated ferric oxide, Fe203·3H20. It
However, with concentrated nitric acid, these metals become has yellow, brown or red colour.
passive. 2. Carbonate ore:
(d) Action of alkalies: These metals are not affected by Siderite or Sepathic iron, FeC03• It is also called clay-
alkalies. iron stone due to the presence of excess of clay in it.
(e) Action of halogens: These metals directly combine 3. Sulphide ores:
with halogens. (i) Iron pyrites, FeS2' It is mainly used for the manu-
2Fe + 3Clz ~ 2FeCl 3 facture of sulphur dioxide (sulphuric acid). It is not used for
Ferric chloride extraction of iron.
Co + Clz ~ CoCl2 (ii) Chalcopyrites, CuFeS2' It is used for the extraction
Cobaltous chloride of copper.
Ni + Cl2 ~ NiCl2 Iron ores have been reported at many places especially in
Nickelous chloride EngIdS an, wen,ed G US
ermany, ..A ., RUSSla,
. BeI'
glUm, France,
Fel3 is unstable and gets reduced to Fe12. Canada and India. Huge deposits of red haematite are available in
2Fel3 ~ 2Fel2 + 12 India in Mayurbhanj (Orissa), Singhbhum (Jharkband), Madhya
(I) Action .of carbon monoxide: All the three metals, Pradesh and Mysore (Karnataka). On the whole, India possesses
combine with carbon monoxide to fDrm vDlatile carbonyls, about one fourth of the total world reserves of iron ore.
viz., Fe(CO)5, C02(CO)S and Ni(COk Iron is extracted from its oxide ores especially from the
Ni + 4CO ~ Ni(CO)4 magnetite, haematite and limonite ores. The extraction involves
(g) Isomorphous sulphates: All form isomorphous. the following steps:
sulphates. (i) Concentration of ore: The concentration of ore is
FeS04·7H20, CDS04·7H20, NiS04·7H20 done by gravity process. The ore is crushed tD small pieces
All these sulphates form double sulphates which are alSD and washed with water to remDve siliciDUS impurities. The
iSDmorphous. For example, (~hS04·FeS04·6H20 Mohr's washed .ore is then subjected to electrDmagnetic separatiDn.
salt and (~hS04·NiS04·6H20 nickel ammonium sulphate (ii) Calcination and roasting: The cDncentrated ore is
are isomDrphDus. heated in excess of air. This treatment prDduces the fDllowing
(h) Complex compounds : All form complex salts. SDme, results.
examples are given below: (a) Moisture and carbDn dioxide are removed.
~Fe(CN)6 2Fe203·3H20 ~ 2Fez03 + 3H20
Potassium ferrocyanide Potassium cobaltocyanide
FeC03 ~ FeO + CO2
K2Ni(CN)4 K3Co(N02)6
Potassium nickelocyanide Potassium cobaltinitrite (b) Sulphur, phosphorus, arsenic, etc., are Dxidised to their
oxides and are, thus, remDved as vDlatile gases.
Nickel has a cDordination number 4 Dr 6 whereas, iron and
cDbalt show a coordinatiDn number 6 .only. IrDn dDes nDt fDrm S + 02~ S02
amine complex while nickel and cDbalt form amine complexes P4 + 502 ~ P4 0 lO
such as [CD(NH3)6]CI3 and [Ni(NH3)4]CI2. 4As + 302 ~ 2As20 3
(c) Ferrous oxide is oxidised to ferric oxide. The charge is introduced in the furnace by lowering the cup
1 and cone arrangement and at the same time the furnace is lit
2FeO + 2O2 -----7 Fe203
and a blast of hot air is sent upwards through the tuyeres. The
(d) The entire -mass becomes porous. temperature varies from 1600"C to 250°C in the furnace from
(iii) Smelting: The calcined ore is mixed with limestone bottom to top. On the basis of variation in temperature, there
(CaC03) and coke in the ratio of 8 : 1 : 4 and introduced in a are four zones where different chemical changes occur. The
blast furnace for smelting. four zones are :
1. Combustion zone: This is the lowest part of the furnace
!lil Blast Furnace above hearth where the temperature is about 1500"-1600°C, In
Blast furnace is a chimney like tall steel structure lined with this zone carbon burns in presence of hot air producing carbon
fire bricks, 25-60 metre high and 8-10 metre in diameter at its dioxide and a lot of heat.
widest part (Fig. 14.2). The furnace has three main parts: C + O2 -----7 CO 2 + 97.0 kcals.
(1) A double cup and cone arrangements: At the top, Carbon dioxide rises upwards and meets with red hot coke.
the furnace has a hopper which rests over a cup and cone It is reduced to carbon monoxide.
~~~~___~ap-ang~ment. ~Y this ~angeme!l:t ct:~ge is in.trodu~ed into the _______~ __ --~LOZ-+-C- 1500°C) 2CO~__~ ______________
=:;ec~~gi:~ the arrangement prevents the eXit of gases _2. Redllctio_n~ne: . Thi~ is theuppe:most Part of
- (2) Shaft : It'IS -I'Lormed by Jommg
. . . two cones, the upper furnace.
., The temperature.VarIes
. .from 250 C to 7000C, : The
. all
one IS c e d th e body an d th I
e ower one IS. calIed b os h . At the OXide ore 1S reduced to lTon
. m this zone. The reduction takes
. h Ie
upper part, there IS a 0 , ou thr gh whic th
h eo h t b urnt llll'Xture place through the followmg stages:
of waste gases escape. In the lower part, there are openings 3Fe203 + CO 300-400°C) 2Fe304 + CO2
for the insertion of water cooled pipes called tuyeres through
Fe304 + CO 500-600°C) 3FeO + CO2
which a blast of hot air is sent upward in the furnace.
(3) Hearth: This is the lowest part of the furnace and FeO + CO 700°C) Fe + CO2
serves as a large crucible. It is provided with two holes one for However, the oxide ore which escapes reduction, gets
the removal of slag and other for molten metal. completely reduced by carbon above 850"c'
Theory of reduction of oxide ore· of iron-see chapter 4. Iron formed is called spongy iron. In the reduction reactions,
heat is also evolved which decomposes part of carbon
Ore, Limestone and
coke are added monoxide into carbon.
at the top 2CO Hotspongy CO C
iron) 2 +
Hopper
3. Slag formation zone: This is the central zone where
the temperature varies from 800--1000°C. The limestone present
in the charge decomposes into calcium oxide and carbon dioxide.
Hot gases to CaC0 3 lOOOOC) CaO + C02

cowper stoves The calcium oxide acts as a flux as it combines with silica
present as an impurity (gangue) to form a fusible slag of
CaSi0 3 ·
25-60 metre CaO + Si02 -----7 CaSi03
Silicates, phosphates and manganates present as impurities
in ore, are reduced to Si, P and Mn, respectively.
P40 lO + lOC -----7 4P + lOCO
Si02 + 2C -----7 Si + 2CO
Mn02 + 2C -----7 Mn + 2CO
Bustle pipe These are partly absorbed by iron (spongy) and partly by
Moltep slag slag.
Tuyeres
Slag tapped off - - . a - 2Ca3(P03)2 + 3Si02 + lOC -----7 3(2CaO·Si02) + 4P + lOCO
here Iron tapped off
here 3Fe + P -----7 Fe3P
t 4. Zone of fusion: This is a zone just above the zone of
Tap hole
Mollen iron combustion. The temperature ranges between 1200--1500°C.
The spongy iron which has absorbed already C, Si, P, Mn,
Fig. 14.2 Blast furnace for the manufacture of cast iron etc., melts at 13000 e and collects at the bottom of the hearth.
Transition Elements or d-block Elements and I-block Elements
The slag which being lighter floats over the molten iron and
prevents the oxidation of molten metal. The slag and molten
There are three commercial varieties of iron depending on their
metal are removed from their respective holes. The molten
carbon content.
metal is run into moulds and is allowed to solidify.
Iron obtained from the blast furnace is called pig iron. It ill (i) Cast Iron
contains 93% iron, 5% carbon and rest silicon, manganese,
phosphorus, etc., as impurities. The pig iron is remelted and It is the most impure form of iron and contains the highest
percentage of carbon from 2.5 to 5 per cent and about 2 per
cast or poured into moulds. This is known as cast iron. Hence,
after remelting the pig iron becomes cast iron. cent of other impurities like Si, P, Mn and S. Cast iron is of two
types:
When the molten pig iron is cooled at once, the iron is called
white cast iron, which contains carbon in the form of (a) White cast iron: Carbon is present in the form of
cementite, Fe3C,
cementite, Fe3C and when the molten pig iron is cooled slowly
and slowly, the iron is called as grey cast iron, which contains(b) Grey cast iron: Carbon is present in the form of
carbon in the form of graphite. graphite. Cast iron melts at about 1250"C (due to presence of
impurities) whereas pure iron melts at 1530°C. The molten cast
FLOW SHEET FOR EXTRACTION OF .IRON~~._~~iro!!....eM>ll,m!L91t~olidificatiQILand_.hence.iLpro~4ood...-_._-
····-·-···~··---·--·---h~n ··ore~·-~- --~ . ~- castings. Various articles such as stoves, pipes, radiators,rail\Vay
sleepers,gutterpipes; toys, etc:, are prepared from cast iron. Cast
iron does not rust easily and neither be tempered. Due to high
Concentration carbon content, it is hard and brittle and cannot be welded. It has
by very little ductility and thus cast iron is not suitable for forging.
Gravity process followed
by electromagnetic· separation
II (ii) Wrought Iron
-J,
It is the purest form of iron. It contains the lowest percentage
Calcination and Roasting
of carbon from 0.1 to 0.25 per cent and 0.3 per cent other impuri-
Ore + air Heat) moisture, CO2, S02 ties. It is manufactured from cast iron by puddling process.
, A~03 removed Wrought iron is manufactured in a special type of rever-
FeO is oxidised to ferric oxide beratory furnace called puddling furnace, the hearth of which
is lined with haematite, Fe203. The cast iron is melted on the
Smelting in a blast furnace (ore + coke + limestone). The hearth of the furnace by the hot gases and stirred with long
following reactions occur. iron rods. The impurities of cast iron are rapidly oxidised by
Fe203 + 3CO 400 - 700·C ) 2Fe + 3C02 oxygen of haematite (lining). Oxides of carbon and sulphur
Spongy iron being volatile escape while those of Mn, P and Si form slag.
3C + Fe203 ~ 2Fe + 3CO
CaC03 lOOO·C) CaO + CO2
3Si + 2Fe203 ~ 3Si02 + 4Fe
CaO + Si02 ~ CaSi03 (slag)
3Mn + F~03 ~ 3MnO + 2Fe
2CO Hot iron) CO2 + C MnO + Si02 ~ MnSi03 (Slag)
6P + 5F~03 ~ 3P20 5 + lOFe
Si02 + 2C 1200"C) Si + 2CO
P20 5 + Fe203 ~ 2FeP04 (Slag)
Mn0 2 + 2C ~Mn + 2CO With the removal of impurities, the melting point of the
P4010 + lOC ~ 4P + lOCO metal rises and it becomes a semi-solid mass. The semi-solid
Spongy iron + C, Mn, Si, etc. ~ Impure iron mass is taken out in the form of balls and is beaten under steam
hammers to squeeze out as much of slag as possible. This
c.+ 02 1600·C) C02 produces almost pure iron known as wrought iron.
C02 + C 1500"C) 2CO
• Properties
(i) Wrought iron is extremely tough, highly malleable and
Pig iron ductile. (ii) It softens at about lOOO°C and then it can be forged
1 Remelted
and cooled
Cast iron
and· welded. (iii) On account of the presence of very small
percentage of slag, it has fibrous structure and thus, can
withstand high stresses. (iv) Wrought iron is resistant towards
rusting and corrosion.
(Fe =93%; C = 5% and impurities of Mn, P, Si, etc. = 2%)
• Uses
It is used to make chains, nails, hooks, bolts, agticultural
implements, electromagnets, bars, wires, etc.
Molten matte
(iii) Steel + Sand
This is the most important commercial variety of iron. The

percentage of carbon in this form of iron is midway between
that of cast iron and wrought iron, i.e;, 0.25 to 2 per cent.
There are many varieties of steel depending on the amount of
carbon present in it. ~iI-:I::::f"'"-Tuyeres
(a) Mild steels: These contain low percentage of carbon.
Such steels show the properties of wrought iron along with
elasticity and hardness.
(b) Hard steels: These contain high percentage of carbon. Fig. 14.3
____The~are~hanLand brittle~ _ _~_. . ._____ . . . ___ ~._____ afiaaolasrof-hocair-isolowntrnougnirftom the-lJottum~arrd
(c) Special steels or alloy steels: Steel mixed with small
amounCof nickel, cobalt, cnroniium,turigsteri,molybdenuni; keeping the mouth of the converter vertically upwards. SiliB'a=;:::
manganese, etc:, acquires special properties. Such products and manganese present in pig iron are fIrst oxidised and then
are called special steels or alloy steels. Some important alloy combine to form slag.
steels are listed below: . Si + Oz ----7 SiO z
_... - - .- 2Mn + Oz ----7 2MnO
Name oithe I, Me
taladd·
ed' Properties Uses
ailoy steeI MnO + SiOz ----7 MnSi0 3
1. Invar 36% Ni Coefficient of Measuring tapes, In the end, carbon is oxidised to carbon monoxide which
expansion is pendulums bums with blue flame at the mouth of the converter. Some iron
very small is also oxidised which converts the carbon into carbon
2. Chromevan- 1% Cr; 0.15%V High tensile Springs, shafts, mQnoxide.
adiumsteel strength axles
3. Manganese 12-:15% Mn Hard and tough Rock crushing 4Fe + 30z ----7 2Fez03
steel machinery, almirah, Fe203 + 3C ----7 2Fe + 3CO
helmets
4. Stainless 11.5% Cr; Resists Common When whole of the carbon is oxidised, the blue flame
steel 2% Ni corrosion articles suddenly dies out. The air supply is stopped for a while and the
5. Tungsten 14-20% W; Very hard High speed tools requisite amount of spiegeleisen is added. The blast is continued
steel 3-8% Cr just for a moment to ensure complete mixing. The resulting
6. Alnico 60% Fe, 12% Highly magnetic For making perma- product is the manganese steeL
AI, 20% Ni, nent magnets
When cast iron or pig iron contains phosphorus as an
8% Co
7. Permalloy 21% Fe, 78% Strongly magne- For making impurity, a basic lining of CaO or MgO is used in the Bessemer
Ni and carbon tised by electric electromagnets, converter. Phosphorus is oxidised to P4010 which combines
current, loses ocean cables, etc. with CaO to form calcium phosphate as. slag.
magnetism when ,
current is cut off. !
4P + 502 ----7 P4010
6CaO + P4010 ----7 2Ca3(P04h
Manufacture of Steel This slag is used as a fertilizer and known as Thomas slag.
(li) Open hearth process or Siemens-Martin process:
Many methods are used for the manufacture of steel. Some This is the modem process and the furnace used consists of
are described below: an open hearth. The hearth is lined with silica or calcined
(i) The Bessemer's process: The process is based on dolomite (CaO·MgO) depending upon the nature of impurities
the fact that impurities of pig iron are completely oxidised in present in pig or cast iron. Silica lining is used if the impurities
presence of hot air blast, i.e., virtually wrought iron is obtained. are manganese, silicon, etc., and calcined dolomite lining is
This is then mixed with a known amount of spiegeleisen, an used if much of phosphorus is present. A high temperature of
alloy of iron, manganese and carbon to obtain steel. about l500"C is generated by burning producer gas which
The process is carried out in Bessemer converter lined with works on regenerative system of heat economy (Fig. 14.4).
silica bricks. The molten pig iron is introduced in the converter
Transition Elements or d-block Elemt;nts and I-block Elements
(iii) The electric process: This process is similar to

open hearth process with a difference that heating is done
electrically. The steel of much better quality can be obtained
but the process is rather costly.
The process consists in heating of the charge having pig or
cast iron, scrap iron, iron ore(haematite) and lime in an electric
Hearth lining furnace using vertical carbon electrodes. When the arc is struck
Basic: CaO or MgO
Acid: Si02 between the electrodes, the high temperature of about 2000°C
Fig. 14.4 generated melts the charge and chemical reactions start
instantaneously. The impurities are oxidised by iron ore in the
The charge consists of pig or cast iron, iron scrap, iron ore same fashion as in the open hearth process. .
(haematite) and lime. The charge is heated on the hearth of the
furnace. The impurities are oxidised by iron ore.
3Si + 2Fe203 ~ 4Fe + 3Si02
3Mn + F~03 ~ 2Fe + 3MnO
MnO + Si02 ~ MnSi03 (Slag)
--- ~------.-~---.--.---
Door for
loading
12P + lOFe:z03 ~ 3P4010 + 20Fe .
6CaO + P4010 ~ 2Ca3(P04h (Slag)
CaO + Si02 ~ CaSi03 (Slag)
2Fe203 + 3S ~ 3S02 + 4Fe
Samples of steel are drawn from time to time and tested for
carbon content. Finally spzegeleisen (an alloy of iron, manganese
and carbon) is added to the molten mass to obtain desired steel.
The process takes about 8 to 10 hours for completion. The
process takes longer time than Bessemer's process but it has
following advantage over the Bessemer's process. Fig. 14.5
(a) The temperature can be controlled as the heating is done
externally. This method is especially useful for the production of the
(b) As it is a slower process, it can be controlled in better alloy steels.
way. The composition and quality can be well controlled.
(c) The loss of iron in this process is only 4% while the loss ~ Heat Treatment of Steels
is about 15% in Bessemer's process.
The properties of steel depend on three factors:
(d) In this process scrap iron is reused.
(i) Carbon content: With the increase of carbon content
(e) This yields better quality of steel.
the hardness and tensile strength of the steel increases while
(f) A considerable economy of the fuel is achieved by using
ductility decreases.
the regenerative system.
COMPAPilSON OF CAST IRON, WROUGHT IRON AND STEEL
Property Cast iron Wrought iron Steel

1. Chemical composition Iron 93-95% Iron 99.5-99.8% Iron 98-99.5%
Carbon 2.5-5% Carbon 0.1-0.21% Carbon 0.25 to 2.0%
Impurities about 2% Impurities about 0.3%
2. Melting point Lowest about 12000c Highest about 1500·C Between 1300-1400"C
3. Hardness Very hard Soft . Medium hardness
4. Malleability Brittle Malleable Malleable and brittle
5. Welding Cannot be welded Can be welded easily Can be welded with difficulty
6. Tempering Cannot be tempered Cannot be tempered Can be tempered
7. Magnetisation Cannot be permanently magnetised Magnetisation is not permanent but easy Can be permanently magnetised
8. Structure Crystalline I Fibrous Granular
(ii) Presence of other metals: The presence of Si gives or passive. Such behaviour is not only shown by iron but also
steel a fibrous structure. Presence of Mn produces elasticity by many other metals like Cr, Co, Ni, Al, etc. This phenomenon
and increases tensile strength. Cr imparts resistance to chemical is known as passivity and the chemical substances which
action. bring passivity are called passivators.
(iii) Heat treatment : The hardness and elasticity of the ''The inertness exhibited by metals under conditions
steel can be changed by heating the steel at different when chemical activity is to be expected is called chemical
temperatures and then allowing to cool it in different ways. passivity." Iron can be rendered passive by other oxidising
The following heat treatments are given to steel: agents like chromic acid, KMn04, cone. H 2S04, etc. The
(a) Annealing: It is a process of heating steel to bright passivity of the iron is believed to be due to formation of an
redness and then cooling it very slowly. This treatment makes extremely thin film (invisible) of oxide on the surface of iron.
the steel soft and ductile. This type of steel is used in fabrication Passive iron can be made active by scratching or heating in a
process. reducing atmosphere of H2 or CO, or heating in HN03 upto
(b) Quenching: It is a process of heating steel to bright 75°C.
redness and then cooling it suddenly by plunging it in water or
oil. Such a steel is extremely hard and brittle. It has very low 14.1~! COMPOUNDS OF IRON
.elasticityL ..~.~ ..__..___ .__.._~~~.~_... ~~___....._.~.. ~.___.......
(c) TemperiIlg : .... !~is ~. ~rocess of heating the que~che?--~-Ferrot..ls sliijihate(Greenv1triolf,~FeS~~mo--~~
steel to a temperature much l5elow redness and then cooling!t _ . . 4 2
slowly. Such steel is neither so hard nor so brittle. In the This is the best 'known ferrous salt. It occurs in nature as
process of tempering, a thin film of the oxide is formed on the copperas and is formed by the oxidation of pyrites under the
surface of steel. The colour of the oxide film depends on the action of water and atmospheric air.
temperature at which the quenched steel is heated. 2FeS2 + 702 + 2H20 ~ 2FeS04 + 2H2S04
Temperature range Colour of the oxide film It is commonly known as harakasis.
Preparation. (i) It is obtained by dissolving scrap iron in.
200--23O"C Yellow
dilute sulphuric acid.
225-270"C Brown
Fe + H 2S04 ~ FeS04 + H2
300"C Blue The solution is crystallised by the addition of alcohol as
The surface treatment of the steel is done by the following ferrous sulphate is sparingly soluble in it.
two processes: (ii) It can also be prepared in the laboratory from the Kipp's
(a) Case hardening: The process of producing a thin waste. The excess of sulphuric acid is neutralised by heating
coating of hardened steel on the surface of the mild steel is with a small quantity of iron fillings. The solution is then
called case hardening. This is done by heating the mild steel crystallised.
with charcoal and then plunging into oil. This produces a thin Manufacture: Commercially, ferrous sulphate is obtained
coating of hardened steel on the surface. Such a steel becomes by the slow oxidation of iron pyrites in the presence of air and
resistant to wear and tear. moisture. The pyrites are exposed to air in big heaps.
(b) Nitriding: The process of producing a hard coating 2FeS2 + 2H20 + 702 ~ 2FeS04 + 2H2S04
of iron nitride on the surface of steel is called nitriding. Steel The free sulphuric acid is removed by the addition of scrap
is heated in the atmosphere of dry ammonia at 500-600°C for iron. On crystallisation green crystals are obtained.
about 3 to 4 days when a hard coating of iron nitride is produced
on the surface. • Properties
14~1_~i~ PASSIVITY OF IRON (i) Hydrated ferrous sulphate (FeS04·7H20) is a green

crystalline compound. Due to atmospheric oxidation, the crystals
The following are the common properties of iron. acquire brownish-yellow colour due to formation of basic
(a) It evolves hydrogen gas, when made to react with dilute ferric sulphate.
HCI or dilute H2S04, 4FeS04 + 2H20 + O2 ~ 4Fe(OH)·S04
Basic ferric sulphate
(b) It precipitates silver from silver nitrate solution and
copper from copper sulphate solution. . (li) Action of heat: At 300°C, it becomes anhydrous.
The anhydrous ferrous sulphate is colourless. The anhydrous
But if a piece of iron is first dipped in concentrated nitric
salt when strongly heated,breaks up to form ferric oxide with
acid for sometime and then made to react with the above
the evolution of S02 and S03'
reagents, neither hydrogen is evolved nor silver or copper are
precipitated. Thus, iron by treatment with concentrated nitric 300"C High
FeSO 4 ·7H 20 -7H o)2FeS0 4 ) Fe203 +S02 + S0 3
acid has lost its usual properties or it has been rendered inert Green 2 White temp.
Transitio.n Elements o.r d-block Elements and I-blo.ck Elements
(iii) The aqueo.us so.lutio.n o.f ferro.us sulphate is slightly (ii) It is used as a mo.rdant in dyeing.
acidic due to. its hydro.lysis. (iii) It is also used as an insecticide in agriculture.
(iv) It is emplo.yed as a labo.rato.ry reagent and in the
FeS04 + 2H20 ~ Fe(OHh + H2S04
Weak base Strong acid
preparatio.n o.f Mo.hr's salt.
(iv) Ferrous sulphate is a stro.ng reducing agent.
Ferrous Ammonium Sulphate (Mohr's salt)
(a) It deco.lo.urises acidified po.tassium permanganate.
(NHd2S04·FeS04-6H20
2KMn04 + 3H2S04 ----7 K 2S04 + 2MnS04 + 3H20 + 5[0]
Preparation: The do.uble salt is best prepared by making
saturated so.lutio.ns o.f pure ferro.us sulphate and pure ammo.nium
sulphate in air free distilled water at 40"C. Bo.th the so.lutio.ns
are mixed and allo.wed to. co.o.l. Generally, few drops o.f sulphuric
acid and a little iro.n wire are added befo.re crystallisatio.n as to.
(b) It turns po.tassium dichro.mate (acidified) green as prevent o.xidatio.n o.fferro.us sulphate into. ferric sulphate. The
dichro.mate is reduced to. chromic salt (green). salt is o.btained as pale green crystals.
K2Cr207 + 4H2S04 ----7 K2S04 + Cr2(S04)3 + 4H20 + 3[0]
~~~2Feoo.r+~~.+-.Q-----+-Fe2(SO<t):r+-H20}x3- ......- ...~~- Pro~erti~~L_~._ ...----~---~------~.--~-.-----
It is pale gre.encry~~.neCQJ:npou.ndwhich does no.t.~c
6FeS04 + KZCr:i07 + 7H2S04 ----7 3Fei(S04h +K2S04 efflo.resce like ferro.us sulphate. It is less readily o.xidised in the
+ Cr2(S04)3 + 7H20 so.lid state. It is, therefo.re, a better vo.lumetric reagent in
(c) It reduces go.ld chlo.ride to. go.ld. preference to. ferro.us sulphate. Chemically, it is similar to. ferro.us
sulphate. All the chemical reactio.ns o.bserved in the case o.f
AuC1 3 + 3FeS04 ----7 Au + Fe2(S04)3 +FeC13
ferro.us sulphate are given by ferro.us ammo.nium sulphate,
(d) It reduces mercuric chlo.ride to. mercuro.us chlo.ride.
[2HgC12 ----7 HgzCl 2 +2Cl] x 3 Ferric Chloride, FeCI3
[3FeS04 + 3Cl ----7 Fez(S04)3 + FeCI3] x 2 This is the mo.st impo.rtant ferric salt. It is kno.wn in
6HgCl2 + 6FeS04 ----7 3Hg2Cl2 + 2Fe2(S04h + 2FeCl3 anhydro.us and hydrated fo.rms. The hydrated form co.nsists o.f
six water mo.lecules, FeCI3·6H20.
(v) A co.ld so.lutio.n o.f ferro.us sulphate abso.rbs nitric o.xide .
Preparation: (i) Anhydro.us ferricchlo.ride is o.btained by
fo.rming dark brown additio.n co.mpo.und, nitro.so. ferro.us
passing dry chlo.rine gas o.ver heated iron fillings (Fig. 14.6).
sulphate.
The vapours are co.ndensed in a bottle attached to. the o.utlet
FeS04 + NO----7
Nitroso ferrous sulphate
o.f the tube.
(Brown) 2Fe + 3Cl2 ----7 2FeC13
The NO gas is evo.lved when the so.lutio.n is heated. To fuming
(vi) It fo.rms do.uble sulphates o.f the co.mpositio.n cup board
Iron
R2S04·FeS04·6H20 where R =an alkali metal o.r NHt radical.
(NH4)2S04·FeS04·6H20 (ferrous ammo.nium sulphate) is
kno.wn as Mo.hr's salt. .
(vii) It co.mbines with po.tassium cyanide (excess) fo.rming
po.tassium ferro.cyanide, ~e(CN)6.
FeS04 + 2KCN ----7 Fe(CNh + K2S04 Ferric chloride
Fe(CNh + 4KCN ----7 ~Fe(CN)6 (FeeI 3)
• Uses Fig. 14.6
(i) Ferro.us sulphate is used fo.r making blue black ink. The (ii) Hydrated ferric chlo.ride is o.btained by the actio.n o.f
ink is prepared by mixing a so.lutio.n o.f tannin and ferro.us hydro.chlo.ric acid o.n ferric carbo.nate, ferric hydroxide o.r ferric
sulphate. A co.lo.urless iron salt o.f tannic acid is fo.rmed. A blue o.xide.
dye (usually indigo.) is added. The writing with this ink is blue Fe2(C03)3 + 6HCI----7 2FeCl 3 + 3H20 + 3C02
but so.o.n o.n expo.sure to. air, it beco.mes black o.n acco.unt o.f Fe(OH)3 + 3HCl ----7 FeCl3 + 3H20
o.xidatio.n o.f co.lo.urless ferro.us salt into. black ferric salt.
Fe203 + 6HCI----7 2FeC13 + 3H20
~ The solution on evaporation and cooling deposits yellow 4FeCl3 + 3~Fe(CN)6 ~ Fe4[Fe(CN)6h + 12KCI
crystals of hydrated ferric chloride, FeCI3·6H20. Prussian blue
(Ferri ferrocyanide)
• Properties (ix) On heating hydrated ferric chloride FeCI3·6H20,

anhydrous ferric chloride is not obtained. It is changed to
(i) Anhydrous ferric chloride is a dark red deliquescent
Fez03 with evolution of H20 and HCl.
solid. It is sublimed at about 300°C and its vapour density
corresponds to dimeric formula, Fe2C~, The dimer dissociates
at high temperatures to FeCI3.The dissociation into FeCl 3 is Hydrated ferric chloride may be dehydrated by heating with
complete at 7500c. Above this temperature it breaks into ferrous thionyl chloride.
chloride and chlorine.
FeCI 3·6H20 + 6S0C12~ FeCl3 + 12HCI + 6SOz
Fe2Cl6 2FeCl3 ~bove 750"<; 2FeCl2 + Cl2
• Uses
(ii) Anhydrous ferric chloride behaves as a covalent
compound as it is soluble in non-polar solvents like ether, (i) The alcoholic solution is used in medicine under the
alcohol, etc. It is represented by chlorine bridge structure. name tincture ferri perchloride. (li) It is used as a laboratory
reagent in the detection of acetates and phenols and also as an
~ ~~ -oxidising-agent-Eiii)-ft~~ilsed--for~ma:kiHgJ:)mssian--blHe,----
(iii) It dissolves in water. The solution is acidic in nature due Corrosion is defined as the gradual transformation of a
to its hydrolysis as shown below : metal into its combined state because of the reaction with
FeCl3 + 3HOH ~ Fe(OHh + 3HCI the environment. Metals are usually extracted from their
The solution is stabilised by the addition of hydrochloric ores. Nature tries to convert them again into the ore form. The
acid to prevent hydrolysis. process by which the metals have the tendency to go back to
(iv) Anhydrous ferric chloride absorbs ammonia. their combined state, is termed corrosion.
FeCl 3 + 6NH3 ~ FeC13·6NH3 Rust (Fe203 + H2 0)
(v) Ferric chloride acts as an oxidising agent. Water _---------~

(a) It oxidises stannous chloride to stannic chloride.
2FeC13 + SnCl2 ~ 2FeC12 + SnC14
(b) It oxidises S02 to H 2S04.
2FeC13 + S02 + 2H20 ~ 2FeCl2 + H2S04 + 2HCI
(c) It oxidisesH2S to S.
2FeCl3 + H 2S ~ 2FeCl2 + 2HCI + S Fig. 14.7
(d) It liberates iodine from KI. When iron is exposed to moist air, it is found covered with
2FeCl3 + 2KI ~ 2FeCl2 + 2KCl + 12 a reddish-brown coating which can easily be detached. The
(e) Nascent hydrogen reduces FeCl3 into FeCI2. reddish-brown coating is called 'rust'. Thus, the corrosion of
FeCI3 + H ~ FeCl2 + HCI iron or formation of the rust is called rusting. The composition
of the rust is not certain but it mainly contains hydrated ferric
(vi) When ammonium hydroxide is added to the solution of
oxide, 2Fe203·3H20, together with a small quantity of ferrous
ferric chloride, a reddish-brown precipitate of ferric hydroxide
carbonate. The rust is formed by the action of water on iron
is formed.
in presence of dissolved oxygen and carbon dioxide. It has
FeCl3 + 3NH40H ~ Fe(OHh + 3~CI been observed that impure iron is more prone to rusting.
(vii) When a solution of thiocyanate ions is added to ferric The following are the favourable conditions for the rusting
chloride solution, a deep red colouration is produced due to of iron:
formation of a complex salt. (i) Presence of moisture
FeCl3 + NH4CNS ~ Fe(SCN)CI2 + ~CI (ii) Presence of a weakly acidic atmosphere
or FeCl3 + 3NH4CNS ~ Fe(SCNh + 3~CI (iii) Presence of impurity in the iron.
(viii) Ferric chloride forms a complex, prussian blue with Various theories have been proposed to explain the
potassium ferrocyani~. phenomenon of rusting of iron but the accepted theory is the
Transition Elements or d-block Elements and I-block Elements 615-----
modem electrochemical theory. When impure iron comes iii between VIIl and fiB groups of the periodic table. Their
contact with water containing dissolved carbon dioXide, a voltaic inclusion in the same subgroup is justified on the basis of:
cell is set up. The iron and other impurities act as electrodes (a) same electronic configuration and
while water having dissolved oxygen and carbon dioxide acts (b) similar characteristics or gradation iii the properties.
as an electrolyte. Iron atoms pass into solution as ferrous ions. 1. Electronic configuration: They have similar
Fe~ Fe2+ + 2e electronic configuration. The distribution of the electrons in
various energy shells of these atoms is shown below:
Iron, thus, acts as anode.
The impurities act as cathode. At the cathode, the electrons Cu 29 2,8, 18, 1 Ii, 2i2p6, 3i3p63d lO,4s1
are used in forming hydroxyl ions. Ag 47 2, 8, 18, 18, 1 Ii, 2i2p6, 3i3p63d lO,
H20 + 0 + 2e~ 20H- 4i4p64dlO,5s1
In presence of dissolved oxygen, ferrous ions are oxidised Au 79 2, 8, 18, 32, 18, 1 Ii, 2i 2p6, 3s23p63dlO,
to ferric ions which combine with hydroxyl ions to form ferric
hydroXide.
Fe3+ + 30H- ~ Fe(OHh
Rust 5i5p65dl05f14, 6i6p66d lO, 7s 1
~--[2Fe2+-+-H20+0-~-2Fe3+-+20H-,;;;;r---- -------Tfi.eelectfunic coiifiguraiion showS-that -the outermost sheU--
Corrosion or rtistiIig is asurfarepneu()menon and thus, the °hi thl-Iese el~men18ts-hlasonee[l(ectr°ln) ~S~d) l~]hi~ethe-penalultiIfinfiate--=
. . s e contams e ectrons n - s p z.e. gener co 1-
protectIOn of the surface prevents the corrOSIon. Iron. can be . 2 -6 10 I' ,
protected from the rustiIig by use of following methods: -
guratIOn (n - l)s ~n - l)p .<~ l)d ns. However, (n - l)d
(i) ApplyiIig paiIits lacquers and enamels on the surface of shell has not attamed stablhty and one or more electrons
iron.' sometimes jump to the outermost shell thereby increasing the
(ii) By forming a firm and coherent protective coating of valency electrons. As a result, the atoms or ions take up the
ferrosoferric oXide. This is done by passing steam over hot new configuration.
iron. Cu ........(8 + 9), 2
(iii) By coating a thin film of zinc, tin, nickel, chromium, Ag........(8 + 9), 2
aluminium, etc.
Au........(8 + 8),3
POSITION OF COINAGE METALS IN It is for this reason that these elements are considered as the
end members of transition series. In higher valency states
PERIODIC TABLE
these elements, therefore, show properties similar to those of
the corresponding transition elements of VIll group.
~
, vpI , m lIB
Period (8) (9) . (10) (11) (12) 2. Valency: Being transition elements, these show
- -
variable valency. Copper forms both cuprous (Cu+) and.cupric
4 Fe 26 Co 27 Ni 28 Cu 29 Zn 30 (Cu2+) ions. The cuprous ions, however, have a tendency -to-
5 Ru 44 Rh 45 Pd 46 Ag 47 Cd 48 change into cupric and thus, soluble cuprous salts are not
stable.
6 Os 76 Ir 77 Pt 78 Au 79 Hg 80
2Cu+ ~ Cu2+ + Cu
m subgroup (group 11) of the periodic table consists of The insoluble cuprous salts as CU2CI2, CU212, CU2(CNh
four metals----copper (Cu), silver (Ag), gold (Au) and unununium
CU2(CNSh are stable. -
(Uuu)*. These are collectively called as copper metals (copper
Silver shows maiIily monovalency. The compounds of
being the predominant member) -or coinage metals or currency
divalent silver are rare.
metals because these (Cu, Ag and Au) have been used in the
Gold like copper also forms two series of salts showing
past in makiIig coins for currency. These are d-block elements
monovalency (aurous salts, Aul and trivalency (auric salts,
as the differentiatiIig electron is accommodated on (n - l)d
Au3+). The aurous salts are not stable and change into auric
energy shell. Copper is a member of 3d series, silver is a
salts.
member Of 4d series, Au is a member of 5d series and Uuu is
3Au+ ~ Au 3++2Au
a member of 6d series. They show relationship with Ni, Pd and
Thus, stable valencies are: Copper; Divalency
Pt (group VIll) which are their left hand neighbours and also
Silver; Monovalency
with Zn, Cd and Hg (group fiB) which are their right hand
Gold ; Trivalency
neighbours in the periodic table. Thus, these occupy position
*Uuu is a synthetic and radioactive element. It is unstable and not much is known about its properties.
3. Physical Properties: (a) These are tough, ductile 2, 8, 18 (3io)

and highly malleable metals. Silver and gold are more ductile 2, 8, 18, 18 (4i~
and malleable than copper. (b) They are good conductors of 2, 8, 18, 32, 18 (5io)
heat and electricity. Silver is the best conductor. (c) They have
The salts in higher oxidation states are coloured as unpaired
high melting and boiling points. The availability of inner d
orbital or orbitals are present in (n ~ l)d energy shell.
electrons enhances the bonding between atoms in the metal
crystal and results in the greater hardness and higher melting Cu 2+ 2, 8, 17 (one 3d orbital singly occupied)
points of these elements like other transition elements. Ag2+ 2, 8, 18, 17 (one 4d orbital singly occupied)
Metal Cu Ag Au Au 3+ 2, 8, 18, 32, 16 (two 5d orbitals singly occupied)
M.Pt. (OC) 1083 961 1063 Cu (ll) salts are generally bluish or green, and Au (ill) salts
B.Ft (oq 2595 2180 2700 are yellow.
(d) Atomic size : The atomic size are relatively small. (i) Magnetic nature: Cu (I), Ag (I) and Au (I) ions are
Gold and silver have nearly the same atomic size. (This is due diamagnetic as all the orbitals are fully paired while Cu (II), Ag
to lanthanide contraction associated with the filling of the (ll) and Au (ill) ions are paramagnetic as one or two orbitals
4/ shell). The atomic volumes are also small and both silver are singly occupied .
... ~~andgold~hav~th~--same~yalues.-~~~~ .~~~~~~--~_~ .... ~_~_~~_~-"_ ~hf!J1lic~LPr()PJ1lrties:~~ Ihe~~hemical activity of a
metal depends on the three hypothetical stages, ~ each~on:e----···~
irivolvir(g an energy change.
Atomic radii A 1.17 1.34 1.34
(Sublimation (Ionisation
Atomic volume 7.1 10.3 10.2 energy)
Metal ----.:::::..:.-4) Gaseous atoms potential) ) Ions
(e) Density: These are heavy metals. Density increases (Hydration
gradually as the atomic number increases. energy) .
---=:::~4) Hydrated Ions.
Metal Cu Ag Au A high heat of sublimation and high ionisation potential will
Density 8.96 10.5 19.3 reduce the tendency of the metal to react. In the case of
(f) Ionisation Energy: Because of the smaller atomic coinage metals both sublimation energy and ionisation potential
size and increased nuclear charge, their ionisation energies are have very high values and thus, coinage metals are less reactive.
high. The ionisation energies do not show the expected trend The chemical activity decreases from Cu to Au.
with increasing atomic number; the values decrease from copper (a) Action uf air : Gold and silver are not affected by air
to silver but increase in going to gold. but copper on long exposure becomes converted with a greyish
Metal Cu Ag Au
green film of basic carbonate, CuC03Cu(OH)z,
I.E. (eV) 7.72 7.57
(b) Affinity for oxygen: Their affinity for oxygen
9.2
decreases from copper to gold. Only copper combines with
The unexpected behaviour from Ag to Au is due to the fact oxygen on heating. Copper oxide when strongly heated is
that the atomic size of Ag and Au are the same while atomic reduced to cuprous oxide, silver oxide breaks up into silver and
charge increases from 47 to 79. oxygen at about 300"C whereas gold oxide breaks up at 250°C.
(g) Oxidation potentials: The standard oxidation poten- CU 20 difficult to break.
tials of coinage metals are negative.
2Ag20 300'C) 4Ag + O 2
Cu ----:y Cu2+ + 2e E~x == -0.34 volt
2Au20 250"C) 4Au + O2
Ag ~ Ag + + e E~x == -0.80 volt
Au ----:y Au3+ + 3e E"ox == ~ 1.42 volt (c) Action of water: The coinage metals are not affected
Cu ----:y Cu+ + e E"ox == -0.52 volt by water or steam. However, copper is attacked by steam at
Au ----:y Au+ + e E"ox = ~1.70 volt red hot state.
Cu (red hot) + H20 ----:y CuO + H2
The values suggest that the atoms of coinage metals have
little tendency to lose electron or electrons. Thus, these elements (d) Action of sulphur: Both copper and silver combine
are feebly electropositive. The nobility increases in the order directly with sulphur. Both copper and silver are found in the
Cu ----:y Ag ----:y Au. Because of nobility, they are frequently nature in the form of sulphides.
found in their native state (silver and gold almost exclusively). (e) Action of halogens: Coinage metals react much more
(h) Colour of the salts: The monovalents salts are readily with the free halogens than with any other element.
colourless as they have (n l)d lO configuration. Copper combines with halogens at ordinary temperatures.
Cu + X2 ----:y CUX2
Silver reacts slowly while, gold reacts with dry halogens on (g) Alloy formation: Copper, silver and gold readily form
heating. alloys with each other and with many other metals. They form
2Au + 3X2 ~ 2AuX3 amalgams with mercury.
(f) Action of acids: Copper, silver and gold do not liberate (h) Complex formation: These metals have strong
hydrogen from dilute acids as they are present below hydrogen tendency to form complex compounds. A \ariety of anionic
in the electrochemical series. Copper dissolves in h.::t dilute and cationic complexes are formed. The principal coordination
acids HCI or H2S04 only in presence of air or oxygen. numbers are 2 or 4. Some complex compounds are listed
below:
Cu + 2HCI + ~ O2 ~ CuCl2 + H20
K3[Cu(CN)41 K[Ag(CNh] K[Au(CNhl
1
Cu + H2S04 + 2" O2 ~ CUS04 + H 20 Pot. cuprocyanide Pot. argentocyanide Pot. aurocyanide
(dil.) K[AuC4]
Copper and silver dissolve readily in acids which act as Cuprammonium Silver ammonium Pot. auric chloride
oxidising agents, e.g., diI. and conc. HN03, conc. H2S04. sulphate chloride
........ _.._.__________ .1i2.§.Q.4i<:one·t::::::=:L!f,0 +...§.Q2..:t-Q---.. ---------5.-Nature--of-CempeUAds-------- -----........-..- - - - -
C..t',..}i?~()4c,.. ():::;2__c:ll~Q4.:+J:I29.. c (a)Oxides: The monoxides ofthe-typeM20are weakly.=:
basic. The basicity does not vary regularly in the group, Ag20
being most basic. These are insoluble in water. CuO shows
H2S04 (cone.) ~ H20 + S02 + 0 basic nature while AU203 shows acidic nature as it dissolves
2Ag + H2S04 + 0 ~ Ag 2S04 + H 20 in strong alkalies.
CuO +- H2S04 ~ CUS04 + H20
2HN03 (cone.) ~ H20 + 2N02 + 0

Sodium aurate
Cu + 2HN03+ 0 ~ Cu(N03h + H20 The oxides of silver and gold are thermally unstable. These
Cu + 4HN03 ~ Cu(N03h+2N02+ 2H20 can be easily reduced with reducing agents. The hydroxides
are weak bases. The hydroxides of Ag and Au are unstable.
2HN03 (cone.) ~ H20 + 2N02 + 0 (b) Halides: Halides of Cu +, Ag + and Au+ are insoluble in
2Ag + 2HN03 + 0 ~ 2AgN03 + H 20 water except AgE The halides of silver get decomposed in
light. AgCI is soluble in ammonia solution. AgBr is partially
2Ag + 4HN03 ~ 2AgN03 + 2N02 + 2H20
soluble while AgI is insoluble.
2HN03 (diI.) ~ H20 + 2NO + 3[0]
AgCI + 2~OH ~ Ag(NH3hCI + 2H20
[Cu + 2HN03 + 0 ~ CU(N03h + H20] X 3 Soluble
3Cu + 8HN03 ~ 3Cu(N03h+2NO +4H 20 (C) Sulpbides: Cu, Ag and Au form sulphides, CU2S,
CuS; Ag2S; AU2S and AU2S3. Copper and silver sulphides are
2HN03 (diI.) ~ H20 + 2NO + 3[0] insoluble in ammonium sulphide but gold sulphides dissolve
[2Ag + 2HN03 + 0 ~ 2AgN03 + H20] X 3 forming thioaurates.
(d) Oxysalts: Copper forms stable oxysalts in divalent
6Ag + 8HN03 ~ 6AgN03 + 2NO + 4H20
state while silver stable oxysalts are known in monovalent
or 3Ag + 4HN03 ~ 3AgN0 3 + NO + 2H20 state. Gold does not form oxysalts. The oxysalts of copper and
Gold only dissolves in aqua-regia. silver decomposes on heating.
[HN03 + 3HCI ~ NOCI + 2H20 + 2CI] X 3 CuC0 3 ~ CuO + CO2
(conc.) (conc.)
1
Ag 2C03 ~ 2Ag + CO2 + 2: O2
[Au + 3CI ~ AuCl3J x 2
1
[AuC13 + HCI~ Cu(N0 3h ~ CuO + 2N02 + "202
Chloro auric acid 1 .
AgN03 ~ Ag + N02 + "202
2Au + 3HN0 3 + llHCI~ 2HAuCI4 +3NOCl+6H20
1
CUS04 ~ CuO + S02 + 2: 02
or HN03 + 3HCI ~ NO + 2H20 + 3CI
Ag 2S04 ~ 2Ag + S02 + O 2
Au + HCI + 3CI ~ HAuC4
Au + HN03 + 4HCI ~ HAuC4 + NO + 2H20
Similarities of Copper with Nickel and Zinc (v) Both form hydrated sulphates, CuS04·5HzO and
ZnS04·7HzO. They also form double sulphates of the type,
II (1) Similarities with Nickel (NH4hS04·MS04·6HzO.
(i) Both are transition metals. These are hard, malleable and (vi) Hydrated chlorides cannot be dehydrated by heating.
ductile. They have high melting and boiling points. They are ZnClz·2HzO ~ Zn(OH)CI + HCI + HzO
good conductors of heat and electricity. (vii) Both have a tendency to form complexes.
(ii) Both the metals show variable valency. The stable valency
(Cu(NH3)4]S04 (Zn(NH3)4]S04
is the divalency. Both form two series of salts: cuprous and
cupric; nickelous and nickelic. Stable salts are cupric and K 3[Cu(CN)4] Kz[Zn(CN)4]
nickelous (divalency). The salts are coloured--<::upric salts are (viii) Both form a number of alloys.
bluish and green while nickelous salts are green. (ix) Basic carbonates of the general formula MC0 3·M(OHh
(iii) Their MZ+ ions are similar in size. are precipitated on treating their salts with sodium carbonate.
Cuz+ = 0.69A Niz+ = o.nA Normal carbonates are obtained by using sodium bicarbonate.
(iv) Both form black sulphides, CuS and NiS.
,_ _
~"' __ Cl~ _ _ • ___ ... _____ . _ .. __ ~ _ _ _ .... ___ ~ _ _ _ _ _ _ _ _ _ _ _ _ _ __
~------U--(vrBotli~are acteaupon bYOXldislOg aciOs~--u-
(vi) Both form similarsulphates .. Copper has been known-to mankind from prehistoric times. It=:::~-=--==:~
CuS04·5HzO NiS04·7HzO was alloyed with other metals and the use of bronze in Egypt
is reported as early as 350 B.c. Romans and Greeks obtained
Both are soluble in water and form double sulphates of the
this metal from the island of Cyprus from which the name
type, (NH4}zS04·MS04·6HzO.
'cuprum' waS derived.
(vii) The oxides of both can be obtained by heating their
Occurrence: Copper constitutes only 0.0001 per cent of
carbonates or nitrates.
the earth's crust. Its deposits, however, are concentrated.
NiC03 ~ NiO + COz Copper is found in nature in the following forms.
CuC0 3 ~ CuO + COz 1. Native state: Copper is found in the metallic condition
Ni(N03}z ~ NiO + 2NOz + ~ 0z in large quantities near lake Superior in U.S.A.; in the Ural
mountains (Russia) and Sweden.
Cu(N03h ~ CuO + 2NOz + ~ Oz 2. Combined state: The principal ores of copper are
Cuo and NiO are basic in nature. These can be reduced sulphides, oxides and basic carbonates.
with hydrogen.
(viii) Basic carbonates of the general formula MC03·M(0H)z • Sulphide Ores
are precipitated on treating their salts with sodium carbonate. (i) Chalcopyrites or copper pyrites, CuFeSz
Normal carbonates are obtained by using sodium bicarbonate. (ii) Chalcocite or copper glance, CuzS
(ix) Both have a tendency to form complexes. They usually (ill) Bornite, CU3FeS3
show coordination number 4.
(CU(NH3)4]S04 (Ni(NH 3)4]S04 • Oxide Ore
K3(Cu(CN)4] Kz[Ni(CN)4] Cuprite (red), CuzO
(x) Both of them show catalytic properties.
(xi) Both form a number of alloys. • Basic Carbonates
(i) Malachite (green), CuC0 3·Cu(OH}z
If (2) Similarities with Zinc (ii) Azurite (blue), 2CuC03·Cu(0H)z
(i) Both are metals. Copper is found to a very minute extent in the animal body
(ii) Both show divalency. where it is said to catalyse the action of iron in the formation
(ill) Both form oxides of the type MO, i.e., CuO and ZnO. of haemoglobin. It is present in traces in the cereals and potatoes.
These can be obtained by heating their carbonates or nitrates. It occurs as a red colouring matter of the feathers of certain
birds. Milk has a very low copper content.
ZnC0 3 ~ ZnO + COz
India is not rich in copper ores. Copper is found in India
Zn(N03h ~ ZnO + 2NOz + 0z ! mainly in Singhbhum district (Jharkhand), Matigara and
(iv) Both form similar compounds. Sulphides, phosphates Dharwar. The copper belt in Rajasthan (Khetri) is at present
and carbonates are insoluble in water while chlorides and under extensive development.
sulphates are soluble in HzO.
Transition Elements or d~block Elements and f-block Elements 679
• Extraction Waste gases
Copper may be extracted by different methods depending

upon the nature of the ore and the % of copper. The methods ii
may be divided into two categories.
1. From sulphide ores:
(a) Dry process or smelting process : This is applied to
those ores in which copper content is more than 3%.
(b) Wet process or hydro-metallurgical process: This
is applied to poor ores containing small percentage of copper.
2. From non-sulphide ores: Leaching process.
Dry process for the extraction of copper: Copper is
extracted mainly from copper pyrites by dry process or smelting
process. The process of extraction of copper from copper
pyrites involves the following steps :
---WConcentratTon-oflhe ore:-The--concentration of . .
the·sulphideores1s~doneby··froth·f1oatatiortptbtess::Theores
are powdered and sieved and then thrown into tanks of water Fig. 14.9
to which pine oil and potassium xanthate have been added. A
strong stream of air is passed which agitates the whole mass. (c) The pyrite is converted into cuprous sulphide and ferrous
Froth is produced which carries along the particles of the ore sulphide with evolution of sulphur dioxide.
2CuFeS2 + 02 ----7 CU2S + 2FeS + S02
(d) The sulphides of copper and iron are partially oxidised.
2FeS + 302 ----7 2FeO + 2S02
2CU2S + 302 ----7 2CU20 + 2S0 2
(iii) Smelting: The roasted ore is mixed with coke and
silica and transferred to a small blast furnace (Fig. 14.10). The
Charging
door
Water jacket
Fig. 14.8 Fire bricks
to the surface of the liquid while the impurities settle to the

bottom of the tank (Fig. 14.8). The froth is continuously Air blast
separated. This is the concentrated ore.

(ii) Roasting: The concentrated ore is heated strongly
in a current of air on the hearth of the reverberatory furnace
(Fig. 14.9). During roasting the following changes take
place.
(a) Free sulphur is oxidised and removed as sulphur dioxide.
S + O2 ----7 S02 Fig. 14.10
(b) The arsenic and antimony present in the ore are removed
as volatile oxides. mixture is heated in the presence of excess of air. The modem
4As + 302 ----7 2As 20 3 blast furnace is made of steel lined inside with refractory bricks
and is about 15 to 20 feet in height. It is water jacketed through-
4Sb + 302 ----7 2Sb20 3
out and is provided near the top with a waste gas outlet.
The air blast enters the furnace through tuyeres. The verter and part of cuprous sulphide is oxidised which combines
following changes occur in the blast furnace. with remaining cuprous sulphide to form free copper metal.
(a) The cuprous oxide reacts with ferrous sulphide. 2CU2S + 302 ~ 2CU20 + 2S02
FeS + CU20 ~ FeO + CU2S CU2S + 2CU20 ~ 6Cu + S02
[Iron has greater affinity for oxygen than copper. The This presents an example of auto-reduction.
copper oxide formed reacts with unchanged iron sulphide to The molten copper is poured off and allowed to cool. During
form iron oxide and reproduce copper sulphide. So it is cooling, the dissolved sulphur dioxide comes out and large
difficult to oxidise cuprous sulphide until whole of the iron blisters are formed on the surface. Hence, the metal formed is
sulphide is oxidised]. given the name 'blister copper'. Blister copper consists 98%
(b) Most of the iron sulphide is oxidised to ferrous oxide. copper and 2% impurities.
2FeS + 302 ~ 2FeO + 2S02 (v) Refining: Blister copper is subjected to refining by
(c) Ferrous oxide combines with silica and forms ferrous either of the following two methods.
silicate. By this reaction most of the iron is removed as slag. (a) Refining by poling: The impure metal is melted in a
FeO + Si02 ~ FeSi03 reverberatory furnace lined with silica. A part of copper metal
"~--~"-""--"""~~--~---""""-"--~-""- - - - ""---Femrus-silicate------"------"-js oxidiSea-tocuptous-oxiOewhiclrl:liss-otv{.$-tn-the~meltand-~ """""-
(Slag) supplies oxygen to the more "basicelementscontainedjn iLas==~~"
The lowest point of the furnace consists of a shallow hearth impurity. These oxides either volatilise or combine with silica
in which the molten mass collects which is known as 'Matte'. forming slag. The oxide of copper which remains in the mass
The matte contains mostly cuprous sulphide with a little iron is reduced by introducing poles of green wood. The gas
sulphide. (hydrocarbons) bubbles originating from the wood act as
(iv) Bessemerisation: The matte obtained from reducing agents. The mass is stirred vigorously with these
smelting is transferred to a Bessemer converter. Some sand poles. The process is thus called poling.
(silica) is added and a blast of air is blown through the molten This process produces copper of about 99.5% purity and
mass. The Bessemer converter is usually a pear shaped steel is known as tough pitch copper.
vessel lined with magnesite and quartz. It is fitted with air-blast (b) Electrolytic refining: Copper is usually refined
tuyeres and mounted in such a way that it can be tilted in the electrolytically. The electrolytic bath consists about 15% copper
desired direction (Fig. 14.11). sulphate solution having 5% sulphuric acid. The anodes are of
The following reactions occur in the Bessemer converter. blister copper and cathodes are thin sheets of pure copper
(a) Remaining ferrous sulphide gets oxidised. (Fig. 14.12).
2FeS + 302 ~ 2FeO + 2S02 As the current flows, copper from anodes dissolves while
pure copper is deposited on the cathodes.
Cathode c:==;::=======:;::::======::;=======::::!--
Anode +
Impure
copper
Copper
Fig. 14.11
Fig. 14.12
(b) Ferrous oxide combines with silica to form slag which
is drained out at intervals by tilting the vessel. In about three CUS04 ~ Cu 2+ + sol-
~~
hours time, all the iron is removed as ferrous silicate.
FeO + Si02 ~ FeSi03 Cathode
Anode
2
(Slag)
Cu + + 2e ---+ Cu Cu + SO~- ---t CuS04 + 2e
(C) The blast of air is continued for almost another two The more electropositive impurities like Fe, Zn, Ni,
hours. Excess of silica is absorbed by basic lining of the con- Co, etc., dissolve in the solution and less electropositive
impurities such as Ag, Au and Pt collect below the anode in the 2Cu2S + 502 ~ 2CuS04 + 2CuO
form of anodic mUd. Electrolytic copper has a purity of 99.96- CUS04 + Fe ~ Cu + FeS04
99.99%. (ppt.)
Wet process or Hydrometallurgical process: The 2. Extraction of copper from non~sulphide ores: The
essential principle of this process consists in the conversion of oxide and carbonate ores are crushed and concentrated by
copper present in the ore into soluble copper compound and gravity process. The concentrated ores are calcined in
precipitation of copper by addition of iron or by electrolytic reverberatory furnace. The carbonate decomposes to form the
process. oxide and the impurities either volatilise or are oxidised.
Big heaps of copper sulphide ores are exposed to air and
CuC03·Cu(OHh ~ 2CuO + C~ +H20
rain. Water is also sprayed at times, if necessary. After a year's
The oxide so formed is either reduced with carbon in
time, the copper sulphide is slowly oxidised to copper sulphate.
reverberatory furnace or leached with dilute H2S04,
The liquor which flows from the bottom of the heaps is run
into pans. Copper is precipitated from the liquor by the CuO + C ~ Cu + CO
addition of scrap iron. The precipitate is dried, melted and CU20 + C ~ 2Cu + CO
~-~'!:!!!'~~--<~-~--...~--<~~~- ...... - ..---------~~---------~-----~.-- --- _---OL__ --CUO±~S04-~ __ LCUS04-±..H2D_~ _________
-~-.--
.-.=~,-,-=~-~~--.--- ---,-, -~FL.QW~SHEE-Tc-F-OR-4HE~E-Xl'oRAGrION-~c.COP--PER.-'-=--===- =~~,=_c_._==~~
Copper pyrites
(CuFeS2r
J,
Crushed and sieved
J,<--
Concentration by froth floatation
Powdered ore + water + pine oil + air ~ sulphide ore in the froth
J,
Roasting in reverberatory furnace in presence of air
S +02~S02
4As + 302 ~ 2As203
2CuFeS2 + O2 ~ Cu2S + 2FeS + S02
-1
Silica + coke ~ Roasled ore
Smelting in blast furnace in presence of air

2FeS + 30 2 ~ 2FeO + 2S02
FeO + Si02 ~ FeSi0 3 (Slag)
J,
Silica) Matte (CU2S, FeS)
Bessemerisation in bessemer converter in presence of air

2FeS + 302 ~ 2FeO + 2S0 2
FeO + Si02 ~ FeSi03 (Slag)
2CU2S + 302 ~ 2CU20 + 2S02
Auto C
2CU20 + CU2S reduction) 6 u + S02
J,
Blister copper (98% Cu + 2% impurities)
Electrolytic refining
Anode-Impure copper plates
Cathode-Pure copper plates
Electrolyte-CuS04 soIn. + H 2S04
Pure copper deposited at cathode
.!-.
Pure copper
(99.6-99.9%)
Copper sulpQate solution obtained is then electrolysed using H2S04 ~ H20 + S02 + 0
copper sheet as cathode ~d lead plate as anode. Copper can Cu + 0 + H2S04 ~ CUS04 + H 20
also be recovered by using scrap iron.
CUS04 + Fe ~ Cu + FeS04
Dilute HN03 : NO is evolved on heating.
• Properties 2HN03 ~ H20 + 2NO + 3[0]
Physical: (a) It is a reddish coloured lustrous metal.
(b) It is highly malleable and ductile.
(c) It has specific gravity 8.9. 3Cu + 8HN03 ~ 3Cu(N03h + 2NO + 4H20
(d) It has high melting and boiling points (m.pt. 1083°C, Conca HN0 3 : N02 is evolved on heating.
b.pt. 2580°C). 2HN03 ~ H20 + 2N02 + -0
(e) It is good conductor of heat and electricity (next to
silver).
(f) Its atomic radii is l.17A and ionisation potential is Cu + 4HN0 3 ~ Cu(N03h ~ 2N02 + 2H20
···T:.rceV:~-~~~--~-~---~.-~.-~---~ .~~~~~ Copper metal reacts with hydrobromic acid (RBr) and
(g) Molt~ncopperabsorbssulphur_dioX1de~whlchlLglves~_ ~hydrotodi:c-acio~fotiIlifig~ com:plexes~'
out on cooling.
. al
ChernIe: Copper IS
. : t . . ' all
cuemIc y Iess reactIve. as 1't has 2Cu + 2HBr ~ 2CuBr + H2
high heat of sublimation and high ionisation potential. 2CuBr + 2HBr ~ H2[Cu2Br4]
(a) Action of air and oxygen: Copper is not affected by Copper plates are slowly attacked by acetic acid (vinegar)
dry air at ordinary temperatl1res but when exposed to air and in presence of air to form basic copper acetate (verdigris):
moisrure, it is covered by a green thin film which was formerly
supposed to be the basic carbonate but consists of bronchantite, Basic copper acetate (Verdigris)
CuS04·3Cu(OHh or atacamite, CuCI2·3Cu(OHh due to
(d) Action of ammonia: Copper is dissolved by aqueous
presence of S02 and HCI in the atmosphere.
ammonia in the presence of air or oxygen with the formation
8Cu + 6H20 + 2S02 + 502 ~ 2[CuS04·3Cu(OH)z] of a complex.
2Cu + H20 + CO2 + 02 ~ CuC03·Cu(OH)z 2Cu + 8NH3 + 2H 20 + ~ ~ 2[Cu(NH 3)4](OHh
Basic carbonate
However, when ammonia gas is passed over red hot copper,
The layer protects the rest of the metal from further action. the nitrogen is absorbed by the metal leaving hydrogen free.
When heated in oxygen,. it first forms red cuprous oxide (e) Action of halogens: Copper combines with halogens
(CU20) which changes into black cupric oxide (CuO). IT the directly.
temperarure is raised above ll00"C, cupric oxide changes back
to cuprous oxide. Cu + Cl2 Heat) CuClz
4Cu + ~ ~ 2CU20 (red) Cu + Br2 Heat) CUBr2

2CU20 + O2 ~ 4CuO (black)
Cu + 12 Heat) CUI2
2CuO ..::..::..;:..:....:~ CU20 + 2I O2 Moist chlorine rapidly attacks copper even at ordinary
(b) Action of water: Water at ordinary temperarure has temperatures.
no action on copper. However, when steam is passed over red (f) As a reducing agent: Copper reduces oxides of
hot copper, hydrogen is evolved. nitrogen to elementary nitrogen and ferric ion to ferrous ion.
Cu + H20 Red heat) CuO + H2 2Cu + 2NO ~ 2CuO + N2
2Fe3+ + Cu ~ 2Fe2+ + Cu2+
(c) Action of acids: Non-oxidising acids (HCI and dil.
H 2S04) do not have any effect on copper. However, they The etching of designs on copper plates using ferric chloride
dissolve the metal in presence of air. is based on this property.
2Cu + 4HCI (dil. or conc.) + O 2 ~ 2CuCl2 + 2H20 2FeCl3 + Cu ~ CuCl2 + 2FeClz
2Cu + 2H2S04 (dil.) + 02 ~ 2CUS04 + 2H20 (g) Displacement reactions: Copper displaces Ag, Au
and platinum metals from their salt solutions.
Copper is readily affected by oxidising acids (conc. H 2S04,
dilute and conc. HN03.) 2AgN03 + Cu ~ 2Ag + Cu(N03h
Conca H 2S04 : S02 is evolved on heating. 3Cu + 2AuCl3 ~ 3CuCl2 + 2Au
Transition Elements or d-block Elements and i-block Elements 683
• Uses (iii) 2CUS04 + 2NaI + S02 + 2H20----7

2CuI + Na2S04 + 2H2S04
Copper is most useful metal (only next to iron) on account Cuprous iodide
of its properties as it is stable in air and water and good (iv) 2CUS04 + 2NaCN + S02 + 2H20 ----7
conductor of heat and electricity. 2CuCN + Na2S04 + 2H2S04
It is used, Cuprous cyanide
(i) in the manufacmre of electrical wires, cables, etc. (V) 2CUS04 + 2NaCNS + S02 + 2H20----7
(li) for making vacuum pans, heating utensils, calorimeters, 2CuCNS + Na2S04 + 2H2S04
Cuprous thiocyanate
etc.
(iii) for electroplating and electrotyping.
The reactions (iii) and (iv) can take place even in absence
(iv) for making coins, ornaments and jewellery. of sulphur dioxide.
(v) for making various compounds which are used as 2CUS04 + 4NaI ----7 2CuI + 2Na2S04 + 12
insecticides, pesticides and pigments. 2CUS04 + 4NaCN ----7 2CuCN + 2Na2S04 + (CNh
(vi) for making a large number of alloys. The important The true molecular formula of cuprous compounds is
alloys are listed below : still doubtful. There are experimental evidences for dimeric
~IDolecule;----~------ -------------------
The most important compound of this classiscuprous cc
(a) Brass Cu 60-80%, Domestic utensils, chloride.

Zn 40-20% condensers, cartridges
cases, etc. Cuprous Chloride, CU2CI2
(b) Bronze Cu 75-90%, Coins, statues, utensils,
Sn 25-10% machine parts, bells,_ etc.
Cu 56%, Zn 24%, Utensils, ornaments,
• Preparation
(c) Gennan
silver Ni 20% resistance coils. It is prepared-
(d) Gun metal Cu 87%, Sn 10%, Machine parts, guns. (i) by heating excess of copper with concentrated hydro-
Zn 3%
chloric acid in presence of a little potassium chlorate.
(e) Rolled gold Cu 95%, Al5% Artificial jewellery.
(t) Constantan Cu 60%, Ni 40% Electrical resistances. Cu + 2HCI + 0 ----7 CuCl2 + H20
(g) Monel metal Cu 30%, Ni 67%, Chemical plants, CuCl2 + Cu ----7 CU2Cl2
Fe 3% automobile engine parts. (ii) by boiling copper SUlphate solution with excess of copper
(h) Phosphorus Cu 85%, Sn 13%, Gears, aerials,
mrnings in presence of hydrochloric acid.
bronze P2% propellers, etc.
CUS04 + 2HCI----7 CuCl2 + H2S04
14~1lt~ COMPOUNDS OF COPPER
c~-;*~
CuCl2 + Cu ----7 CU2Cl2
(iii) by heating cupric chloride with zinc or sulphur dioxide.
~ Copper Forms two Series of Compounds 2CuCl2 +Zn ----7 CU2Cl2 + ZnCl2
1. Cuprous compounds: In which copper is monovalent. 2CuCl2 + 2H20 + S02 ----7 CU2Cl2 + 2HCI + H2S04
Most of the cuprous compounds are colourless and diamagnetic (iv) by passing S02 through the solution containing copper
as 3d-shell is completely fIlled. CU20 and CU2S are red and sulphate and sodium chloride.
black:, respectively, which are exceptions. Cuprous compounds 2CUS04 + 2NaCI + 2H20 + S02 ----7 CU2Cl2 + Na2S04
are generally insoluble in water. The soluble compounds are + 2H2S04
unstable in aqueous solutions, since they disproportionate to
Cu2+ and Cu. • Properties
2Cu+ ----7 Cu2+ + Cu
(i) It is a white solid. It is insoluble in water but soluble in
Cuprous compounds can be obtained by passing sulphur excess of hydrochloric acid.
dioxide through a solution containing copper sulphate and
CU2Cl2 + 4HCI ----7 2H2CUCl3
sodium salt. Some examples are given below :
or CU2Cl2 + 6HCI ----7 2H3CuCl4
(i) 2CUS04 + 2NaCI + S02 +2H 20 ----7
2CuCI + Na2S04 + 2H2S04 The solution again gives a white precipitate on dilution.
Cuprous chloride (li) It gradually mrns green on exposure in air due to
(li) 2CUS04 + 2NaBr + S02 + 2H20----7 oxidation.
2CuBr + Na2S04 + 2H2S04 2CU2Ch + 2H20 + O2 ----7 2[CuCh·Cu(OHhl
Cuprous bromide
Basic cupric chloride
(iii) The solution of cuprous chloride in HCI is oxidised by formation of blue hydrated ion, [Cu(H20)4]2+ or [Cu(H20)6]2+.
air or oxidising agents into cupric chloride. 2
Compounds of Cu + ions are paramagnetic due to presence of
1
CU2Cl2 + 2HCI + 2: O2 ~ 2CuCl2 + H 20 one unpaired electron in 3d energy shell, i.e., configuration of
2 9
(iv) The solution of cuprous chloride in HCI absorbs carbon Cu + is 3d . Some important cupric compounds are described
monoxide and forms an addition compound. here.
CU2Cl2 + 2CO ~ 2CuCI·CO Cupric Oxide, CuO
The addition compound decomposes on heating evolving
It is called black oxide of copper and is found in nature as
carbon monoxide. The reaction is utilised for the removal of
tenorite.
carbon monoxide.
(v) It dissolves in aqueous ammonia forming a colourless
• Preparation
solution due to the formation of the complex Cu(NH3hCI.
(vi) The ammonical cuprous chloride solution absorbs It is prepared-
acetylene to form bright red precipitate of cuprous acetylide, (i) by heating CU20 in air or by heating copper for a long
.CU2-C2.------ _____n____________ ______ . _ _ _ _ _ _n_ tiI@.iI!.lli!(the_tempe!"atu1"e...§hollkLnot~~~eed abo,,~lLOO."g_.__ ._
2Cu(NH3hCI + C2H2 ~ CU2C2 + 2NH3 + 2NH4C l c : :u2Q ±~Q2=-----?4C::llO __
Acetylene can be regenerated by treating the acetylide with 2Cu + O ~ 2CuO
2
strong HCI. The reaction is, therefore, used for the purification
(ii) by heating cupric hydroxide,
and separation of acetylene.
Cu(OHh ~ CuO + H20
CU2C2 + 2HCI ~ C2H2 + CU2Cl2
(iii) by heating copper nitrate,
(vii) Cuprous chloride with caustic alkalies gives a yellow
precipitate of cuprous oxide which gradually changes to red. 2Cu(N0 3h ~ 2CuO + 4N0 2 + O2
Cu2Cl2 + 2NaOH ~ CU20 + 2NaCI + H20 (iv) on a commercial scale, it is obtained by heating malachite
Yellow changing which is found in nature.
to red
CuC0 3·Cu(OHh ~ 2CuO + C02 + H 20
(viii) With H 2S, cuprous chloride forms a black precipitate
of cuprous sulphide. II Properties
CU2Cl2 + H2S ~ CU2S + 2HCI
(a) It is black powder and stable to moderate heating.
(ix) With sodium chloride or potassium chloride solution (b) The oxide is insoluble in water but dissolves in acids
cuprous chloride forms a soluble complex. forming corresponding salts.
CU2Cl2 + 6NaCI ~ 2Na3CuCl4 CuO + 2HCI ~ CuCl2 + H20
CU2Cl2 + 6KCI ~ 2K3CuCl4 CuO + H 2S04 ~ CUS04 + H20
(x) Dry cuprous chloride forms addition compounds with CuO + 2HN0 3 ~ Cu(N0 3h + H 20
ammonia gas of the formula CuCI·nNH3 where n = 1, 1 ~, 3. (c) When heated to 1100-1200°C, it is converted into cuprous
CU2Cl2 + 2NH3 ~ 2CuCI·NH3 oxide with evolution of oxygen.
4CuO ~ 2CU20 + O2
• Uses (d) It is reduced to metallic copper by reducing agents like
(i) Ammonical solution of cuprous chloride is used for hydrogen, carbon and carbon monoxide.
absorbing acetylene. CuO + H2 ~ Cu + H20
(ii) HCI solution of cuprous chloride is used for absorption CuO + C~Cu + CO
of carbon monoxide.
CuO + CO~ Cu + CO2
(iii) It is also used for absorption of ammonia gas.
(iv) It is used as a catalyst in Deacon's process for the
manufacture of chlorine gas.
• Uses
2. Cupric compounds: In which copper is divalent, cupric It is used to impart green to blue colour to glazes and glass.
compounds are more stable, more common and generally more It is used in organic analysis for the estimation and detection
stable. Most of the anhydrous cupric compounds are colourless of carbon. It is also used in petroleum for the removal of
while the hydrated compounds are generally blue due to the sulphur.
- - -
• Uses
It is used as a catalyst in Deacon's process. It is also used
• Preparation in medicines and as an oxygen carrier in the preparation of
(i) The metal or cupric oxide or cupric hydroxide or copper organic dyestuffs.
carbonate is dissolved in conc. HCl. The resulting solution on
crystallisation gives green crystals of hydrated cupric chloride.
Copper Sulphate (Blue Vitriol), CuS04·5H20
2Cu + 4HCI + O2 ~ 2CuCl2 + 2H20 Copper sulphate is the mo.st CQmmQn cQmpo.und o.f co.pper.
It is called as blue vitriol or nila tkotka.
CuO + 2HCl ~ CuCl2 + H20
Cu(OHhCuC03 + 4HCI ~ 2CuCl2 + 3H20 + CO2 • Preparation
(ii) Anhydrous cupric chloride is obtained as a dark brown
(i) Copper sulphate is prepared in the labo.ratory by disSQlving
mass when copper metal is heated in excess of chlorine gas or
cupric oxide Qr hydrQxide Qr carbonate in dilute sulphuric acid.
by heating hydrated cupric chloride in HCI gas at 150°C.
The solution is evapQrated and crystallised.
Cu + Cl2 ~ CUCl2
CuO + H2S04 ~ CUS04 + H20
150"C )
. _CuCh·2H2Q---Hergas····· . CnC12_+_2H2-0 ___ _ _~.Cu(OHh_+.~S04_ . _LCuS04_±-2H20 ....
Cu(QHhCuCQ3+ 2H2SQ4 ~.2CUS()4 + 3I:h(). + C.P2·
• Properties (ii) On a cQmmercial scale, it is prepared frQm scrap cQPper.
(i) It is a deliquescent compound and is readily sQluble in The scrap CQPper is placed in a perfQrated lead bucket which
water. The dilute sQlutiQn is blue but concentrated solution is, is dipped into. hQt dilute sulphuric acid. Air is blown through the
hQwever, green. It changes to. yellow when CQnc. HCI is added. acid. CQPper sulphate is crystallised from the sQlution.
The blue colour is due to. complex catio.n [Cu(H20)4f+ and
Cu + H 2S04 + ~02(air) ~ CUS04 + H20
yellQw colo.ur due to. complex anion [CuC4]2- and green when
both are present. • Properties
(ii) The aqueous solutiQn is acidic due to. its hydrolysis.
(a) It is a blue crystalline co.mpound and is fairly so.luble in
CuCl2 + 2H20 ;;:=::: Cu(OHh + 2HCI
water.
(iii) The anhydrous salt on heating forms CU2Cl2 and Ch (b) Heating effect: CuS04·5H20 crystals effloresce on
2CuCl2 ~ CU2Cl2 + Cl2 exposure and converted into a pale blue powder, CuS04·3H20.
while the hydrated salt on stro.ng heating gives CuO, CU2CI2, When heated to. 100°C, bluish white monQhydrate CUS04·H20
HCI and C12. is formed. The mQnohydrate loses last mo.lecule Qf water at
230°C giving the .anhydro.us salt, CUS04, which is white.
3CuC12·2H20 ~ CuO + CU2Cl2 + 2HCI + Cl2 + 5H20
Exposure
(iv) It is readily reduced to CU2Cl2 by co.pper turnings, or CuS04·5H20 , ' CuS04·3H20 ~===== CUS04·H 20
S02 gas, or hydrogen (Nascent-obtained by the action of HCI Blue Pale blue Bluish white
on Zn) or SnCI2. CUS04
White
CUC12 + Cu ~ CU2Cl2
2CuCl2 + S02 + 2H20 ~ CU2Cl2 + 2HCI + H2S04 Anhydrous cQPper sulphate (white) regains its blue colo.ur
when moistened with a drQP of water (test of water).
2CuCl2 + ~H ~ CU2Cl2 + 2HCI
If the anhydrQus salt is heated at nooc,
it decomposes into.
2CuCl2 + SnCl2 ~ CU2Cl2 + SnCl4 cupric Qxide and sulphur triQxide.
(v) A pale blue precipitate Qf basic cupric chloride, CUS04 720°C) CuO + S03
CuCI2·3Cu(OHh is o.btained when NaOH is added. J,
CUCl2 + 2NaOH ~ Cu(OHh + 2NaCI S02 + l02
CuCl2 + 3Cu(OHh ~ CuCI2·3Cu(OHh (c) Action of NHtOH: With ammQnia sQlutiQn, it forms
It dissolves in ammonium hydro.xide fQrming a deep blue the so.luble blue co.mplex. First it forms a precipitate o.f Cu(OHh
so.lution. On evaporating of this solutio.n deep blue crystals of which dissolves in excess o.f ammo.nia so.lutio.n.
tetrammine cupric chloride are obtained. CUS04 + 2NH40H ~ Cu(OHh + (NH4hS04
CuCh + 4NH40H ~ CU(NH3)4CI2·H20 + 3H20 Cu(OHh + 2NH40H +(NH4hS04 ---t CU(NH3)4S04 + 4H20
Tetrammine cupric
sulphate
The complex is known as Schwitzer's reagent which is 2CUS04 + ~Fe(CN)6 ~ CU2Fe(CN)6 + 2K2S04
used for dissolving cellulose in the manufacture of artificial (h) Addition of electropositive metals: Electropositive
silk. elements like zinc and iron precipitate copper from a solution
(d) Action of alkalies: Alkalies form a pale blue precipitate
of copper sulphate.
of copper hydroxide.
CUS04 + Fe ~ Cu + FeS04
CUS04 + 2NaOH ~ Cu(OHh + Na2S04
CUS04 + Zn ~ Cu + ZnS04
(e) Action of potassium iodide: First cupric iodide is
formed which decomposes to give white cuprous iodide and (i) Action of H 2S: When H 2S is passed through copper
iodine. sulphate solution, a black precipitate of copper sulphide is
formed.
[CUS04 + 2KI ~ CU12 + K 2S04] x 2
CUS04 + H 2S ~ CuS + H 2S04
2CuI2 ~ CU212 + 12
The black precipitate dissolves in conc. HN0 3.
2CUS04 + 4KI ~ CU212 + 2K2S04 + 12
3CuS + 8HN0 3 ~ 3Cu(N0 3h + 2NO + 3S + 4H20
(f) Action of potassium cyanide: First cupric cyanide (j) Action of potassium sulphocyanide: Cupric sulpho-
... _ _ js__ fonned_which_dec_omposeLto__ giy.e___c_uPI"QUS___c.y.anide~_and cyanide-is-fonnect----- - - - - -- --- --~--- --
cyanogen gas. Cuprous cyanide. dissolves in excess of
potassiiiin cyanide to form acomplex; potassium cupro cyarude CuSO~ + 2KCNS ~ Cu(CNSh +K-2,S04
[K3CU(CN)4]· If S02 is passed through the solution, a white precipitate of
[CUS04 + 2KCN ~ Cu(CNh + K 2S04] x 2 cuprous sulphocyanide is formed.
2Cu(CNh ~ CU2(CN)2 + (CNh 2CUS04 + 2KCNS + S02 + 2H20 ~ CU2(CNSh + K2S04

CU2(CNh + 6KCN ~ 2K3Cu(CN)4 + 2H2S0 4
[This is the general method for obtaining cuprous compounds.]
2CUS04 + lOKCN ~ 2K3Cu(CN)4 + 2K2S04 + (CNh (k) Double sulphates: Copper sulphate forms double
(g) Action of potassium ferrocyanide: Reddish brown salts with alkali sulphate K2S04·CUS04·6H20 and with
precipitate of cupric ferrocyanide is formed. (test of Cu 2+ ion) ammonium sulphate as (NH4hS04·CUS04·6H20.
Cu
Cu 2CI 2 ~ HCI
Cuprous
chloride
PROPERTIES OF COPPER SULPHATE AND PREPARATION OF VARIOUS COPPER COMPOUNDS

(1) Action of sodium tbiosnlphate: Sodium thiosulphate by-product but no workable deposits of silver are found in
reacts with copper sulphate to form cupric thiosulphate which India.
is reduced by sodium thiosulphate. The cuprous compound The ores of silver are usually associated with large amounts
thus formed dissolves in excess of sodium thiosulphate to of rock, silica and clay. The silver content hardly exceeds 1.0
form a complex. per cent. Most of the silver (nearly four-fifth of the total
CUS04 + Na2S203 ~ CUS203 + Na2S04 production) is obtained from argentiferous lead and from the
anodic mud formed during electrolytic refming of copper. Thus,
2CuS 20 3 + Na2S203 ~ Cu2S20 3 + Na2S406
silver is obtained from the following sources.
3CU2S20 3 + 2Na2S203 ~ Na4[CU6(S203h] (i) From the ores of silver
Sodium cuprothiosulphate
(n) From native silver
(iii) From argentiferous lead
• Uses (iv) From the anodic mud in copper refining.
(i) Copper sulphate is used for the preparation of other
copper compounds. I'i! 1. Extraction of silver from argentite ore
(n) It finds use in electroplating, electrotyping, calicoprinting (Cyanide process)
and dyeing. Cyanide process is the: ll1QQe:!!Lm:Qc~~dort:lli:_e~tra~tioRQL~_.-
. -Oii}-It--is..used -in-agFiealrure-as-afungieide--and--gemricide.- - ·slfver.-The-process--is- atso called as Mac-Arthur and F()resL~
.. i)ordeaux mi!ttIre(:on..§istingc;QPper l'lllphat~and limejs process.~lt-is-based -Orttwopoints.
used to kill moulds and fungi on vines, trees, potatoes, etc. (i) Silver compounds (or even free silver) dissolve in
(iv) It is used as a laboratory reagent especially in the sodium cyanide solution forming a complex salt, NaAg(CNh,
preparation of Fehling's sol,ution. in presence of air.
(v) It fmds use as an antiseptic in medicine. (n) Silver is precipitated from this complex salt by the
(vi) It is extensively used in electric batteries. addition of zinc.
14:11 SILVER The process involves the following steps:

(i) Concentration of the ore : Concentration of the ore
Occurrence: Silver is a rare element as it forms only 10-8 is done by froth floatation process. The ore is crushed and
per cent of the earth's crust. However, it was known in taken in a tank fllied with water to which pine oil and potassium
prehistoric times and used for its colour and beauty as a precious xanthate have been added. The whole mixture is agitated by
metal. Silver is found in nature in two forms. passing a strong stream of air. The ore particles come to the
surface alongwith froth while silicious impurities settle to the
II! 1. Native State bottom.
(ii) Cyanidation: The concentrated ore is ground to a
It occurs in the metallic condition usually associated with
copper, gold and platinum metals. Native silver has been reported very fine powder in ball mill. The fmely powdered ore is
in a few places in Canada, United States of America, Mexico treated with dilute solution (0.4 to 0.6%) of sodium cyanide
and Peru. and a current of air is blown through the whole mass. The
silver present in the ore dissolves in the solution slowly to form
II 2. Combined State sodium argentocyanide.
The important ores of silver are: Ag 2S + 4NaCN < \ 2NaAg(CNh + Na2S

(a) In the form of snlpbide: . The above reaction is reversible. The air which is blown in
(i) Argentite or silver glance, Ag2S serves an important function in removing sodium sulphide
(n) Pyrargyrite or Ruby silver, 3Ag2S·Sb2S3 from the equilibrium mixture and causing the reaction to
(iii) Stromeyerite or silver copper glance, (Cu, Ag)zS proceed in the desired direction.
(iv) Silver is also associated in the form of Ag2S in the lead 4Na2S + 502 + 2H20 ~ 2Na2S04 + 4NaOH + 2S
ore, galena (PbS). The lead extracted usually contains silver
The soluble sodium argentocyanide is removed by filtration.
and called argentiferous lead. Silver is recovered before lead is
[Metallic silver and silver chloride (Horn silver) also dissolve
put into use.
in sodium cyanide solution.
(b) In the form of halide:
Chlorargyrite or Horn silver, AgCl. 4Ag + 8NaCN + 2H20 + 02 (air)~ 4NaAg(CNh + 4NaOH
In India, it occurs mainly as Ag2S associated with lead and AgCI + 2NaCN ~ NaAg(CNh + NaCl]
zinc ores at Bawdivin and also associated with gold, in the (iii) Recovery of silver: Silver is precipitated from the
native gold ores of Kolar. From these, silver is obtained as a solution by addition of zinc powder in a fmely divided condition.
Silver is precipitated as a dark amorphous mass while zinc Some mercury is then added to the product. Silver chloride
goes into the complex. reacts with mercury liberating silver.
2NaAg(CNh + Zn ----t Na2Zn(CN)4 + 2Ag 2AgCI + 2Hg ----t 2Ag + Hg2Cl2
Sodium zinco-
cyanide
[Zinc is more electropositive than silver.] FLOW SHEET FOR THE EXTRACTION OF SILVER
The precipitated silver is removed by filtration, dried and Silver ore
fused with potassium nitrate in a crucible in furnace. The (Argentite)
impurities are oxidised and rise as a scum on the surface. 1
Liquid silver on cooling appears as compact mass. CONCENTRATION BY FROTH FLOATATION PROCESS
Powdered ore + Water + Pine oil + Air ----t
Waste gases Froth carrying SUlphide particles
1
CYANIDATION
Concentrated ore + NaCN solution (0.4-0.6%) + Air
Ag 2S + 4NaCN ~ 2NaAg(CNh + Na2S
---- 4Na:t&T·Se2·+-~H#--+-2Na~02t+4NaQH-+-2S
PRECIPITATION OF SILVER WITH ZINC

2NaAg(CNh + Zn ----t 2Ag + Na2Zn(CN)4
Black ppt.
BlackpptofAg-+KN0 3 Fuse) Compact mass

(Silver metal)
Fig. 14.13
(iv) RefIning: The main impurities are of lead, copper . ELECTROLYTIC REFINING
and gold. These are removed by following methods. Anode : Impure silver
(a) Cupellation process: Cupel is a big oval dish with a Cathode : Pure silver plate
shallow hearth and is made of bone-ash or porous cement. The Electrolyte : AgN03 solution + HN0 3
impure silver is fused on the hearth of the cupellation furnace Pure silver deposited on the cathode
and a strong current of air is blown over it. The silver dissolves in excess of mercury to form an
Lead is oxidised to lead oxide (Litharge: PbO) which is amalgam. It is washed and then distilled when silver is left
blown away by air. Other impurities are also oxidised and rise behind in the retorts.
to the surface and removed as scum. The oxides may also be
absorbed by the lining of the cupel. The completion of the 3. Extraction of silver from argentiferous lead
process is indicated by the appearance of bright shining surface
(Desilverisation of lead)
of the molten silver.
(b) Electrolytic process: The impure silver is made as Lead ores, especially galena, contain a very small percentage
anode and pure silver plate as cathode. The electrolytic solution of silver sulphide. During the extraction of lead, silver remains
is of silver nitrate containing 10% nitric acid. On passing in the metal. On account of its high value, silver is removed
electric current silver ions start depositing on cathode and from the lead before it is used for any purpose. The crude lead
equivalent amount from anode comes into solution. In this way contains upto 2% of silver. This poor amount of silver requires
silver is transferred from anode to cathode. Copper goes into to be concentrated before desilverisation. The recovery of
solution as copper iritrate while gold collects below the anode silver from crude lead (argentiferous lead), thus involves two
as anodic mud. steps:
(i) Partial separation of lead (a) by Pattinson's process or
2. Amalgamation process (b) by Parkes process.
This is the old method of extraction. It is still in use in some (n) Removal of lead as lead oxide by cupellation process.
countries. The sulphide ore is crushed and converted into a (a) Pattinson's process: This process is based on the
slime with a solution of cupric chloride. fact that silver-lead system has an eutectic mixture with 2.6%
Ag2S + CuCl2 ----t 2AgCI + CuS silver melting at 303°C whereas pure lead melts at 327°C.
When the molten argentiferous lead is allowed to cool slowly, the solution in the form of nitrates. The excess of nitric acid
crystals of pure lead are deposited until the silver content of the is boiled and the solution is treated with dil. HCI when a white
mixture has risen to 2.6%. The crystals of pure lead are precipitate of silver chloride is obtained. This is separated and
removed with the help of perforated ladles. The alloy rich in converted into silver by any of the following methods.
silver content is then subjected to cupellation to remove the (a) Silver chloride is fused with sodium carbonate in a
remaining lead. crucible.
(b) Parkes process: This is at present the most commonly 1
2AgCI + Na2C03 Fuse) 2Ag + 2NaCI + CO2 + - O2
used method. It depends on the following points : 2
(i) Zinc and lead are not miscible. (b) The precipitate of AgCI is reduced with nascent hydrogen
(li) Silver is more miscible with zinc than lead.
produced by the action of zinc and dilute H2S04.
(iii) Zinc-silver alloy is lighter than molten lead and have a Zn + H2S04 ~ ZnS04 + 2H
higher melting point. AgCl + H ~ Ag + HCI
Lead containing silver is melted in large pots. Zinc dust to (c) AgCI is dissolved in potassium cyanide solution when a
the extent of only I % is added and thoroughly stirred. The complex salt, potassium argento-cyanide is formed.
temperature is raised above the melting point of zinc. Zinc
AgCl-+.2:KCN~-KAg(CNh+KCl-·
-dIsSolves·sirver·aiid·comesup·on thesurfa.cewheie Zlnc=slIver Ag is obtained from the solution by addition of zinc.
alloy· forms a crust. 'Fhis is skimllled off by perforated ladles; -
More zinc is added and the operation is repeated for several 2KAg(CNh + Zn ~ K 1Zn(CN)4 + 2Ag
times till lead shows almost no trace of dissolved silver. It is Soluble
possible to reduce the silver content to 0.0005%. (d) By boiling silver chloride with caustic soda and glucose.
The zinc-silver alloy containing some lead is now distilled 2AgCl +2NaOH ~ Ag20 + .2NaCl + H 20
with a little charcoal when zinc distills over. The recovered
Ag20 + C6H 120 6 ~ 2Ag + C 6H 120 7
zinc is used again. The lead silver alloy left behind is now put
Glucose Gluconic acid
to cupellation as to remove lead. The pure silver is, thus,
obtained. The silver thus obtained, is purified by fusion with borax
and nitre followed by electrolytic purification.
~ 4. Recovery of silver from anodic mud of Separation of silver from gold: The separation of silver
copper refining and gold is technically known as parting. This is done by
following methods:
The mud is treated with nitric acid and the solution is filtered. (a) Parting with sulphuric acid: The alloy having gold,
The filtrate contains nitrates of silver and lead. To the filtrate less than 20%, is treated with boiling concentrated sulphuric
HCI is then added when silver and lead settle down as chlorides acid. Silver dissolves as silver sulphate and gold remains as
in the form of white precipitate. The chlorides are separated, spongy mass. The solution is diluted with water and the solution
dried and fused with sodium carbonate in a crucible when an is filtered. The filtrate is then treated with scrap iron or copper
alloy of Ag and Pb is obtained. To remove lead, the alloy is put or zinc to separate silver.
to cupellation.
Ag2S04 + Zn ~ 2Ag + ZnS04
Anodic mud + RN0 3 ~ Nitrates of Ag and Pb If the percentage of gold in the alloy is more than 20%,
(Filtrate)
some silver is added to alloy as to reduce the percentage of
1 +HCI gold less than 20% and then the process of parting is applied.
(b) Parting with 'Moebius' electrolytic process: The
Ag Cupellation) Ag-Pb ( Fused AgCl·PbCI 2
with Na2C03 alloy of silver and gold is made the anode while pure silver plate
Alloy
as cathode. The electrolytic solution consists of a dilute solution
Pb(N03h + 2HCl ~ PbCl2 + 2RN0 3 of silver nitrate acidified with nitric acid. On passing electric
AgN0 3 + HCI ~ AgCI + RN0 3 current silver dissolves from the anode and deposits on the
1 cathode. Gold remains undissolved and deposits as a slime in
PbCl2 + Na2C03 ~ Pb + 2NaCI + CO2 + 2 O2
canvas bags surrounding the anode.
1
2AgCI + Na2C03 ~ 2Ag + 2NaCI + CO2 + 202 AgN03
5. Silver from coins or ornaments

1l
Ag + + e ~ Ag cathode f - - Ag + + N0 3 ~ Ag anode
Coins and ornaments are alloys of silver and copper. The N0 3- + Ag~ AgN0 3 + (-
alloy is treated with nitric acid. Both copper and silver go into
• Properties Silver ornaments and utensils usually contain 80% silver and
Physical: (a) It is a lustrous white metal. It melts at 20% copper. A silver coin has generally the composition Ag
961°C and boils at 21800C. Its specific gravity is 10.5. (b) It 50%, Cu 40%, Zn 5% and Ni 5%.
is very good conductor of heat and electricity (better than even
copper). (c) On heating, the molten mass absorbs oxygen
which is again released on cooling. This property is called
spitting of silver. (d) It is hard, malleable and ductile.
Chemical: (a) Action of atmosphere: Silver remains
untarnished in air free from hydrogen sulphide. Air contaminated
with hydrogen sulphide covers it with an adherent film of
black silver sulphide.
2Ag + H2S ~ Ag 2S + H2
(b) Action of oxygen and water: Silver is not affected
by oxygen and water.
Potassium argentocyanide
(c) Action of halogens: Silver combines slowly with solution
. freehalogens~even.aLroomtemperatuI:e~ Ihe.reactionis..rapid ..
at red heat. Fig. 14.14
.
2Ag + X2 ~ 2AgX (X2 =Clz, Br2 or 12)

(ii) Silver is used for plating articles of base-metals. The
(d) Action of acids: Silver is not affected by dilute and article to be plated is made the cathode while the anode consists
concentrated hydrochloric acid. It is also not acted upon by of pure silver. The electrolyte is the solution of potassium
dilute sulphuric acid. argentocyanide, As the complex ion is very stable, the concen-
In concentrated sulphuric acid, silver dissolves on heating tration of silver ion in solution is very small at any time.
with evolution of sulphur dioxide.
[Ag(CNhr ~ + 2CN-
H2S04 ~ H20 + S02 + 0
Silver is deposited slowly and uniformly when electricity is
2Ag + H2S04 + 0 ~ Ag2S04 + H20 passed through the solution.
2Ag + 2H2S04 ~ Ag 2S04 + S02 + 2H20 (iii) Silver amalgam is used in filling teeth and in silvering
mirrors.
Silver dissolves in both dilute and concentrated nitric acids. (iv) Silver leaves are used in Ayurvedic and Yunani
Dilute HN03 : medicines.
(v) It is used for making silver salts used in silvering of
mirrors, photography and medicine.
6Ag + 8HN0 3 ~ 6AgN03 + 2NO + 4H20
or 3Ag + 4HN03 ~ 3AgN03 + NO + 2H20 14.1i~ COMPOUNDS OF SILVER
'-"_,~-_..._\i~
Cone. HN03 : 2HN03 ~ H20 + 2N02 + 0

2Ag + 2HN0 3 + 0 ~ 2AgN03 + H20 Silver nitrate (Lunar caustic), AgNOa
2Ag + 4HN03 ~ 2AgN03 + 2N02 + 2H20 Silver nitrate is the most common and important salt of
silver.
or Ag + 2HN03 ~ AgN03 + N0 2 + H20
(e) Action of alkalies: Alkalies have no action on silver • Preparation
even when fused.
It is prepared by heating silver with dilute nitric acid. The
(0 Action of alkali cyanides: Silver dissolves in the
solution is concentrated and cooled when the crystals of silver
solution of alkali cyanides in the presence of oxygen forming
nitrate separate out.
the complex argentocyanide.
4Ag + 8KCN + 2H20 + O 2 ~ 4K[Ag(CN)z] + 4KOH 3Ag + 4HN03 3AgN03 + NO + 2H20
(Dilute)
4Ag + 8NaCN + 2H20 + O 2 ~ 4Na[Ag(CNh] + 4NaOH
• Properties
• Uses
(a) It is a colourless crystalline compound, soluble in water
(i) Silver is used in making coins, ornaments, silver-ware,
and alcohol. It melts at 212°C.
decoration pieces, etc. Pure silver is too soft to be used for (b) In contact with organic substances it blackens due. to
these purposes and is. therefore, alloyed generally with copper. decomposition into metallic silver. Thus, it leaves black stains
Transition Elements or d-block Elements and f-block Elements
when comes in contact with skin and clothes. It produces When heated at red heat, it further decomposes to metallic
burning sensation like caustic and leaves a white stain (.usually silver.
a black stain) like the moon luna on skin and thus, called Lunar 2AgN0 3 - - t 2Ag + 2N02 + 02
caustic. It is decomposed by light also and therefore stored in (d) Solutions of halides, phosphates, sulphides, chro-
coloured bottles. ' mates, thiocyanates, sulphates and thiosulphates, all give a
(c) On heating above its melting point, it decomposes to precipitate of the corresponding silver salt with silver nitrate
silver nitrite and oxygen. solution.
2AgN03 - - t 2AgN0 2 + O2
Chlorides --t white precipitate of AgCl,
AgN0 3 + NaCI - - t AgCl + NaN0 3
Bromides - - t pale yellow ppt. of AgBr,
AgN0 3 + NaBr - - t AgBr + NaN0 3
Iodides - - t yellow ppt. of AgI,
Phosphates --t_yellow.ppt. ofAg'3f'04,

3AgN03 + Na3P04 - - t Ag3P04 + 3NaN03
Silver nitrate -1---4 Sulphides - - t black ppt. of Ag2S,
(AgN0 3) 2AgN03 + Na2S - - t Ag2S + 2NaN03
Chromates - - t brick red ppt. of Ag2Cr04,
2AgN03 + K2Cr04 --t Ag 2Cr0 4 + 2KN0 3
Thiocyanates --t white ppt. of AgCNS,
AgN03 + NaCNS - - t AgCNS + NaN03
Sulphates --t white ppt. of Ag 2S04,
2AgN03 + Na2S04 - - t Ag2S04 + 2NaN03
Thiosulphate white ppt. of Ag 2S20 3 which gradually
changes to black due to hydrolysis.
2AgN03 + Na2S203 - - t Ag2S20 3 + 2NaN03
Ag2S20 3 + H 20 - - t Ag2S + H2S04
(Black)
On account of these reaqtions, silver nitrate is an excellent 2AgN03 + Na2S203 - - t Ag 2S 20 3 + 2NaN03

laboratory reagent for the identification of various acidic radicals. Ag2S 20 3 + 3Na2S203 - - t 2Na3[Ag(S203h]
(e) Solid AgN0 3 absorbs ammonia gas with the formation Sodium argentothiosulphate
of an addition compound, AgN03' 2NH3. (i) AgN0 3 reacts with iodine in two ways :
(f) When treated with a solution of NaOH, it forms precipitate (a) 6AgN03 (excess) + 312 + 3H20 - - t
of silver oxide. Originally, it has brown colour but turns black
AgI03 + 5AgI + 6HN03
when dried.
(b) 5AgN03 + 312 (excess) + 3H20 - - t
2AgN03 + 2NaOH - - t Ag 20 + 2NaN03 + H 20
Hl03 + 5AgI + 5HN03
(g) When KCN is added to silver nitrate, a white precipitate (j) Silver is readily displaced from an aqueous silver nitrate
of silver cyanide appears which dissolves in excess of KCN solution by the base metals, particularly, if the solution is
forming a complex salt, potassium argento cyanide. somewhat acidic,
AgN03 + KCN - - t AgCN + KN0 3 2AgN03 + Cu - - t 2Ag + Cu(N03h
AgCN + KCN - - t KAg(CN)z 2AgN03 + Zn - - t 2Ag + Zn(N03h
Potassium argentocyanide
(k) Phosphine, arsine and stibine all precipitate silver from
(h) When sodium thiosulphate is added to silver nitrate, a
silver nitrate solution.
white precipitate of silver thiosulphate appears. This precipitate,
however, dissolves in excess of sodium thiosulphate forming PH3 + 6AgN03 + 3H20 - - t 6Ag + 6HN03 + H3P03
a complex salt.
AsH3 + 6AgN03 + 3H20 ~ 6Ag + 6HN03 + H3As03 • Properties

(1) All halogen acids, except HF, precipitate silver halides (a) It is a pale yellow solid. It is insoluble in water and
from aqueous solution of AgN03. ~ concentrated acids. It is partially soluble in strong solution of
AgN0 3 + HX ~ AgX + HN03 ammonium hydroxide due to complex formation.
(m) When NH40H is added to silver nitrate solution, a AgBr + 2NH40H ~ Ag(NH3hBr + 2H 20
brown precipitate of silver oxide appears which dissolves in (b) On heating, it melts to a red liquid.
excess of ammonia forming a complex salt. (c) It is most sensitive to light. It undergoes photoreduction.
2AgN03 + 2NH40H ~ Ag 20 + 2NH4N03 + H20
2AgBr --"'--=' 2Ag + Br2
Ag20 + 2NH 4N0 3 + 2NH40H ~ 2[Ag(NH3h]N03 + 3H20
(d) It dissolves in potassium cyanide.
The ammonical solution of AgN03 gives the following
AgBr + 2KCN ~ KAg(CNh + KBr
reactions: Potassium argento-
(a) It reacts with acetylene to form white compound, silver cyanide (Soluble)
acetylide. (e) It dissolves in sodium thiosulphate.

2A~N<h_+2NH40H::I-_Cili2:::=±Ag~~::I-_2r-.lJI4i'J:03± 21hQ_ _ ~~~r:!~N'a2~2,()J_~ Na~~~(S~03)2] + NaBr
Sodium argento- ----- - ---~-
Silver acetylide
thi()sulphate (Soluble)
(br It corrvertsglucosefogIlicofiit acid:-
(f) AgBr is reduced to silver, when treated with zinc and
Ag20 + CI#1206 ~ 2Ag + C 6H 120 7 dilute H2S04.
(c) It oxidises formaldehyde to formic acid. Zn + H2S04 ~ ZnS04 + 2H
Ag20 + HCHO ~ 2Ag + HCOOH 2AgBr + 2H ~ 2Ag + 2HBr
[Note : All above reactions are also observed in the case of
• Uses However, it is white and fairly soluble in ammonium hydroxide.
(i) It is used as a laboratory reagent for the identification of It is sensitive to light.]
various acidic radicals especially for chloride, bromide and
iodide. The ammonical silver nitrate solution, i.e., Tollen's
• Uses
reagent is used in organic chemistry for testing aldehydes, It is used for making photographic films and plates because
reducing sugars, etc. it is sensitive to light.
(ti) Silver nitrate used for making silver halides which are
used in photography. 14.19 GOLD
(iii) It is used in the preparation of making inks and hair
dyes. Occurrence: Gold is mainly found in native state either
(iv) A very dilute solution is used in causterisation of eyes. mixed with quartz in ancient rocks (vein gold) or scattered in
The salt is sometimes used as a dental antiseptic. sand and gravel (placer gold) or in the alluvial sand (alluvial
(v) It is used extensively for the preparation of silver gold) of certain rivers which pass over auriferous rocks. It is
mirrors. The process of depositing a thin and uniform layer of also found to a small extent in combined state as sulphide,
silver on a clean glass surface is known as silvering of mirrors. telluride or arsenosulphide. The important sources of gold are:
It is employed for making looking glasses, concave mirrors (i) Alluvial sand or gravel
and reflecting surfaces. The process is based on the reduction (ii) Calaverite AuTe2
of ammonical silver nitrate solution by some reducing agent (iii) Sylvanite AuAgTe2
like formaldehyde, glucose, etc. The silver film deposited on
Mainly gold comes from the mines of South Africa. India
the glass is first coated with a varnish and finally painted with
produces about 2% of the total world production. Kolar
red lead to prevent its being scraped off.
Mines in Karnataka produce about 99% of our gold output.
Silver bromide, AgBr Extraction: (i) From alluvial sa· From alluvial
sands, gold is recovered by making use of its high specific
• Preparation gravity (19.3). The oldest method is pan washing. In big pans
made of iron or zinc, the gold bearing sand is agitated by
It is prepared by the reaction of silver nitrate with a soluble giving a rotatory motion to the pan when the heavier gold
bromide. particles settle down whereas the sand is washed away. This
AgN0 3 + NaBr ~ AgBr + NaN0 3 has now been replaced by placer mining.
Gold bearing sand is introduced in a sluice way system and
powerful streams of water are passed over it. A sluice way Thus, percentage of gold in 18 carats is 1~ x 18, i.e., 75
system is an inclined channel made up of wood having a series and the percentage of other metals is 25.
of sluices, i.e., troughs and cross wire strips known as riffles.
The gold particles are retained in the sluice whereas sand 14.20;1 POSITION OF ZINC FAMILY
particles are taken away by the water. IN PERIODIC TABLE
(ii) From auriferous quartz: The bigger pieces of
Group 12 (liB) of the long form of periodic table consists
auriferous quartz are crushed and broken into small pieces by
of four elements namely zinc (Zn), cadmium (Cd), mercury
rock crushers and then powdered by a battery of stamp mills
(JIg), and ununbium(Dub)*. These are collectively called as
working in series. The powdered ore is washed out of stamp
zinc metals as zinc is the predominant member. These elements
mill by a current of water, when only fine particles can pass
are the end members of the four series ofd-block elements as
through the screen.
the last differentiating electron is accommodated on (n l)d
~ Amalgamation process energy shell. Zinc is the last member of 3d series, cadmium is
the last member of 4d series, mercury is the last member of
_..... Tbe_slulI)'..from the_stampJnilLispassed.O\leLamalgamated. . - ··5d-series-and·ttnunbittm--is-the-last-memberof-6d-series;--
copperplates placed just infront. of stamP. mills. The gold
r~
..
'·-~][(A .
-···~~~~IIIr~ -.~~ -~-~
--~--nr---
combines with mercury to form amalganiwliich is· n::moved

..
from the plates. (11) (12) (13)
The amalgam is then distilled when the mercury passes over
4 Cu Zn Ga
leaving behind gold. This process can remove 70-80% of the
(29) (30) (31)
• gold. The residual part is known as tailings.
The tailings or the concentrated ore of gold is put in large Ag Cd In
5
vats made of wood or cement having perforated false bottoms (47) (48) (49)
covered with coconut mattings. This is treated with 0.1 %
6 Au Hg Tl
solution of NaCN in the presence of excess of air. The gold (81)
(79) (80)
dissolves according to the following reaction.
7 Duu Dub Dut
4Au + 8NaCN+ 2H20 + O2 - - t 4Na[Au(CNh] + 4NaOH (111) (112) (113)
The gold solution obtained is treated with zinc dust when
gold being less electropositive gets precipitated. 3d series Sc (1st member, 3i) ...Zn (last member, 3d lO )
lO
2Na[Au(CNh]+ Zn - - t Na2Zn(CN)4 + 2Au 4d series Y (1st member, 4i) ...Cd (last member, 4d )
lO
The precipitated gold is recovered by filtration. 5d series La (1st member, 5i) ...Hg (last member, 5d )
lO
The crude gold contains silver, copper, zinc, lead, etc., as 6d series Ac (1st member, 6i) ...Dub (last member, 6d )
impurities. These impurities are removed by cupellation and lIB group is present between m (Transition elements) and
parting process. Gold can be refined by electrolytic process IlIA (Normal elements). Thus, the elements ofIm show mixed
also. properties of transition elements and normal elements. The
inclusion of Zn, Cd, Hg and Dub in the same sub-group of the
[(ell Fineness of Gold periodic table is justified by the similarities and gradation in
Gold is a precious and noble metal. It is very stable towards their properties as the atomic number increases from Zn to
common reagents and resists the action of the atmosphere. It Dub.
is not attacked by air or oxygen or water at any temperature.
Since it re.tains its bright surface untarnished, it is used for 1. Electronic configuration
making ornaments, jewellery and watches. Generally, small They have similar 'electronic configuration. The distribution
quantities of other metals, especially copper, are added to the of the electrons in various energy shells of these atoms is
gold to make it harder. The purity or fineness of gold is generally .shown below :
expressed in carats, pure gold being known as 24 carats. Zn 30 2, 8, 18, 2 .................. 3dlO, 4i
Ornaments available these days are made of 18 carats. This is Cd 48 2, 8, 18, 18, 2 ................. .4dlO, 5i
an alloy of gold containing 18 parts gold and 6 parts other Hg 80 2, 8, 18, 32, 18, 2 .................. 5dlO,
metals. Uub 112 2, 8, 18, 32, 32, 18, 2 ..................6d lO , 7i
*Ununbium is recently discovered synthetic radioactive element. Not much is known about its properties.
These configurations show that outermost shell has two (d) Ionisation energy and oxidation potential: These
electrons while the penultimate shell contains 18 electrons, metals have fairly high values of ionisation energies. The
lO
i.e., they have general configuration (n - l)d ni. Thus, these values indicate that these metals should be less reactive. In
are d-block elements but do not show many properties which fact, they are even more reactive than the coinage metals. This
are shown by d-block elements. For example, (i) They do not is due to their high values of oxidation potentials which are
show variable valency. (ii) Most of their compounds are positive for Zn and Cd. The ionisation potential does not follow
colourless. (iii) Their melting and boiling points are very low. the regular trend. The electropositive nature and the chemical
(iv) These are diamagnetic. (v) These are more electropositive activity decreases from Zn to Hg. Hg is somewhat noble in
as the oxidation potentials for zinc and cadmium being positive. nature.
This is due to the completion of (n - l)d energy shell which . Element Zn Cd Hg
has 10 electrons (the maximum capacity of d-subshell). First ionisation potential (eV) 9040 9.00 10040
Oxidation potential (volt) 0.76 0040 -0.85
l:~ 2. Valency
(e) Other physical properties: All the three metals are
All the elements show divalency as only ni electrons are good conductors of electricity. These are greyish white lustrous
IpMhy these elements. M2+ i01).fiProdllcedL~~~~lli-=Ddl~ -metals. Thesearemalleable-anddm:tile.-The-malleability-and.---
configuration. This configuration is- stable and hence cannot ductility decreases from Zn to Cd. Except Hg, other two metals.~=~
IoseanYiiioreeIearoiis.Howevei,-rilerc~foims-twO serres; are moderately hard.
of salts, viz., mercurous salts containing Hg 2+ ion and mercuric
salts containing Hg2+ ion. Both these ions show divalency of -.iJ 5. Chemical nature of the metals and their
mercury. Mercurous ion does not exist as Hg+ but as Hg~+. compounds
Thus, mercurous chloride exists as CI-Hg-Hg-CI and not
as Hg-Cl. (a) Action of air and water: The effect of atmosphere
decreases from Zn to Hg. Zinc is slowly coated with a bluish
~ 3. Occurrence white protective film of oxide in moist air, cadmium is much
less affected while mercury is not affected at all.
They do not occur in free state. All these metals occur as Zinc decomposes boiling water slightly but at red heat, zinc
sulphides which constitute their important ores. Cadmium is decomposes steam easily. Cadmium resembles zinc but is much
usually found in the ores of zinc. However, mercury occurs in less reactive. Mercury is not affected under any conditions.
small quantities in the native state.
Zn + H 20 -----? ZnO + H2
~ 4. Physical characteristics (b) Action of oxygen: All form oxides of the type MO
when heated in air or oxygen. Basic properties increases. ZnO
(a) Physical state: Zinc and cadmium are solids while is amphoteric while CdO and HgO are basic in character.
mercury is a liquid at ordinary temperature. The interatomic These are insoluble in water.
forces of attraction are considerably weak. These are so small
ZnO + 2HCI -----? ZnCl 2 + H 20
in mercury that it exists in liquid state.
ZnO + 2NaOH -----? Na2Zn02 + H 20
(b) Melting and boiling points: The melting and boiling Sodium zincate
points are low as electrons froin (n - l)d-shell are not available
HgO + H 2S04 -----? HgS04 + H 20
for bonding.
The stability of the oxides towards the action of he'at
Element Zn Cd Hg
decreases in the order of Zn, Cd, Hg. Zinc oxide and cadmium
M.pt. eC) 419.5 320.9 -38.4
oxide sublime.HgO does not sublime because it decomposes
B. pt. ("C) 907 765 357
on heating.
These metals are volatile in nature and easily come into 2HgO -----? 2Hg + O2
vapour state.
The colours of these oxides are interesting. Zinc oxide is
:' .. '~" ..• ~:~mi(· yolume and density: The
white at room temperature but turns yellow on heating. At high
atomic radii are fairly large, i.e., more than coinage metals but
temperature metal excess non-stoichiometry is shown by ZnO.
less than alkaline earth metals. Atomic radii, atomic volume and
density gradually increases from Zn to Hg. Cadmium oxide has chocolate brown colour but is white at
liquid air temperature. Mercury oxide is known in two forms:
Element Zn Cd Hg yellow and red. The colour difference is due to particle size.
Atomic radii 1.25 1.41 1.44
Both Zn and Cd form peroxides, Zn02 and CdOz, when
Atomic volume 9.20 13.10 14.80
their hydroxides are treated with H 20 2 solution. These peroxides
Density 7.10 8.60 13.60
are less stable. Hg does not form peroxide.
(c) Action of acids: Both zinc and cadmium dissolve in 2Zn(N03)2 ~ 2ZnO + 4N02 + O2
dilute hydrochloric acid and sulphuric acid with evolution of Hg 2C03 ~ HgO + Hg + CO2
hydrogen but mercQIT remains unattacked.
3HgS04 ~ Hg 2S04 + Hg + 2S02 + 202
Zn + 2HCI ~ ZnCl2 + H2
2Hg(N0 3)2 ~ 2HgO + 4N0 2 + O2
Cd + 2HCI ~ CdCl2 + H2
All the three elements form double sulphates crystallising
Zn + H 2S04 ~ ZnS04 + H2 with six molecules of water, for example, K2S04·ZnS04·6H20.
Cd + H2S04 ~ CdS04 + H2 (h) Complexes: All the three elements form complexes
Zinc and cadmium dissolve in dilute and concentrated nitric particularly with cyanide ions, ammonia, halide ions and many
acid forming N 20, NO, N0 2 or NH3 depending on the other ligands. The complexes of Hg2+ are much more stable
concentration of the acid. However, Hg with dilute RN0 3 than Zn2+ and Cd2+. The most common coordination number
forms mercurous nitrate and nitric oxide and with concentrated of Zn and Cd in the complexes is four. Quite a few six
nitric acid it forms mercuric nitrate and nitrogen dioxide. coordinated complexes are also known. Some examples are
given below:
6Hg + 8RN03 (dil.) ~ 3Hg2(N0 3h +2NO+ 4H 20
. __LZ.n(NH:V41SQ4-- nnLCd(NH~)4-1S_0-4-___.__~ _ _ __
Hgu+n4HN03tcurrc~) ·~·rHg(N03ri-+2NOi·'F 2HiO-
n ___
~.K2ZJ)(CI\n4~~ ___ ~_ .. !<.2Cd{Q\DA______~_~ __ ~~ . - .•

Hot concentrated sulphuric acid dissolves all the metals
with the evolution of sulphur dioxide. [Zn(en)3]2+ [Cd(e~h]2+
(en = ethylene diarnine)
M + 2H2S04 ~ MS04 + S02 + 2H20
(Hot and cone.) The common coordination numbers of mercury are 2 and
(d) Action of alkalies: Zinc dissolves in caustic alkalies 4. For example, Hg(NH2)CI and K2HgI4.
with formation of zincates and evolution of hydrogen. Cadmium (i) Alloys and amalgams: Zinc forms a number of alloys
and mercury are not affected. with other metals. Cadmium is used for making low melting
alloys with lead, bismuth and tin. Mercury forms a series of
Zn + 2NaOH ~ Na2Zn02 + H2
combinations with other metals known as amalgams.
(e) Halides: These metals directly react with halogens.
M+ X2 ~MX2 1 ZINC
The nature of the bond depends on the polarising power of Occurrence: Zinc is usually found in the combined state
the cation and the polarisability of the anion. It is observed that although traces of the metal in the native state have been
polarising power increases from Zn to Hg and from F to I. The reported from Melbourne (Australia). Its chief ores are:
covalent nature of halides increases from Zn to Hg and from I. Zinc blende, ZnS. It is found in Burma, Belgium, Silesia
F to I. All the halides except HgI2 are white solids, they have and Oklahoma.
low melting points and are easily volatile. HgI2 is red but it 2. Calamine or zincspar, ZnC0 3
becomes yellow on heating at 126°C. All the halides, except 3. Zincite, ZnO
fluorides, form halo complexes of the type MX"3 and MX~ 4. Willemite, Zn2Si04
with halide ions. Traces of zinc in the form of organo-metallic compounds
(f) Sulpbides :. All form sulphides of the type MS, which have been reported in the animal cells and in snake-poison. In
can be precipitated by passing H 2S through their salts solutions. India, zinc is mainly found at Zawar in Rajasthan.
Extraction: Zinc is extracted from its ores by two methods:
ZnS CdS HgS
I. Reduction process
White Yellow Black
2. Electrolytic process.
The solubility products of the sulphides decrease from Zn
to Hg. ZnS is soluble in dilute acids, CdS is soluble in lllIl 1. Reduction Process
concentrated acids but HgS is insoluble even in concentrated It involves the following steps:
acids. HgS is soluble in aqua-regia.
(i) Concentration: When zinc blende is used, the
(g) Oxysalts: The sulphates, nitrates, acetates and perchlo- powdered ore is concentrated by froth floatation process. In
rates of these metals are soluble in water. The carbonates and the case of calamine ore, the concentration is done by gravity
oxalates are insoluble. Various salts are thermally less stable. process. If the ore contains iron oxide, the latter is removed
The ease of decomposition increases from zinc to mercury. by magnetic separation.
Mercury salts yield mercury in some cases. (li) Roasting: The concentrated ore is heated in excess
ZnC03 ~ ZnO + CO2 of oxygen at about 900°C. Zinc sulphide is oxidised to zinc
2ZnS04 ~ 2ZnO + 2S02 + O2 oxide. If some of the ore is oxidised to zinc sulphate, it also
decomposes at 900°C into ZnO.
2ZnS + 302 - - ? 2ZnO + 2S02 Charging door

ZnS + 202 - - ? ZnS04
2ZnS04 2ZnO + 2S02 + O2 "'" Waste gases
--?
I
When .the ore is calamine, it shall decompose into oxide with . Condenser 1
evolution of carbon dioxide.
ZnC0 3 - - ? ZnO + CO2 Producer
gas+Air-
For roasting, a reverberatory furnace may be used.
(iii) Reduction: The principal reaction that takes place
during reduction is the conversion of the oxide into the metal
with the help of carbon.
ZnO + C --? Zn + CO
There are different types of reducing furnaces for the
Heating jacket
reduction of the oxide. All make use of the same principle but
~if~~~_()n!y_il1_the d~!~I~_()f~~tlstrl1~tioIliln~l!l~t~o~~y which
the metal is separated.
(a) -Belgian-process: It isanoldprocess:-The roasted
ore is heated with coke to about llOO°C in a small fIreclay
retorts. The heating is often done by producer gas. Each retort
Fig. 14.16
feeding of roasted ore and powdered coke. Retorts are made

of highly refractory silicon carbide bricks capable of with-
standing high temperature 1300°C. The retorts are heated
externally by producer gas. There is an extension at the bottom
through which ash can be removed. The open end of the retort
is connected with condensers. Zinc vapour and carbon
monoxide pass into the condensers when zinc liquefies. Molten
zinc is periodically taped off from the condensers and carbon
Fig. 14.15 monoxide is used as fuel for heating the furnace.
(iv) Purification: The zinc obtained above is impure
is filled with a mixture of 2 parts ore and one part coke. The containing 97.8% zinc and rest impurities oflead, iron, cadmium,
retorts are about 1.5 metre long and 25 cm in diameter. Each arsenic, etc. This impure zinc is known as spelter. This is put
retort is circular or elliptical in shape and closed at one end. to further purification by distillation. The distillation is cairied
The mouth of each retort is provided with an earthenware around 950-1 OOO°C when only zinc (b. pt. 907°C) and cadmium
condenser. The temperature is raised to about 1100"C, the CO (b. pt. 767°C) distil over. From this sample, cadmium is removed
fonned during the process burns at the mouth of the retorts at 800°C.
and when the colour of the flame changes from blue to greenish The impure zinc can also be purified electrolytically. The
white, the condensers are fitted there on. These condensers impure metal is made anode and cathode consists of sheets of
are cooled by air and the metal condenses in these partly as a pure aluminium. A solution of zinc sulphate acts as an electrolyte.
fused metal (spelter) and partly as a powder (zinc dust). Zinc dissolves from anode and deposits on cathode when
Reactions: ZnO + C - - ? Zn + CO electric current is passed. Zinc is scraped off from the
aluminium sheets.
ZnO + CO - - ? Zn + CO2
C02 + C~ 2CO 2. Electrolytic Process
There are number of such retorts which are arranged in This method is gradually replacing the reduction process.
three or four rows one above the other. The roasted ore is dissolved in dilute sulphuric acid and the
(b) Vertical retorts process: This is a continuous process solution is filtered. The solution is freed from iron, aluminium,
and is largely used these days. It is economical also. silica, etc., by treatment with calcium hydroxide. Copper and
In this process the vertical retorts of about 7.5 metre height cadmium are removed by precipitation with zinc dust at 75°C.
are used. Each is connected with an arrangement for continuous
FeS04 + Ca(OH)z ----? Fe(OH)z + CaS04 Conc. HN03 : Nitrogen dioxide is evolved.
CdS0 4 + Zn ----? Cd + ZnS04 Zn + 2HN03 ----? Zn(N03h + 2H
CUS04 + Zn ----? Cu + ZnS04 [HN03 + H ----? N0 2 + H20] x 2
The filtered solution is subjected to electrolysis by using a
Zn + 4HN0 3 ----? Zn(N03)z + 2N02 + 2H20
sheet of pure aluminium as cathode and pure lead plate as
anode. The zinc is removed from cathode by melting. The zinc (d) Action of alkalies: Zinc dissolves in hot caustic
obtained is 99.95% pure. alkali solutions forming alkali zincate and evolving hydrogen.
Granulated zinc is made by melting the metal in a crucible Zn + 2KOH ----? K2Zn02 + H2
and pouring the drops in ,¥ater. Zinc sheet is formed by heating Pot. zincate
the metal at 150°C when it becomes soft and then can be rolled (e) Electropositive nature: Zinc displaces many metals
into sheets. such as lead, copper, silver, gold, etc., from their salt solutions
as it is highly electropositive.
• Properties Zn + CUS04 ----? ZnS04 + Cu
Physical: (a) It is a bluish white metal. It acquires grey Zn + 2AgN03 ----? Zn(N03)z + 2Ag
colour_ when exposed-to moist- atnlosphere.-(b-)It--mBltsat - . - (fTAcfionoCammoIiUl.:Zinc decomposes ammonia -_ at
...- - - _..
419SCandboils at 90'?°C. (c) IIh~s sp~cificgra.vity7.1. red heaL ..--_.

(d) Ii IS -mafieabfe and-ductile. (e) It is good conductor of heat
and electricity. 3Zn + 2NH3 ----? Zn3N2 + 3H2
Chemical: (a) Action of air: It is not affected by dry (g) Action of halogens: It reacts with halogens directly.
air. In moist air, a protective thin film of basic carbonate is Zn + X2 ----? ZnX2
formed on its surface. When heated in air strongly, it burns (h) Action of sulphur: When heated with sulphur, it
forming a white smoke which settles down to soft wooly forms zinc sulphide.
s
flocks of zinc oxide called the philosopher wool or pompholyx.
Zn + S ----? ZnS
2Zn + O 2 ----? 2ZnO
(b) Action of water: Pure zinc is not affected by water. • Uses
The commercial zinc decomposes boiling water. At red heat,
(i) Zinc is used in the manufacture of various important
the metal decomposes steam evolving hydrogen.
alloys such as brass, german silver, etc.
Zn + H20 ----? ZnO + H2 (ii) Zinc is used in Parkes process for the extraction of
(c) Action of acids: Pure zinc is aHacked slowly by acids silver from argentiferous lead. Zinc dust is used for the extraction
but commercial zinc reacts readily wiLL all acids. It dissolves of Ag and Au by cyanide process. .
in HCI (dilute and conc.) and dilute H 2S04 evolving hydrogen. (iii) Zinc dust is used in the laboratory as a reducing agent.
Zn + 2HCI ----? ZnCl 2 + H2 (iv) Zinc rods are used in making electric batteries.
(v) The most important use of zinc is for the galvanising
Zn + H2S04 ----? ZnS04 + H2
of iron. Galvanising is a process of depositing a thin layer of
It dissolves in concentrated H2S04 with evolution of S02. zinc over the surface of iron. The zinc coating protects the
H 2S04 ----? H 20 + S02 + 0 iron from corrosion. The iron articles to be galvanised are first
Zn + H 2S04 + 0 ----? ZnS04 + H 20 cleaned by means of a sand blast and then dipped in dilute
H2S04 and finally washed with water. The galvanisation is
Zn + 2H2S04 ----? ZnS04 + S02 + 2H20 done either by spraying the molten zinc or dipping in molten
Dilute nitric acid gives nitrous oxide or ammonium nitrate zinc or electrolytically.
depending on the strength of the acid.
Very dilute HN03 : Ammonium nitrate is formed. 14.22:~ COMPOUNDS OF ZINC
[Zn + 2HN03 ----? Zn(N03h + 2H] x 4 Zinc oxide, ZnO: Zinc oxide is also called zinc white or
2HN03 + 8H ----? Nl4N03 + 3H20 chin~se white or philosopher's wool. It occurs in nature as the
mineral zincite or red zinc ore.
4Zn + IOHN03 ----? 4Zn(N03h + NH4N0 3 + 3H20
Dilute HN03 : Nitrous oxide is evolved. • Preparation
[Zn + 2HN03 ----? Zn(N03h + 2H) x 4 It is obtained by the combustion of zinc or by the calcination
2HN03 + 8H ----? N 20 + 5H20 of zinc carbonate, zinc nitrate or zinc hydroxide.
2Zn + 02 ----? 2ZnO
ZnC03 ~ ZnO + CO2 Zinc Chloride, ZnCI 2 ,2H 20

2Zn(N0 3h ~ 2ZnO + 4N02 + O2
Zn(OHh ~ ZnO + H20
• Preparation
Very pure zinc oxide is prepared by mixing a solution of zinc It is obtained by treating zinc oxide or zinc carbonate or zinc
sulphate with sodium carbonate. The basic zinc carbonate hydroxide with dilute hydrochloric acid. The solution on
thus, precipitated on heating gives pure zinc oxide. concentration and cooling gives hydrated zinc chloride crystals,
ZnCI2·2H20.
4ZnS0 4 + 4Na2C03 + 3H20 ~ ZnC03·3Zn(OHh
ppt. ZnO + 2HCI ~ ZnC1 2 + H 20
+ 4Na2S04 + 3C02 ZnC03 + 2HCI ~ ZnCl2 + CO2 + H20
ZnC03·3Zn(OHh Heat) 4ZnO + 3H20 + CO2 Zn(OHh + 2HCI ~ ZnC1 2 + 2H20
Anhydrous zinc chloride cannot be obtained by heating
• Properties crystals of hydrated zinc chloride as hydrolysis occurs and
(i) It is a white powder. It becomes yellow on heating and basic chloride (zinc hydroxy chloride) is formed w1p.ch on
again tIlmswhTie on cooIIng.-(ii ntis very lignClf is insoluble . further-· heating-giv-es---zinG--oode-.-· . c ........ .
in water. It sublimes at AOO°C. (iii) It is an amphoteric oxide ZnCI2·2H20~.Zn(OH)Cl + HCI +,H20==~
and dissolves readily in acids forming corresponding zinc salts Zn(OH)Cl ~ ZnO + HCI
and alkalies forming zincates. The anhydrous zinc chloride is obtained by heating zinc in
ZnO + H2S04 ZnS04 + H20 the atmosphere of dry chlorine or dry HCl gas.
ZnO + 2BCl ~ ZnCl 2 + H20 Zn + Cl2 ~ ZnCl2
ZnO + 2NaOH ~ Na2Zn02 + H20 Zn + 2HCI ~ ZnCl2 + H2
Sodium zincate
This can also be formed by distilling zinc pl;wder with
(iv) When heated in hydrogen above 400"C, it is reduced to mercuric chloride.
metal.
ZnO + H2~ Zn + H20 Zn + HgCl2 ~ ZnCl 2 + JIg
It is also reduced by carbon into zinc. • Properties
ZnO + C~Zn+ CO
(a) Anhydrous zinc chloride is a white solid, deliquescent
(v) When zinc oxide is heated with cobalt nitrate, a green and soluble in water. It melts at 660°C and boils at 730°C. (b)
mass is formed due to formation of cobalt zinc ate which is Hydrated zinc chloride on heating forms zinc hydroxy chloride
known as Rinmann's green. or zinc oxychloride.
2CO(N03h ~ 2CoO + 2N02 + 02 ZnCl 2·2H20 ~ Zn(OH)Cl + HCI + H20
ZnO + CoO ~ CoZn02 or CoO·ZnO 2ZnC12·2H20 ~ Zn20Cl2 + 2HCI + 3H20
Zinc oxychloride
• Uses (c) When H2S is passed through the solution, a white
(i) Zinc oxide is used as a white pigment (paint). No doubt precipitate of zinc sulphide, is formed.
its covering power is less than white lead but it is superior ZnCl2 + H2S ~ ZnS + 2HCI
because it is not blackened in atmosphere of hydrogen sulphide. (d) When NaOH is added, a white precipitate of zinc hydroxide
It can be used both as oil and water paint. appears which dissolves in excess of sodium hydroxide forming
(ii) It is used to prepare Rinmann's green which is employed sodium zincate.
as a green pigment.
ZnCl2 + 2NaOH ~ Zn(OHh + 2NaCI
(iii) It finds use as a catalyst along with Cr203 in the
manufacture of methyl alcohol from water gas. Zn(OHh + 2NaOH ~ Na2Zn02 + 2H20
(iv) It is used as a filler for soft rubber imd as an absorbent (e) On adding NH 40H solution, a white precipitate of zinc
in surgical dressing. hydroxide appears which dissolves in excess of ammonia
(v) It is also used as zinc ointment in medicine and as a glaze forming a complex salt.
in ceramics. ZnCl2 + 2~OH ~ Zn(OHh + 2NH4CI :1
(vi) It is used for cosmetic powders and creams.
Zn(OHh + 2NH40H + 2NH4Cl ~ [Zn(NH3)4]CI2 + 4H20
Tetrammine zinc
chloride
(f) When the solution of zinc chloride is treated with a
solution of sodium carbonate, a white precipitate of basic zinc ZnS04 800"C) ZnO + S03
carbonate is formed.
4ZnCI2+4Na2C03+3H20 ~ ZnC03·3Zn(OHh+8NaCI+ 3C02
1S02 + 202
1
Basic zinc carbonate

(c) When sodium hydroxide is added to the solution of zinc
But when a solution of sodium bicarbonate is used, a white sulphate, a white precipitate of zinc hydroxide appears which
precipitate of normal zinc carbonate is formed. dissolves in excess of NaOH forming. sodium zincate.
ZnCl2 + 2NaHC0 3 ~ Zn~03 + 2NaCI + H 20 + CO2 ZnS04 + 2NaOH ~ Zn(OHh + Na2S04
(g) Anhydrous zinc chloride absorbs ammonia gas and torms Zn(OHh + 2NaOH ~ Na2Zn02 + 2H20
an addition compound. (d) When sodium carbonate solution is added to the solution
ZnCl 2 + 4NH3 ~ ZnCl24NH3 of zinc sulphate, a white precipitate of basic zinc carbonate is
(h) Its syrupy solution dissolves cellulose. formed.
(i) Its syrupy solution when mixed with zinc oxide, ZnO, 4ZnS04 + 4Na2C03 + 3H20 ~ ZnC03·3Zn(OHh
.. setsJoa hard~massforming_anQx)'chloride,_ZnC12: 3ZnQ.... + 4Na:2.~()4±}C_O ___2____
However, when the solution of sodium bicarbollate i~ addecl,_
• Uses nolihal Zinc carbOhate is forriled ..
(i) The concentrated solution of zinc chloride is used for ZnS04 + 2NaHC03 ~ ZnC03 + Na2S04 + H 20 + CO2
impregnating timber to prevent its destruction from the action (e) With alkali metal sulphates and (NH4hS04, it forms
of micro-organisms. double sulphates such as K2S04·ZnS04·6H20.
(ii) The mixture of syrupy zinc chloride solution and zinc
oxide is used for dental filling. • Uses
(iii) It is used as dehydrating agent.
(iv) Being acidic in aqueous solution, it is used for cleaning (i) A dilute solution of zinc sulphate is used as eye lotion.
the surface of metals before soldering. (ii) It is used for the preparation of lithopone (ZnS + BaS04),
(v) It is employed in making parchment paper; vulcanised a popular white paint.
fibre, cold water glues and adhesives. It is also used in the (iii) It is employed as a mordant in dyeing and calicoprinting.
manufacture of dry cells. . (iv) The solution of zinc sulphate is used for zinc plating and
in the electrolytic refining of zinc.
Zinc Sulphate (White vitriol), ZnS04,7H20 (v) Zinc sulphate is used as a starting material for the
preparation of other zinc compounds.
• Preparation
ZnS
It is prepared by reacting zinc with dilute sulphuric acid. It
can also be prepared by dissolving zinc oxide or carbonate in
dilute sulphuric acid. The solution on concentration and
crystallisation below 39°C gives colourless crystals of zinc
sulphate, ZnS04·7H20.
Zn + H2S04 ~ ZnS04 + H2
Zno + H 2S04 ~ ZnS04 + H20
ZnC03 + H2S04 ~ ZnS04 + H20 + CO2
• Properties 14.23; MERCURY

(a) It is a colourless, crystalline solid. It is an efflor"escent Occurrence: Mercury ores are rare. It occurs in small
substance. It is freely soluble in water. quantities in the native state. Cinnabar, HgS. is the most important
(b) On heating, the following changes occur. ore and is found in Spain and Italy and small quantities in
Russia, United States of America, Mexico, China and Japan.
°
ZnSO4·7H2 Above °
39"C) ZnSO4.6H2Above70"C)ZnSO
Below 70.C . 4·H2 ° Extraction: The extraction of mercury from cinnabar
Above 280"C 1 ore is comparatively simple and consists mainly the roasting
and distillation. The extraction involves the following steps :
~ + S02 + ZnO (800"C ZnS04
(Anhydrous)
(i) Crushing and concentration: The ore is crushed

Ore and
and finely powdered in ball mills and concentrated by froth charcoal
,--------,
floatation process.
(ii) Combined roasting and distillation: There are two
principal processes available which differ only in the type of
furnace used.
(a) Idrian furnace used in Almaden (Spain). This is the old Ore chamber
process.
(b) Shaft furnace-This is the modem continuous process.
Waste
(a) Idrian Furnace r:===-.... gases
Water
The concentrated ore is taken on the perforated arches and
heated by the flame (Fig. 14.17).
Mercury receivers
Fig. 14.18
HgS + CaO ~ HgO + CaS

2HgO ~ 2Hg + O2
(iii) Purification: Commerciai· mercury is usually coiita-
minated with other elements such as zinc, Coppel, lead, etc. It
may be purified by the following methods.
(a) To remove suspended particles mercury is squeezed
Fig. 14.17 through linen or chamois leather.
(b) The more basic metals such as lead and zinc, which are
The mercuric sulphide undergoes oxidation with evolution easily oxidised, are removed as scum of their oxides when dust
of sulphur dioxide. The mercuric oxide thus formed decomposes free air is passed through mercury at 150°C.
at 300°C to give mercury vapours. (c) The mercury is dropped in a long tube filled with dilute
2HgS + 302 ~ 2HgO + 2S02 nitric acid (about 5%). The base metals dissolve in dilute nitric·
2HgO ~ 2Hg + 02 acid as their nitrates.
(d) Further purification is done by vacuum distillation.
The vapours of mercury are condensed in a series of
condensers on either side of the furnace. Most of the metal
• Properties
collects in the first three condensers and in the last condenser,
the condensation is assisted by water spray or wet straw dust. Mercury is a silvery white heavy liquid (Sp. gr. l3.6). It
solidifies at -38.9°C to a white lustrous mass and boils at
(b) The Shaft Furnace 357°C. Its vapour is very poisonous. It has a high surface
tension and forms spherical drops easily.
The ore chamber is cylindrical, standing on a hexagonal
It is not affected by air or oxygen at ordinary temperature
base. The concentrated ore, mixed with charcoal is added to
but when heated at 340°C in air, it slowly combines with
the furnace by a cup and cone arrangement. There are three
oxygen forming a red scum of HgO on the surface. When
fire places communicating with the chamber on the alternate
exposed to ozone, it gets superficially oxidised and loses its
sides of the hexagon. The furnace is heated to a red heat. Air
meniscus and sticks to the glass.
is admitted along with the flames. Gases with mercury vapours,
When rubbed with sulphur, it forms mercuric sulphide,
pass through iron pipes into watercooled condensers. There is
HgS. It vigorously combines with chlorine, slowly with bromine
an opening in the bottom of the furnace for the removal of
and iodine.
spent ore.
It is not attacked by water and alkalies. Hydrochloric acid,
The ore is sometimes mixed with lime before roasting. This
dilute sulphuric acid and very dilute nitric acid have no action
helps in the oxidation of mercuric sulphide.
on mercury. Hot concentrated sulphuric acid, dilute and
concentrated nitric acid dissolve it.
Transition Elements or d-block Elements and f-block Elements 701-
With cone. H2S04: (iii) It can be obtained by passing sulphur dioxide through
H2S04 -----7 H20 + S02 + 0 the solution of mercuric chloride.
Hg + H 2S04 + 0 -----7 HgS04 + H 20 2HgCl2 + 2H20 + S02 -----7 Hg 2Cl2 + H2S04 + 2HCI
(iv) Mercurous chloride for medicinal purposes is prepared
Hg + 2H2S04 -----7 HgS04 + S02 + 2H20
by heating a mixture of mercuric chloride and mercury in an
With dilute HN03 : iron pot. The sublimate is ground and boiled with water to
2HN0 3 -----7 H20 + 2NO + 3[0] remove traces of mercuric chloride.
[2Hg + 0 -----7 Hg 20] x 3 HgCl 2 + Hg -----7 Hg 2Cl2
[Hg20 + 2HN03 -----7 Hg 2(N0 3h + H 20] x 3
• Properties
6Hg + 8HN03 -----7 3Hg2(N0 3h + 2NO + 4H 20
(i) It is an amorphous, tasteless, odourless white powder.
With cone. HN03 : It is sparingly soluble in water. It sublimes at 373°C. It is non~
2HN0 3 -----7 H20 + 2N02 + 0 poisonous.
Hg + 2HN03 + 0 -----7 Hg(N0 3h + H 20 (ii) It dissolves in hot concentrated nitric acid forming
. mercuricchloride··andmercuric-nitrate: ..._-_ . .- -
3Hg2Cl2 +8HN03 -----7 3HgCh+3Hg(N03h+4H20+2NO=C-::==---
Mercury is acted upon by HI on account of the formation
(iii) It dissolves in chlorine water, aqua-regia or a mixture
of a complex ion [HgI4f-.
of KCI0 3 and concentrated HCI.
Hg + 2HI -----7 HgI2 + H2 Hg 2Cl 2 + 2CI-----7 2HgC12
HgI2 + 2HI -----7 H2Hgl4 (iv) On heating, it decomposes into mercuric chloride and
Mercury dissolves many metals and the combinations are mercury.
called amalgams. Gold, silver, tin, lead, magnesium, copper, Hg2Cl2 -----7 Hg + HgC12
sodium, potassium, etc., when rubbed with mercury form (v) When caustic soda solution is added in excess to a
amalgams. Iron, cobalt and nickel do not form amalgams mercurous chloride solution in HCI, a black precipitate of
directly. mercurous oxide is formed which is decomposed under the
action of light.
• Uses
Hg 2Cl2 + 2NaOH -----7 Hg20 + 2NaCI + H20
Mercury is used (i) in themlOmeters, barometers, and other
Hg 20 -----7 HgO + Hg
physical apparatus (ii) in the extraction of Ag and Au (iii) in the
manufacture of caustic soda by the electrolytic process (iv) in (vi) It turns black when treated with ammonium hydroxide.
the form of amalgams as reducing agents. (v) in mercury The black substance is a mixture of mercury and mercuric
vapour lamps which give out bluish light. (vi) in making dental amino chloride.
NH 2
plastic (vii) in the manufacture of vermilon (HgS).
14.24 COMPOUNDS OF MFRCURY

Hg 2Cl 2 + 2NH 40H-----7 Hg
, <C~
+ Hg + NH 4CI + 2H 20
Black
,
Mercurous Chloride, Hg 2CI 2 (Calomel) (vii) It is reduced to mercury with stannous chloride.
SnCl2 + Hg 2Cl2 -----7 2Hg + SnCl4
• Preparation (viii) It absorbs ammonia gas and forms an addition
(i) By adding dilute hydrochloric acid or sodium chloride compound.
solution to a mercurous salt solution, usually mercurous nitrate, Hg 2Cl 2 + 2NH3 -----7 Hg 2Cl2·2NH3
a white precipitate of mercurous chloride is fonned.
Hg2(N0 3h + 2HCI-----7 Hg 2Ch + 2HN03 • Uses
Hg2(N03h + 2NaCI -----7 Hg2Cl 2 + 2NaN03 (i) As a purgative in medicine.
(ii) Metallic mercury is boiled with concentrated sulphuric (ii) For making calomel electrodes.
acid and the product, mercuric sulphate is then ground
thoroughly with common salt and metallic mercury. The mixture Mercuric Chloride (Corrosive sublimate), HgCI2
is sublimed to separate Hg 2C1 2.
• Preparation
Hg + 2H2S04 -----7 HgS04 + S02 + 2H20
HgS04 + 2NaCI + Hg -----7 Hg2Cl2 + Na2S04 (i) The compound was formerly prepared on commercial
scale by heating a mixture of mercuric sulphate with common HgCl2 + Na2C03 ~ HgO + 2NaCI + CO 2
salt. A little manganese dioxide was added to prevent the HgCl 2 + 2NaOH ~ HgO + 2NaCI + H20
formation of any mercurous chloride. Mercuric chloride
sublimes off and condenses on the cooler parts of the vessel. (viii) Potassium iodide forms a scarlet precipitate of mercuric
iodide when added to HgCl2 solution. The precipitate of mercuric
HgS04 + 2NaCI ~ HgCl2 + Na2S04 iodide dissolves in excess of potassium iodide forming a
(ii) The compound is now commercially made by heating complex, K2HgI4.
the metal in a current of chlorine.
HgCl 2 + 2KI ~ 2KCl + HgI2
Hg + Cl2 ~ HgCI2
HgI2 + 2KI ~ K2HgI4
(iii) It can be prepared by dissolving mercuric oxide in
hydrochloric acid. The alkaline solution of this complex is known as Nessler's
reagent. This reagent is used for testing ammonia. When
HgO + 2HCI ~ HgCl2 + H20
ammonia or ammonium salts are present, the brown precipitate
(iv) It can also be prepared by dissolving Hg or Hg2Cl2 in is obtained. This precipitate is said to be the iodide of Millon's
aqua-regia. base, probably having the composition:
3HCI + RN03 ~NOCI + 2H20 + 2CI
. Hg + 2CI ~ HgCl2
.HgiCi2 +2CI ~ 2HgCi2
• Properties (A) (B)

(i) It is a white crystalline compound. It is less soluble in
cold water but more soluble in hot water. It behaves like a The formation of the iodide of Millon's base can be explain(;fl
covalent compound as it is soluble in organic solvents and very as follows:
slightly ionised in water.
(ii) It has corrosive action. It is highly poisonous. It sublimes
on heating .. It is, therefore, known as corrosive sublimate.
(iii) It is reduced by stannous chloride flrst into mercurous
chloride (white) and then into mercury (black), +
NH2 IHg H
2HgC1 2 + SnCl2 ~ Hg 2Cl2 + SnCl4
White
Hg2Cl2 + SnCl2 ~ 2Hg + SnC14
Hg<
I
+ HgI2-4
[IHg) N <H j I-
Black (A)
(iv) When aqueous ammonia is added to the solution of
mercuric chloride, a white precipitate of mercuric amino chloride
is fonned.
HgCl 2 +2NH40H~ Hg
< NH 2
CI
+NH4Cl+2H20
(v) Mercuric chloride absorbs gaseous ammonia and forms

a complex salt.
HgCl2 + 2NH3 ~ Hg(NH3hCl2
Mercuric diamine chloride
(vi) When H2S is passed through its solution, it forms a
(i) It is highly poisonous and hence used as germicide. It is
black precipitate of mercuric sulphide. used as an antiseptic. A very dilute solution is employed for the
HgCl 2 + H2S ~ HgS + 2HCI sterilization of surgical instruments. (ii) For the preparation of
(vii) When heated with sodium carbonate or sodium Nessler's reagent which is used for the test of ammonia and
hydroxide in solution, a yellow precipitate of mercuric oxide is ammonium compounds. (iii) It is used in dry cells and as a
formed. wood preservative.
Note : It is a strong poison, its antidote being the white of an egg which
eliminates it from the system in the form of a coagulated mass.
Transition Elements or d-block Elements and f-block Elements 703-
,--_ _ _ _ _ _ ____.-"'K.:::..I-'.:(e;;.:.;xc:.:;.6::;.::SS:L..)_ _ _ _ _ _ _.. K2Hgl4
I SnCI2
' - 1 ----'-~--l
,..--!'~!2...- CI2 Hg2CI 2
~~
Q oft., \?
~ "il
"+ ~
Hg(N0
3
h ____-=--"-'L_ _
Soln.
14. PHOTOGRAPHY object through the lens falls on the film or plate. The silver
bromide is affected by light and gets activated. This is not a
The art of obtaining an exact impression of an object ona plate
visible change but is called formation of latent image.
or paper by a chemical reaction initiated by light is called
The light reduces silver bromide. The effect produced on
photography. It is based on the nature of silver halides. Except
the film or plate is directly proportional to the intensity of light.
AgF, the silver halides are photosensitive. Silver halides,
particularly silver bromide, undergo decomposition in light and 2AgBr ~ 2Ag + Brz
turn black due to formation of free silver. Bromine is absorbed by gelatine and helps in the decomposition
Light of silver bromide. According to one theory (Gumey-Mott
2AgBr ) 2Ag + Brz theory), the following sequence of events occur:
The entire process of photography involves the following (i) An incoming quantum of light hv kicks an electron out
steps: of Br- to form Br and e-.
(ii) The electron wanders through the crystal of AgBr and
~ 1. Preparation of photographic plate or fUm eventually gets trapped at a surface defect.
(iii) An interstitial Ag+, such as is commonly found in AgBr,
An emulsion of silver bromide is prepared in a dark room
diffuses to the trap site where the Ag + and the trapped e-
by mixing silver nitrate solution with ammonium bromide
combine to give Ag.
solution containing gelatine with constant stirring.
(iv) A second quantum of light energy hv comes along and
N1L(Br + AgN03 ~ AgBr + NH4N0 3 ejects a second electron which migrates to Ag and converts it
The emulsion is allowed to stand at about 45°C for some time into Ag-.
so that the particles of silver bromide may grow in size. This (v) A second interstitial Ag + subsequently diffuses over and
treatment is termed as· the ripenin,g of emulsion. The emulsion combines.
is now cooled in ice as to solidify. It is washed with water in Ag+ + Ag- ~ Ag2
order to make it free from ammonium nitrate. It is warmed to (vi) The process repeats until a clump of about 50 silver
melt it again. atoms is built up. The AgBr grain is now "activated".
The melted emulsion is applied uniformly on a celluloid film
or smooth glass plate. Whole of this operation should be done ~ 3. Developing
in a dark and dust-free room.
The treatment of the exposed photographic film with reducing
iJii 2. Exposure agents is called developing of the film. The chemicals used for
developing as reducing agents are called developers. A developer
The light-sensitive film or plate is loaded in a camera which is usually a weak reducing agent such as potassium ferrous
is focussed on the object to be photographed. When the shutter oxalate or an alkaline solution of pyrogallol or an alkaline solution
of the camera is opened for a few seconds, the light from the of quinol, etc.
The exposed film or plate is kept in a solution of a developer

AgBr AgBr
for some time. The parts activated by light are reduced to
deposit more of black silver.
2AgBr + CJ-I4(OHh ---7 2Ag + 2HBr + C 61402
Quinol Quinone
--7)~1 Ag
Object Photographic Exposed D9V910Id pial'
The developer does not affect those parts of the photographic plate plate
film or plate which are not activated by light. On the developed
film or plate the shades of the object are reversed, i.e., the
bright parts of the object appear dark and the dark parts appear ~(--~NOAgBr
bright. The plate or film is, therefore, called a negative. This
operation is carried out in dark. Print Negative (Fixing)
F~g. 14.19
4. Fixing
In order to ~ake the image permanent, it is necessary to
:remo~Yeti1e uIl,fedllcecl ~~ilYeLbIomicleJr()!!1Jhe~§llrf(lceof tile 14.26, '-Block Elements
developed film. This operation is called fixing of image. Fixing 28 elements from atomic number 58 to 71 (14 elements) and_
is done by dipping the developed filril or plate ins6dium from· atoiriic nuniber 90 to 103 (14 elements) have been
thiosulphate (hypo) solution. The hypo solution dissolves the arranged in two horizontal rows below the periodic table. These
unreduced silver bromide by forming a complex. elements are collectively called f- block elements as the last
AgBr + 2Na2S203 ---7 Na3 [Ag(S 203)z] + NaBr . or differentiating electron in the atoms of these elements is
Sodium argentothiosulphate accoll)lllodated on one of the seven f-orpi~aJs of ~he ante-
(Soluble) penultimate (next to the penultimate) energy shell. These
This operation is also done in dark. elements have also been called inner transition elements
The plate is now thoroughly washed with water and dried. because the ante-penultimate energy shell, i.e., (n -2)f-orbitals,
It can now be taken out of the dark room into light. lie comparatively deep within the kernel (being inner to the
penultimate shell).
r~ 5. P;-inting
f-block consists of two series of elements known as
To get a positive image, the whole process is repeated. The Lanthanides or Lanthanons and Actinides or Actinons.
Printing Out Paper (POP) or bromide paper is used. The .POP The lanthanide series follows lanthanum (At. No. 57), a member
has got a coating of silver bromide emulsion. The negative is of 5d-series. Similarly, actinide series comes after actinium
placed over POP and then exposed to light for a fraction of a (At. No. 89), a member of 6d-series. The 14 members of
second. A negative of the negative plate or positive with respect lanthanide series have been placed along with lanthanum in the
to the actual object is obtained on the print paper. The print third group and sixth period and similarly 14 members of the
paper is then subjected to developing and fixing as usual. The actinide series have been placed with actinium in the third
positive print bas shades exactly similar to those of the object. group and seventh period. The justification for assigning one
place to these elements has been given on the basis of their
6. Toning similar properties. The properties are so similar that the fifteen
It is a technique by which different shades can be given to elements from La to Lu can be considered as equivalent to one
the printed photograph with the help of chemicals. The printed element. The same explanation can be given in the case of
photograph obtained is black and white. This photograph is actinides. In case, these elements are assigned different positions
dipped in a solution containing the salt solution of either gold in order of their increasing atomic numbers, the symmetry of
or platinum or. selenium, etc. The dark silver particles are the whole arrangement would be disrupted. Due to this reason,
replaced by another metal. Thus, gold salt gives golden shade the two series of elements, i.e., lanthanides and actinides are
and platinum salt makes the shade bright grey. placed at the bottom of the periodic table and constitute one
block of elements, i.e., f-block. The general electronic
AuCl 3 + Au + 3AgCI configuration of the f-block elements is:
Golden
PtC4 + 4Ag ---7 Pt + 4AgCl

(n 2)i- 14(n l)d°,lni or 4j1-145d o,1 6i
Steel grey (a) 4fr..,\'ries (Lanthanides); There are fourteen elements
The various steps involved in photography are shown in from cerium (At. No. 58) to lutetium (At. No. 71) in this
Fig. 14.19. series. 4f-orbitals are gradually filled up. In the past, these
Transition Elements or d-block Elements and f-block Elements 705""
elements were called rare earths. This name is not apprC1priate 2. Oxidation states
because many of the elements are not particularly rare.
The common stable oxidation state of all the lanthanides is
Promethium is artificial radioactive element.
. +3. The oxidation states of +2 and +4 are also exhibited by
(b) Sf-series (Actinides): There are fourteen elements
some of the elements. These oxidation states are only stable in
from thorium (At. No. 90) to lawrencium (At. No. 103) in this
those cases where stable 4/, 4/ or 4/4 configurations are
series. Sforbitals are gradually ftlled up. The members of
achieved.
actinium are radioactive and majority of them are not found in
For example, Ce4+(4fO), Tb4+(4f\ Eu2+(4f\ Yb2+(4/ 4)
nature. The elements from atomic number of 93 onwards are
are stable. The oxidation states shown in parantheses in the
called transuranic elements and have been discovered by
above table are less stable. +2 or +4 oxidation states tend to
synthetic methods, i.e., these are man made elements.
revert to the more stable oxidation state of +3 by loss or gain
GENERAL CHARACTERISTICS OF of an electron Sm2+, Eu2+ and Yb 2+ ions are thus good reducing
agents in solutions while Ce4+,Tb4+ ions, etc., are good
LANTHANIDES
oxidising agents. The compounds of lanthanides are mainly
The general characteristics are similar to transition metals, i.e., ionic in nature.
d-block elements.
. ~'-a--~Atomtcancftcrnic-tadii --
ill 1.Electl"Ol'Iic:configuratiQn~ -(lanthallidecoritraCtion)
The energies of Sd- and 4f-orbitals are nearly similar and In lanthanide series, there is a regular decrease in the atomic
thus their fillings show certain irregularities. The electronic as well as ionic radii of trivalent ions (M3+) as the atomic
configurations of the atoms of the lanthanides in their ground number increases from cerium to lutetium. This decrease in
state are given in the following table. These are the most size of atoms and ions is known as Lanthanide contraction.-
commonly accepted configurations. Although the atomic radii do show some irregularities but ionic
radii decrease steadily from La to Lu. However, the decrease
Name of the Atomic Electronic Oxidation
element Symbol . number configuration states is very small. For example,
.......
~
Lanthanum La 57 [Xe]5i6i +3 Ionic radii (pm)

Element Atomic radii (pm) . . (MJ+)
1
Cerium Ce 58 [Xe]4i5d 6s 2 +3, +4
Praseodymium Pr 59 [Xe]4/6i +3, (+4) La 169 103
Neodymium Nd 60 [Xe]4/6i (+2), +3 ce 165 102
Promethium Pm 61 [Xe]4/6i (+2), +3 Pr 164 99
Samarium Sm 62 [Xe14t6i (+2), +3 Nd 164 98.3
Europium Eu 63 [Xe]4/6i +2, +3 Pm 97
Gadolinium Gd 64 [Xe]4/5d 6i
1
+3 8m 166 95.8
Eu 185 94.7
Terbium Tb 65 [Xe]4/6i +3,+4
10 Gd 161 93.8
Dysprosium Dy 66 [Xe14{ 6i +3, (+4)
Tb 159 92.3
Holmium Ho 67 [Xe]4{116i +3
2 Dy 159 91.2
Erbium 68 [Xe]4i 6i +3
Ho 158 90
Thulium Tm 69 [Xe]4{136i (+2), +3
Er 157 89
Ytterbium Yb !
70 I [Xe]4i 46s2 +2,+3
Tm 156 88
4 1
Lutetium Lu I 71 [Xe]4i 5d 6i +3
Yb 170 86.8
The electronic configuration of lanthanum is [Xe]Si6i. It Lu 156 86
I
is expected that 14 elements from cerium to lutetium would be
formed by adding, 1, 2, 3, ... 14 electrons into the 4f level. On moving from Ce to Lu, the decrease in atomic radii occurs
However, it is energetically favourable to move the single electron from l6S to IS6 pm, i.e., the decrease is only 9 pm. Similarly,
on Sd into the 4f level in most of the elements but not in the the decrease in ionic radii occurs from 102 (Ce3+) to 86 (Lu3+)
cases of Ce, Gd and Lu. In Gd and Lu besides si,
the pm, i.e., the decrease is only 16 pm. Thus, for an increase of
4f-orbitals are half filled or fully filled. This gives extra stability 14 in the atomic number, the decrease in atomic radii or ionic
to the core. The extra stability of half filled and fully filled radii are. very small in comparison to the elements of other
4
forbitals is also seen in Eu(4/6i) and Yb(4/ 6i). groups and periods.
Cause of lanthanide contraction: As we proceed from volumes, in general, increase with increase in atomic number.
one element to the next element in the lanthanide series, the But a regular trend is not observed. They have fairly high
nuclear charge, i.e., atomic number increases by one unit and melting points. However, no definite trend is observed.
the addition of one electron occurs at the same time in 41-
energy shell. On account of the very diffused shapes of f- ~ 5. Ionisation energies
orbitals, the 41 electrons shield each other quite poorly from Lanthanides have fairly low ionisation energies. lEI and lE2
the nuclear charge. Thus, the effect of nuclear charge increase values are quite comparable with the values of alkaline earth
is somewhat more than the changed shielding effect. This metals, particularly calcium. The sum of the first three ionisation
brings the valence shell nearer to the nucleus and hence the energies in kJ mol- I for each element are given below. The
size of atom or ion goes on decreasing as we move in the values are low.
series. The sum of the successive reductions is equal to the
total lanthanide contraction. Ce Pr Nd Pm Sm Eu Gd
Consequences of ianthanide contraction: The main 3512 3623 3705 3898 4033 3744 (kJ morl )
consequences of lanthanide contraction are the following: Tb Dy Ho Er Tm Yb Lu
..
(i) Similar chemical properties: Since the change in 3792 3898 3937 3908 4038 4197 3898 (kJ mol-I)
the ionic radii in the lanthanide series is very small, their chemical
. Dueto.low.yaluesof ionisatioJ)en~rgies,Jan~th.anide§. lli:ehighly__. . _ .
properties are siiillIar. Thus~Tfisveryi:lifficun ~foseparate
electropositive in nature. These. elementll rell~L with~old. a~
elements in the pure state; However,hmtnaniae ccontraction hot water to liberatehydrogen:~The reactions are,h()wever;-
brings some differences in properties like solubility, complex slow with cold water but fast with hot water.
ion formation, hydration, etc. These differences help in the The values of standard reduction potential (E' values)
separation of lanthanide elements by fractional crystallisation increase from La to Lu. EO values become less negative in the
or ion exchange methods. series. The values in volts are given.
(0) Basic strength of hydroxides: As the size of the
lanthanide ions decreases from Ce3+ to Lu 3+, the covalent La Ce Pr Nd Pm 8m Eu Gd
character of M-OH bond increases and hence the basic strength -2.52 -2.48 .:..2.46 -2.43 -2.42 -2.41 -2.40 -2.39(Volt)
decreases. Thus, Ce(OHh is most basic while Lu(OHh is Tb Dy Ho Er Tm Yb Lu
least basic. -2.39 -2.35 -2.32 -2.30 -2.28 -2.27 -2.25 (Volt)
(iii) Similarity of second and third transition series: In
All the lanthanides are, thus, strong reducing agents. The
vertical columns of transition elements, there is an increase in
reducing power decreases from La to Lu.
size from first member to second member as expected 'but
from second member to third member, there is very small iftj 6. Coloured ions
change in size and sometimes sizes are same. This is due to
lanthanide contraction. Many of the lanthanide ions are coloured in solid state as
well as in solutions. The colour is due to partially filled f-
Group number 3 4 5 6
1st transition series Sc
orbitals which allow f-f transitions. M3+ ions having 4l, 4/
(144 pm) or 4/ 4 configurations are colourless.
2nd transition series Y Zr Nb Mo 3
(162 pm) (145 pm) (134 pm) (130 pm)
La +(4fo) }
3rd transition series La (Lanthanides) Hf Ta W Gd 3+(4f7) Colourless
(168 pm) (144 pm) (134 pm) (130 pm) Lu 3+(4fI4)
In each vertical column of transition elements, the elements of
Pairs of M 3+ ions having the same number of unpaired
second and third transition series resemble each other more
electrons in 4f-orbitals have the same colour.
closely than the elements of first and second transition series
on account of lanthanide contraction. The pairs of elements
such as Zr-Hf, Mo-W, Nb-Ta, etc., possess almost the same
properties.
~ 4. Physical properties
All the lanthanides are metals. They are soft, malleable and
ductile in nature. They are not good conductors of heat and [Note: The cations namely Ce3+(4fl) and Yb3+ (4f 13) are colourless
electricity. They are highly dense metals and their densities are inspite of the fact that these ions have one f-orbital singly
in the range of 6.77 to 9.74 g cm-3 . The densities and atomic occupied. These exceptions are difficult to explain.]
Transition Elements or d-block Elements andf-block Elements 707
7. Magnetic properties (iii) Lanthanum oxide is used for polishing glass. Neo-
dymium and praseodymium oxides are used for making
Ions having unpaired electrons are paramagnetic while those
coloured glasses for gOifles. Ce02 is used in gas
having all the orbitals paired are diamagnetic. The lanthanide mantles. .
4
ions (M3+) except La3\4l) and Lu3+(4/ ) are paramagnetic (iv) Ceric sulphate is a well known oxidising agent in
since they contain 1, 2, ... 7 unpaired electrons. volumetric analysis.
(v) Many lanthanide oxides are used as phosphorus in colour
;;5 8. Chemical reactivity TV tubes.
All the lanthanides have almost similar chemical reactivity. (vi) Various compounds of lanthanides are used as catalysts
The metals tarnish readily in air and on heating in O 2 form for hydrogenation, dehydrogenation, oxidation and
oxides of the type M 20 3. The one exception is cerium which petroleum cracking.
forms Ce02 rather than Ce203' The oxides are ionic and basic. (vii) The compounds of lanthanides are used in making
The metals react with hydrogen but often require heating up magnetic and ,electronic devices for their paramagnetic
to 300-400°C. The products are solids of formula MH3. The and ferromagnetic properties.
hydrides are decomposed by water and react with 0;. The (viii) Neodymium oxide dissolved in selenium oxy-chloride ..
is used theseditys as it powerful liquid laser.
--~- --~-.---
anhydrous haHdes,MX3,-can be made by heating t1iemetarafid

halogen or by heating the .metal oxide with the appropriate . -
ammonium halide. 14~2ti GENERAL CHARACTERISTICS

-.~
M203 + 6NH4Cl 300"C) 2MCl3 + 6NH3 + 3H20 OF ACTINIDES

Excepting Ac, Th, Pa and U which occur in nature in uranium
The fluorides are very insoluble. The chlorides are deliquescent
minerals, all the remaining actinides are unstable and synthetic
and soluble. At elevated temperatures, lanthanides react with
elements. These have been made by artificial nuclear trans-
N, C, S, P, As, Sb and Bi. A wide variety of oxo salts are
mutations. All the actinides are radioactive. Actinides are
known. The carbonates, phosphates, chromates, oxalates, etc.,
analogous to lanthanides and involve the filling of 5f-orbitals.
are largely insoluble in water while nitrates, acetates, sulphates,
The following general characteristics are shown by actinides:
etc., are soluble.
Because of their similar chemical reactivities, their separation
1. Electronic configuration
from one another is very difficult.
In lanthanides, after lanthanum 4f-orbitals become appre-
9. Complex formation ciably lower in energy than the 5d-orbitals. Thus, in lanthanides
the electrons fill the 4f-orbitals in a regular way with minor
The lanthanides do not have much tendency to form
differences where it is possible to attain a half ftIled shell.
complexes due to low charge density because of their large
Similarly, it might have been expected that after actinium the
size. However, the tendency to form complexes and their stability
5f-orbitals would become lower in energy than the 6d-orbitals.
increases with the increase of atomic number.
However, for the first four actinide elements, Th, Pa, U and Np
•. Uses of Lanthanides the difference in energy between 5f and 6d-orbitals is small.
Thus, in these elements (and their ions) electrons may occupy
The metals are seldom used in pure state. As lanthanides do the 5f or the 6d levels or sometimes both. Later in the actinide
not differ much in their physical and chemical properties, these series the 5f-orbitals do become appreciably lower in energy.
are mostly used in the form of alloys. Some common uses of Thus, from Pu onwards the 5f-shell fills in a regular way and
lanthanides and their compounds are given below: the elements become very similar. The most widely accepted
(i) Misch metal (an alloy): Misch metal is an alloy electronic configurations of actinides are tabulated below. The
consisting lanthanide metals (94-95%), iron (5%) and general electronic configurations of actinides may be written
traces of sulphur, carbon, silicon, calcium and alumi- as:
nium. The main lanthanide metals present are cerium [Rn]5f 1-146d O, 1 7l
(about 40%), lanthanum and neodymium (about 44%).
These alloys are used for making ignition devices such Name of the Atomic Electronic Oxidation
Symbol
as tracer bullets, shells and flints for lighters. element number configuration states
An alloy of magnesium and about 3% misch metal is Actinium Ac 89 [Rn]6d\7i +3
used in making jet engine parts. Cerium-magnesium Thorium Th 90 [Rn]6d 2 ,7i +3, +4
alloys are used in flash light powders. Protactinium Pa 91 [Rn]5l;6d 1,7i +3, +4, +5
(ii) Cerium salts are used in dyeing cotton, in lead Uranium U 92 [Rn]5l,6di,7i +3, +4, +5, +6
accumulators· and as catalyst. Neptunium ... Np. 93 [Rn]5f\6d 1,7i +3, +4, +5,+6, +7
·708 G.R.B. Inorganic Chetnistry for Competitions
Plutonium Pu 94 [Rn]5f 6 ,7i +3,+4,+5,+6,+7 The lower oxidation states tend to be ionic and the higher
Americium Am 95 [Rn]5/,7i +2,+3,+4,+5,+6 ones are .covaIent. M2+ , M 3+ and'MA+ .
. Ions are kn own.
Curium em 96 [Rn]5/,6d1,7i +3', +4 Hydrolysis of these ions occurs quite readily but can be
Berkelium Bk 97 [Rn]5f 9 ,7i +3, +4 suppressed by using acid solutions. Hydrolysis of compounds
Californium Cf 98 [Rn]5l0,7i +2, +3 in the higher oxidation states gives +S-MO~ ions and +6-MO~+
Einsteinium Es 99 [Rn]5f ll ;7;2 +2, +3 ions.
Fermium Fm 100 [Rn] 5f12,7i . +2, +3
._- 3. Physical properties
Mendelevium Md 101 [Rn]5f 13 ,7i +2, +3
4
Nobelium No 102 [Rn]5l ,7i +2, +3 The elements are all silvery metals. The melting points are
Lawrencium Lr 103 [Rn]5f I4 ,6d l ,7i +3 moderately high but are considerably lower than those of
transition elements. The size of the ions decreases gradually
~ 2. Oxidation states along the series because the extra charge on the nucleus is
poorly screened by the f electrons. This results in an 'actinide
The known oxidation states of the actinide elements are contraction' sitnilar to the lanthanide contraction. Actinides
shown in the above table. The actinides exhibit most common have high' densities. Some properties of the actinides up to
oxidation state of +3 like the lanthanides. However, this state berkelium are tabulated below. Not much information is available
IS not illwaysmost siilbleasforthe fustfourefements(Tfi,Pa,
------------------ --------------.--~----- --- - ----------------~--- - ------
about heavy actinides. ..- -------
U and Np). For example, U 3+ is readily oxidisedin air and ill .

Element Melting point Dens~ Radius M3+ Radius M4+
solution. +3 state is the most stable state for the later elements (0C) (g em ) (pm) (pin)
Am ---7 Lr (except No). The most stable oxidation states for the
Thorium 1750 11.8 108 94
first four elements are Th (+4), Pa (+S) and U (+6). These
Protactinium 1552 15.4 104 90
high oxidation states involve using all the outer electrons
Uranium 1130 -19.1 102S 89
including f electrons for bonding. Though Np shows +7
oxidation state but it is oxidising and the most stable state for Neptunium 640 20.5 101 87
Np is +S. Pu shows all the oxidation states from +3 to +7 but Plutonium 640 19.9 100 86
the most stable is +4. Am shows oxidation states from +2 to Americium 1170 13.7 97.5 85
+6. Am2+ has an / configuration. It is the analogue of Eu 2+ Curium 1340 13.5 97 85
but it only exists in solid as fluoride. However, for Am and Berkelium 986 14.8 96 83
almost all the remaining elements +3 state is most stable.
+4 oxidation state exists for all the elements from Th to Bk. t,i:~ 4. Colour of the ions
2+ E 2+ F 2+ Md 2+ d N 2+· . . soIutI
· on.
Cf , s , m , an 0 eXIst as IOns III
Actinide ions are generally coloured. The colour of the ions
Their properties are like alkaline earth metals particularly Bi+.
depends on the number of electrons present in Sf-orbitals. The
It is the most stable state for No and corresponds to an /4
ions having no electron in Sf-orbitals (i.e:, Sl) or seven
configuration.
electrons in Sf-orbitals (i.e.,S/) are colourless. The ions having
+S oxidation state occurs for the elements Pa ---7 Am. A few
5 2 to 6 electrons in Sf-orbitals are coloured both in the crystalline
solid compounds are known in +S oxidation state but M + ions
and in aqueous solution. The colour is due to f-f transition.
do not occur in solution. However, MO~ ions exist between
pH 2-4. These ions disproportionate rapidly in solution. Th4+ U 3+ Np3+ Pu 3+ Am 3+ Cm3+ U 4+ Np4+
(5f 6)
2UO~ + 4W ~ U4+ + UO~+ + 2H20 (5fo) (5l) (5f4) (5l) (5/) (5f) (5/)
(+5) (+4) (+6) Colour- Red Purple Violet Pink Colour- Green Yellow
less less green
+6 oxidation state occurs as fluorides, MF6, for the elements
U, Np, Pu and Am. The +6 state is more widely found as the ¥i 5. Magnetic behaviour
dioxoion, MO~+. The ion is stable and exists both in solution
and in crystals. Majority of the ions of the actinides possess unpaired
3
The Sf-orbitals extend into space beyond. the 6s and electrons, thus they are paramagnetic in nature. Th +(S/),
6p-orbitals and participate in bonding. This is in direct contrast Pa4+(S/), u3+(Sf\ Np5+(Sl), Pu4+(Sf\ Am5+(S/), etc.,
to the lanthanides where the 4f-orbitals are buried deep inside are paramagnetic. Cations of actinides which contain only
in the atom, totally shielded by outer orbitals and thus unable
paired electrons are diamagnetic. Ac 3+(SfO), Th4+(SfO),
to take part in bonding. The participation of the Sf-orbitals
U 6+(SfO), Lr3+(S/\ etc., are diamagnetic in nature.
explains the higher oxidation states shown by earlier actinide
elements.
tiil 6. Formation of complexes 1 COMPARISON OF LANTHANIDES

Actinides have somewhat higher tendency to form complex AND ACTINIDES
compounds in comparison to lanthanides. This is due to their Both lanthanides and actinides are f-block elements, i.e., they
higher charge and smaller size of their ions. Most of the halides involve filling of the j-subshell in the ante-penultimate shells of
of actinides form complex compounds with alkali metal halides. their atoms. Th\fir general electronic configuration can be written
Actinides form chelates with organic compounds such as EDTA as:
and oxine. The degree of complex formation for the ions ~,
MO~+, M3+ and MO"2 decreases in the order
where n = 6 for lanthanides and n = 7 for actinides. Due to
~ > MO~+ > M3+ > MO"2
similar electronic configuration, they show similarities in
properties but differ also in some of therr characteristics.
7. Chemical Reactivity
On account of low ionisation energies, the actinides are ~ Similarities
--~ .. ~--
highly electropositive metals. Theyreact-with-hot water and . (ilIrf theat6ms 6fllie- elements ofbothilie series, three
tamishin air· fonning anoxi<!e:cQatirlg,The:Il:l{~tills~~aGtreadily ~... ..outennoSFslfells-arepartly~filleawhiIe::t1:le~reriirunini~·ihner-;-~-···
with HCI but reactions with other acids are slower than expected. shells are completely filled. Two electrons· are present in the
Concentrated HN03 makes Th, U and Pu passive. The metals outermost energy shell, 18 or 19 electrons are present in the
react with oxygen, the halogens and hydrogen. Actinides act penultimate energy shell [en - l)ip 6do,l] and next to the
as strong reducing agents. penultimate shell contains 18 to 32 electrons [en 2)s2iiO
1 14 . . . .....-
f - ]. However, in two elements lutetium and lawrencium the
8. Radioactivity f-subshell is completely filled. These are the end members· of
All the actinide elements are radioactive in nature. the two series.
(ii) The eiements of both the series show mainly +3
•. Uses of Actinides oxidation state.
(iii) The elements of both the series are electropositive in
Thorium, uranium and plutonium are three actinides which
find uses as such or in the form of compounds. nature. They are reactive metals and act as strong reducing
agents.
(i) Uses of thorium : (a) When thorium dioxide containing
(iv) In both the series, there is contraction in atomic and
1% Ce02 is heated in a gas flame, it emits a brilliant white light.
ionic (M3+ ions) size as the atomic number increases, i.e., like
Because of this, it is used for making incandescent gas mantles.
lanthanide contraction, there is actinide contraction. These
The mantle made from silk fibre is treated with a mixed solution
of 99% thorium nitrate and 1% cerium nitrate. When this contractions are due to the poor shielding effect between the
electrons residing in (n - 2)f-orbitals.
mantle is fixed in the lamp and ignited, the silk fibre bums
away leaving behind a network of thoria (Th0 2) and ceria (v) Cations with unpaired electrons in both the series are
paramagnetic.
(Ce0 2)'
(b) Naturally occurring thorium is almost entirely Th-232. (vi) Most of the cations of lanthanides and actinides are
coloured. The cations having same number of unpaired elec-
This isotope is not fissionable but is converted into U-233
which is fissionable. .trons have almost same absorption spectra. Sharp line like
bands are observed in both the series. These are due to the
232,..."
9o- In
+ 1
on --,
----'0. 233 -L 233 -=L 233
90 Th - - , 91 p a - - , 92 U
jump of an electron from one energy level to another within
(n 2)f-orbitals.
Thus, thorium is used for the production of fissionable material (vii) The nitrates, perchlorates and sulphates of trivalent
needed for atomic reactors. actinides as well as lanthanides are soluble while the hydroxides,
(c) Thorium salts are used in medicines for the treatment of carbonates, fluorides of the elements of both the series· are
cancer. insoluble.
Cli) Uses of uranium: (a) The salts of uranium find use (viii) Ion exchange behaviour is exhibited by both actinides
in glass industry (for imparting green colour), textile industry, and lanthanides.
ceramic industry and in medicines.
(b) The U-235 isotope is used as nuclear fuel in atomic U Dissimilarities
reactors and atom bombs. Differences in some of the characteristics of lanthanides
(iii) Uses of plutonium: Pu-239 is used as a nuclear and actinides are given in the table which is on next page.
fuel. It is obtained from U-238.
S. (iv) Oxides and hydroxides of Oxides and hydroxides of

Lanthanides Actinides lanthanides are less basic. actinides are more basic.
No.
(i) Except promethium, all the All the actinides are radioactive. (v) Lanthanides have less tendency Actinides have more tendency
remaining lanthanides are non- to fonn complex compounds on to fonn comple.x compounds on
radioactive. account of low charge density. account of high charge density.
(ii) Besides +3 oxidation state, lan- Besides +3 oxidation slate, acti- (vi) The rnagneticnature (pararna- The magnetic nature (paramag-
thanides in some cases show nides. show a variety of oxidation gnetic) can easily be explained.netic) cannot be explained easily.
+2 and +4 oxidation states. . states like +2,+4, +5, +6 and +7 The observed values usually do
not tally with expected values,
also.
(iii) 'anthanides do not form oxo- Actinides fonn oxo-ions such as (vii) Most of the tripositive ions are MoSt of the tripositive and
UO~+, PuO~+, UQ+, UO!. etc. colourless. i tetrapositive ions are coloured.
These ions are stable in acid and

aqueous solutions.
Example 1. Give the number of unpaired electrons in the Example 3. Answer the following:
following: ( I') Wh'ICh one 0ifFe 2+ andFe3+ wns
. . more paramagnetIc
IS .
(i) Cr 2+(Z = 24) (ii) Fi+ (Z = 26) and why?
(iii) Mn 2+ (Z = 25) (tv) n4+ (Z = 22) (if) Which of the following ions are expected to be coloured
(v) l£l3+ (Z = 57) (vi) Zn 2+ (Z = 30) and why?
Solution: Cu+, Fi+, Mn 2+, Cr3+, Sc 3+, Ti4+
(Ui) Name the two elements offirst transition series which
Electronic configuration of Cr2+ =3d4 -'-i--L-'----L-'-.--L~____..J
1L have abnormal electronic configuration and why?
=4
Unpaired electrons (tv) Name the lightest and heaviest elements in terms of
2
Electronic configuration of Fe + = 3d
6
'-'-''--'--'--'--'--'--'--'---'--'
density among the transition elements.
(v) How many elements are present in each transition series?
Unpaired electrons 4 = 3d
Why this number cannot be less or more?
2
Electronic configuration of Mn + =3d 5 If lilililil Solution:
Unpaired electrons =5 (i) Fe3+ is more paramagnetic than Fe 2+ as Fe3+ consists
Electronic configuration of Ti4+ = li,2i2p6,3i3p63dOAi five unpaired electrons while Fe 2+ possesses four unpaired
Unpaired electrons =0 electrons.
Electronic configuration of La3+ =2, 8, 18, 18, 8+5do, 6so .(ii) Any ion of transition elements which possesses unpaired
Unpaired electrons 0 d electrons, i.e., d-d transition is possible shows a charac-
Electronic configuration of Zn2+ = 2, 8, 8 + 3io 3d teristic colour" (n-l)do or (n-l)d lO configuration does not
Unpaired electrons =0 Ii Ii I Ii Ii 1
J, J, jJ, J, J, involve d-d transition and hence, is colourless.
Fe2+, Mn2+ and Cr3+ are coloured, while Cu+, Sc 3+ and
Example 2. Why does Mn (II) show maximum para-
Ti4+ are colourless.
magnetic character amongst the bivalent ions of the first
transition series? Calculate the theoretical value of magnetic Ion Configuration Ion Configuratiop.
moment. eu+ 3dlO (colourless); Cr3+ 3d3 (coloured)
Solution: Fe2+ 6
3d (coloured); Sc3+ 3do (colourless)
The value of paramagnetic nature depends on the number Mn 2+ 5 Ti4+
3d (coloured); 3do (colourless)
of unpaired orbitals. Mn (IT) possesses maximum number of
unpaired orbitals amongst divalent ions of the first transition (iii) Chromium and copper.
series and thus, possess maximum value of paramagnetic Chromium attains 3~Asl configuration in which all the d-
character. orbitals are unpaired in order to get extra stability.
Theoretical value of magnetic moment = ~n(n + 2) Copper attains 3dlO ,4s1 configuration in which all the d-
=
.J5 x 7 as n = 5 orbitals are paired in order to get extra stability.
=.J35 = 5.91 B.M. (iv) Lightest element-Scandium;
Heaviest element~smium
(v) Each transition series consists ten elements. This (vi) AgCI dissolves in KCN forming a complex, potassium
number cannot be 9 or 11 as the maximum capacity of d-orbitals argentocyanide. The addition of zinc precipitates silver.
is of 10 electrons which are gradually filled up. AgCI + 2KCN ----7 KAg(CNh + KCI
1st Tr. series 3i-10 Ten elements 2KAg(CNh + Zn ----7 K2Zn(CN)4 + 2Ag
Potassium
2nd Tr. seri~ 4d1- 10 Ten elements zincocyanide
3rd Tr. series 5d 1- 10 Ten elements (vii) ZnO dissolves in NaOH forming sodium zincate,
Example 4. What happens when? ZnO + 2NaOH ----7 Na2Zn02 + H20
(i) Ferric chloride is added to potassium ferrocyanide. (vili)Deep red colouration due to the formation of a complex
(ii) Iron reacts with cold dilute nitric acid. [IJ.T.1990] is developed,
(iii) Potassium ferricyanide is added to ferrous sulphate. FeCl3 + N~CNS ----7 Fe(CNS)CI2 + N~Cl
(i v) Excess ofpotassium iodide is added to mercuric chloride. or FeCl3 + 3NH4CNS ----7 Fe(CNSh + 3NH4C1
(v) Green vitriol is strongly heated. [Roorkee 1990]
(vi) Silver c~loride is treated with aqueous sodium cyanide Example 5. Explain the following:
and~the~ product thusfonned is allowed to .react with zinc in (i) AcidijiedK2Cr207solution . turns. green. when sodium----~
alkaline medium. [M.hN.R.l996] sulphite is added to it.
(vii)Zinc oxide is treated with excess of sodium hydroxide (ii) Partial roasting of sulphide ore is done in the metallurgy
solution. of copper. .
(viii) Ammonium thiocyanate is added to ferric chloride (iii) Zinc becomes dull in moist air.
solution. (iv) In the metallurgy of iron, limestone is added to the ore.
Solution: (v) A little acid is always added in the preparation of
(i) Prussian blue is formed. aqueous ferrous sulphate solution.
4FeCl3 + 3K4Fe(CN)6 ----7 Fe4[Fe(CN)6h + 12KCI (vi) The addition of NaOH solution to a solution of zinc
Prussian blue chloride produces a white precipitate which dissolves onfurther
(Ferri ferrocyanide)
addition of NaOH.
(ii)' Ammonium nitrate is formed.
(vii) The addition of NH40H to ZnS04 solution produces
[Fe + 2HN0 3 ----7 Fe(N03h + 2H] x 4 white precipitate but no precipitate is formed if it contains
HN03 + 8H ----7 NH3 + 3H20 NH4 CI.
NH3 + HN0 3 ----7 NH 4N0 3 (viii) Mercuric chloride and stannous chloride cannot exist
as such if present together in an aqueous solution.
4Fe + lOHN03 ----74Fe(N03h+NH4N03+3H20
(ix) Zinc and not copper is used for the recovery of silver
(iii) Ferrous ion is fust oxidised to ferric ion while from complex [Ag( CN)2r.
ferricyanide ion is reduced to ferrocyanide ion. Then, ferric (x) Why is chalcocite roasted and not calcined in the
ions react with ferrocyanide ions to form potassium ferric extraction of copper?
ferrocyanide (Turnbull's blue). (xi) Copper implements were known to mankind much earlier
Fe2+ -t' [Fe(CN)6]3-·----7 Fe3+ + [Fe(CN)614- than iron implements.
(xii) Copper sulphate dissolves in NH40H solution but
K+ + Fe3+ +[Fe(CN)6]4- K+Pe 3+[Fe(CN)6]4-
Potassium ferricferrocyanide FeS04 does not.
(Turnbull's blue) (xiii) A ferrous salt turns brown in air.
(iv) First scarlet precipitate is formed which then dissolves (xiv) A ferrous salt decolourises acidified KMn04 solution.
in excess of potassium iodide forming a complex. (xv) Cadmium is used to extinguish nuclear fire.
(xvi) Copper hydroxide is soluble in ammonium hydroxide
HgCl2 + 2KI ----7 HgI2 + 2KCI
but not in sodium hydroxide.
HgI2 + 2KI K2HgI4
Potassium tetraiodo mercurate
Solution:
(colourless) (i) Na2S03 is a reducing agent. It reduces acidified K2Cr207
(v) When heated strongly, a mixture of gases consisting to chromic sulphate which is green in colour.
S02 and S03 is evolved and a red residue, Fe203 is formed. K2Cr2~ + 4H2S04 ----7 K2S04+Cr2(S04h+4H20+3[0]
[FeS04·7H20 ----7 FeS04 + 7H20] x 2 [Na2S03 + [0] ----7 Na2S04] x 3
2FeS04 ----7 Fe203 + S02 + S03 K2Cr207 + 3Na2S03 + 4H2S04 ----7 K2S04 + Cr2(S04h
S03 + H20 ----7 H2S0 4 Green
+ 3Na2S04 + 4H 20
2FeS04·7H20 ----7 Fe203 + S02 + H2S04 + 13H20
Green vitriol Red
(ll) The concentrated ore is roasted in reverberatory furnace (viii) HgCl 2 is an oxidising agent while SnCl 2 is a reducing
in a current of air. The volatile impurities such as free sulphur, agent. When both are present, a redox reaction occurs forming
arsenic and antimony are removed as volatile oxides and the Hg and stannic chloride as final products.
ore is partially oxidised. SnCl2 + 2HgCl2 ------7 Hg2Cl2 + SnCl4
4As + 302 ------7 2As203 White
4Sb + 302 --:------7 2Sb 20 3 Hg 2Cl2 + SnCl2 ------7 2Hg + SnC4

Black or grey
S + O 2 ------7 S02 (ix) Zinc is cheaper as well as stronger reducing agent in
2CuFeS2 + O 2 ------7 CU2S + 2FeS + S02 comparison to copper.
2CuFeS2 + 402 ------7 CU2S + 2FeO + 3S02 Zn + 2[Ag(CNh] ------72Ag + [Zn(CN)4P-
2CU2S + 302 ------7 2CU20 + 2S02 (x) Air i3 necessary to convert impurities such as sulphur,
A mixture of sulphides and oxides is formed. The CU20 so arsenic and antimony into volatile oxides and for partial oxidation
formed reacts with unconverted CU2S to form copper. of the pyrite ore. Calcination does not use oxygen while roasting
CU2S + 2Cu20 ------7 6Cu + S02 is done in presence of air. Thus, roasting and not calcination
(iii). When zinc is e~posed to moi~t the surface is affected is done in the metallurgy of copper.
with the formation of a film of basic zinc carbonate on it. Due ·Seereacuons in answer(H):·· .
to this zinc becomes dulL . (xi) Copper occurs in nature also as a free~metarbtitiron . .
[2Zn + 2H20 + O 2 ------7 2Zn(OH)2] x 2 is always found in nature in combined state. The technology
to manufacture iron was developed much later. Hence iron
Zn(OHh + C02 ------7 ZnC03 + H20
implements were used later than copper implements as copper
ZnC03 + 3Zn(OHh ------7 ZnC0 3·3Zn(OHh was known in the early times.
(xii) Copper sulphate dissolves in the ammonium hydroxide
Basic zinc carbonate due to formation of a copper complex. Ferrous sulphate reacts
(iv) Limestone is added asa flux. It is decomposed in the with NH40H to form insoluble Fe(OHh It does not form any
furnace into CaOand CO2. CaO reacts with gangue silica and complex with ~OH.
forms infusible slag, CaSi03. CUS04 + 4NH40H ------7 [CU(NH3)4]S04 + 4H20
CaG03 ------7 CaO + CO2 Deep blue solution
CaO + Si02 ------7 CaSi03 FeS04 + 2NH 40H ------7 Fe(OHh + (NH4hS04
Slag Insoluble
. (v) Ferrous sulphate is a salt of a weak base and a strong (xiii)A ferrous salt turns brown in air due to oxidation to
acid. Thus, its hydrolysis occurs when it is dissolved in water ferric salt.
and solution becomes turbid due to formation of ferrous (xiv) Ferrous salt acts as a reducing agent. It reduces acidi-
hydroxide. fied KMn04 into K 2S04 and MnS04 which form colour-
FeS04 + 2H20 ~ Fe(OHh + H2S04 less solution, i.e., decolourisation of KMn04 solution takes
Addition of a small amount of acid shifts the equilibrium place.
towards, left and thus prevents hydrolysis. 2KMn0 4 + 3H2S94.------7 K2S04 + 2MnS04 + 3H20 + 5[0]
(vi) On addition of NaOH, a white precipitate of Zn(OHh [2FeS04 + H 2S04 + [0] ------7 Fe2(S04h + H20] x 5
is formed which dissolves in excess of NaOH forming sodium
2KMn04 + lOFeS04 + 8H2S04 ------7 K2S04 + 2MnS04
zincate.
+ 5Fe2(S04h + 8H20
ZnCl2 + 2NaOH ------7 Zn(OHh + 2NaCI
(xv) Cadmium absorbs neutrons, stops nuclear fission
Zn(OHh i;. 2NaOH ------7 Na2Zn02 + 2H20
Soluble reaction and extinguishes nuclear fire. . .
(vii) ~OH is a weak hydroxide. It ionises slightly (xvi) Cu(OHh dissolves in NH 40H by forming a complex.
furnishing OH- ions. However, the OH- ions are sufficient to Cu(OHh + 4NH40H ------7 [Cu(NH3)4](OHh + 4H 20
cause the precipitation of Zn(OHh as its solubility product is Cu(OHh is insoluble in NaOH as no such complex is formed.
exceeded.
Zns04 + 2NH40H ------7 Zn(OHh + (NH4hS04
White ppt. (i) Magnesium oxide is used for lining of steel making
In presence of ~a, the ionisation of NH40H is further furnace. .
suppressed and sufficient OH- ions are not available to cause (ii) Cast iron is hard but pure iron is soft in nature.
precipitation as the solubility product is not exceeded. (iii) Fe 3+ is more stable than Fi+.
(iv) Anhydrous FeCl 3 cannot be obtained by heating (b) It reduces CO2 into CO which is used as a fuel
hydrated ferric chloride. - CO2 + C -----7 2CO
(v) The compounds of iron are coloured and paramagnetic. (ix) H2S04 is a covalent compound. Cone. H2S04 does
(vi) Mercuric chloride is called corrosive sublimate. not contain H30+ ions while dilute H2S04 consists H30+ ions
(vii) The colour of mercurous chloride changes from white which react with zinc to liberate hydrogen.
to black when treated with ammonia solution.
. H 2S04 + 2H20 ~ 2H30+ + SO~-
(viii) Excess of carbon is added in the zinc metallurgy.
. (ix) Zinc readily liberates hydrogen from cold dilute H 2S04 Zn + 2H30+ ~ Zn2+ + H2 + 2H20
but not from cold concentrated H2S04. . (x) In the compounds of zinc. m(;:tals, M2+ ions possess
lO
(x) The compounds of Zn, Cd and Hg are usually. white. the penultimate d-orbitals doubly occupied, i.e., (n-l)d
(xi) A dark blue precipitate is formed when sodium hydroxide configuration. There is no d-d transition. Hence, the compounds
solution is added to coppe·r sulphate solution. The precipitate of zinc metals are colourless.
darkens on heating. (xi) NaOH reacts with CUS04 when dark blue precipitate
(xii) Cuprous chloride is insoluble in water and dilute HCi of Cu(OH)z is formed. This precipitate on heating forms CuO
but dissolves in concentrated HCI. which is black in colour. Hence, the colour darkens on heating.
TiliiT CuSisnofpreCipltateabYptisslng H;S through copper CUS04 +2Na6H~ CU(OH)2 +Na.;s6~
.. Blue - ...... .
-'""------
sulphate· solution containIng KCN. ---
(xiv) Silver nitrate solution is kept in dark coloured bottles. Cu(OH)z CuO + H 20
Black
Solution:
(xii) CU2Cl2 dissolves in cone. HCI due to the formation of
(i) MgO is basic in nature. It removes acidic impurities
a copper complex.
present in cast iron used for making steels.
MgO + Si02-----7 MgSi03 CU2Cl2 + 2HCI -----7 2H[CuCI2]
Slag (xiii) CUS04 forms a complex with KCN.
3MgO + P205 -----7 Mg3(P04h CUS04 + 2KCN -----7 CU(CN)2 + K2S04
MgO is also a refractory material as it can tolerate very high 2CU(CN)2 -----7 CU2(CNh + (CNh
temperature of the furnace. CU2(CN)z+6KCN -----7 2K3CU(CN)4~6K++2[Cu(CN)4]3-
(ii) Cast iron consists carbon 2.5 to 5% which is responsible 2
K3CU(CN)4 complex does not furnish Cu + ions. Hence, no
for its hardness.
precipitate of CuS is formed when H2S is passed through
(iii) Fe3+ has the configuration [Arn;, i.e., all the five· solution.
d-orbitals are singly occupied which i<: stable configuration (xiv) AgN03 is photosensitive. It decomposes in presence
in accordance to Hund's rule of maximum multiplicity while of light. To prevent its decomposition, it is kept in coloured
the configuration of Fe2+ is [Ar] 3d in which one orbital is
6
bottles as these do not permit light to pass through.
doubly occupied and rest of the four orbitals are singly occupied. Example 7. Explain the following: .
It is not so stable configuration as it is unsymmetrical in nature.
(i) Copper (I) salts are not known in aqueous solutions.
(iv) On heating hydrated ferric chloride, anhydrous ferric
(li) Ferric iodide is very unstable but ferric chloride is not.
chloride is not formed as water of crystallisation reacts to
(iii) Silver bromide is used in photography.
form Fe203 and HC!.
(v) Iron compounds either has Fe2+ or Fe3+ ions and each (iv) Anode mud in copper refining contains silver and gold.
contains unpaired orbitals which show paramagnetic character. (v) Silver fluoride is fairly soluble in water while other
d-d transition is possible. Hence, the compounds are coloured. silver halides are insoluble.
(vi) HgCl2 is poisonous (corrosive) in nature. It undergoes (vi) Copper is regarded as transition metal though it has
lO
sublimation. Due to these properties, it is called corrosive completely filled d-orbital (d ). [M.L.N.R. 1994]
sublimate. . (vii) Out of cobalt and zinc salts, which is attracted in a
. (vii) Hg2Cl2 reacts with NH3 to form a mixt~e of mercury magnetic field? lRoorkee 1995]
and mercuric amino chloride which is a black substance. (viii) The species [CuCI4]2- exist but [CuI4P- does not.
!l g + Hg(NH z)C~ + HCI
(ix) Copper is Largely used in electrical wiring.
[1.1 T. 1992]
White Bl~ck
(x) A solution of K2Cr04 changes colour on being acidified.
(viii) Carbon has to playa double role,
Solution:
(a) It reduces zinc oxide to zinc.
(i) Cu (I) salts undergo disproportionation in aqueous
. ZnO + C -----7 Zn + CO solution.
ZnO + CO -----7 Zn + C02 2Cu+ -----7 Cu2+ + Cu
(ii) 1- ion is a stronger reducing agent in comparison to Heat CU2 0

CuO+ Cu ~
CI- ion. Fe3+ is easily reduced by iodide ion. Powder
2Fe3+ + 21- ~ 2Fe2+ + 12 or CUS04 ~ Fehling's solution
(iii) AgBr is sensitive to light. It is converted into metallic C6Hlz06 + Fehling's soln. ~ CuzO + C6H 120 7
silver grains when light is incident on it. Glucose' Red ppt. Gluconic acid
(iv) Silver and gold are less basic than copper. These are (iii)Cu + 4HN03 (conc.) ~ Cu(N03)z + 2NOz + 2HZO
not ionised under the applied voltage and get deposited in the 2CU(N03h 2CuO + 4NOz + 02
anodic mud.
Heat
(v) The hydration energy of AgF is higher than its lattice CuO + Cu ~
CU20
energy. Hence, it is ~oluble in water. The hydration energy (iv) By heating a solid mixture of HgS04 and NaCl.
values of other halides are smaller than their lattice energy HgS04 + 2NaCI Heat) HgCl2 + NaZS04
values. Hence, these halides are insoluble in water.
(v) ZnS04·7HzO ZnS04 + 7HzO
(vi) Although copper has 3dlO configuration yet it can lose White vitriol Anhydrous
one electron from this arrangement. Thus, Cu 2+ ion has 3d9
configuration;· So;accordin~to 1hedefinition that transition
Zl1S(h~ea.t) ZDQ-I- SQ3u"n
metal cations have partially filled (n-l)d~subshell, copper is Zno + 2HCl ~ ZnCh + H2Q ...
regarded as a transition metal. ZnC1Z + 2NH4Cl ~ ZnClz'2Nl4Cl
(vii) Of cobalt and zinc salts, the cobalt salts are attracted Double salt
in a magnetic field, because cobalt ion containing unpaired ZnCI2·2~CI -=~ ZnC12 + 2Nl4CI
electrons. is characterised by a permanent magnetic moment. Anhydrous
Zn2+ ion contains 3dlO configuration, i.e., no unpaired electrons, (vi) Zno + H ZS04 ~ ZnS04 +HiO
so zinc salts are not attracted in magnetic field.
ZnS04 + 2NaHC03 ~ ZnC03 + Na2S04 + H 20 + CO2
(viii) 1- ion is a stronger reducing agent than CI- ion. It
(vii) FeS04·(NH4hS04,6H20 + 4NaOH ~
reduces Cu2+ ion into Cu+ ion. Hence, cupric iodide is converted
Fe(OH)z + 2NH3 + 2Na2S04 + 8H20
into cuprous iodide. Thus, the species [CuLi- does not exist. ppt. ~
(ix) Copper is a very good conductor of electricity. Fe(OH)2 + H 2S04 ~ FeS0 4 + 2H20
Moreover, it is not easily affected by the atmosphere.
The solution is put to crystallisation when crystals of ferrous
(x) On being acidified, the chromate ions dimerise to form
sulphate, FeS04,7H20, are obtained,
dichromate ions which are orange coloured. Thus,
2CrO~- + 2H+ ~ Cr20i- + H 20 (viii) 4FeC13 + 3~Fe(CN)6 ~ Fe4[Fe(CN)6h + 12KCI
Prussian blue
(Yellow) (Orange)
(ix) ZnS04;+ BaS ~ ZnS + BaS04
. Example 8. How the following conversions are made? Lithopone
Explain only by giving chemical equations. (x) 2CUS04 + 4Kl ~ CU212 + 2KzS04 + 12
(i) Copper chloride from copper nitrate. Whiteppt.
(ii) Cuprous oxide from copper sulphate. EXample 9. A metal chloride (x) shows the following
(iii) Cuprous oxide from copper.
reactions:,
(iv) Mercuric chloride from mercuric sulphate. (a) When H 2S is passed in an acidified solution of (x) a
(v) Anhydrous ZnCl2 from white vitriol.
black precipitate is obtained..
(vi) Zinc carbonate from zinc oxide.
(b) ,The black precipitate is not soluble in ammonium
( vii) Ferrous sulphate from ferrous ammonium sulphate.
sulphide.
(viii) Prussian blue from K4Fe(CN)6.
(c) The solution of stannous chloride is added to an aqueous
(ix) Lithopone from white vitriol.
solution of (x), a white precipitate is obtained which turns grey
(x) Cuprous iodide from copper sulphate.
on addition of more stannous chloride,
Solution: (d) When; aqueous solution of KI is added to an aqueous
(i) Cu(N03h + 2NaOH ~ Cu(OHh + 2NaN03
ppt.
solution of (x), a red precipitate is obtained which dissolves on
addition of excess of Kl.
CU(OH)2 + 2HCl ~ CuCl2 + 2H 20
Identify (x) and write down the equations for the reactions.
(ii) CUS04 + 2NaOH ~ Cu(OHh + Na ZS04
ppt. fRoorkee 1991]
Solution:
Cu(OHh Strongly) CuO + HzO
heated The acidified solution of (x) gives a black sulphide with H 2S
indicates that the chloride is of a basic cation of second group.
The sulphide is insoluble in ammonium sulphide, hence, the (v) (E) dissolves in ammonia solution giving a colourless
cation belongs to ITA group of mixture analysis. solution of (F). Identify (A) to (F) and give chemical equations
It gives white precipitate with SnCl2 which turns to grey in for reactions at steps (i) to (v). [Roorkee 1995]
excess of SnCl2 suggests that (x) is HgCI 2. It is further Solution:
confirmed by the reaction with KI. On the basis of the given data, the black mineral (A) is silver
Reactions : HgCl2 + H2S ~ HgS + 2HCI glance, Ag2S. It is confirmed by the following:
Black (i) It dissolves in sodium cyanide solution in presence of
2HgCl2 + SnCl 2 ~ Hg2Cl2 + SnCl4 air.
White Ag 2S + 4NaCN + 202 ~ 2[NaAg(CNh] + Na2S04
Hg 2Cl2 + SnCl2 ~ 2Hg + SnC4 Sodium Sodium
Grey .' argento cyanide sulphate
(8) (C)
HgCI 2.-t 2KI ~ HgI2 + 2KCI
Re(f ppt. (n) 2[NaAg(CNh] + Zn ~ Na2Zn(CN)4 + 2Ag
(8) (D)
HgI 2 + 2KI ~ K2HgI4
Soluble
(iii) 3Ag + 4HN03 ~ 3AgN0 3 + NO + 2H20
(D)
··~plelO. -AcertaininorganiccompoundEA)-on-heating
AgN03+ HCI AgCI +JIN03
loses itswaterofcrystallisation.70nfurther heating,ablackish
(E) . 1
brown powder (8) and two oxides of sulphur (C and D) are (iv) 2AgCI + Na2C03 ~ 2Ag + 2NaCI + CO2 + 2: ~
obtained. The powder (8) on boiling with hydrochloric acid (E) (D)
gives a yellow solution (E). When H2S is passed in (E), a white AgCI + 2NH40H ~ Ag(NH3hCI + 2H20
turbidity (F) and apple green solution (G) are obtained. The (E) (F)
solution (E) on treatment with thiocyanate ions gives a blood Colourless -solution
red coloured compound (lI). Identify the compounds from (A) (A) = Silver glance, Ag2S
to (lI). (B) =Sodium argentocyanide, NaAg(CNh
Solution: (C) =Sodium sulphate, Na2S04
The compound (A) on strong heating gives two oxides of (D) =Silver metal, Ag
sulphur, it may be a sulphate. The solution (E) on treatment (E) =Silver chloride, AgCl
with thiocyanate ions gives blood red coloured compound (H) (F) =Diamrnihosilver (I) chloride, Ag(NH3hCI
indicates that the solution (E) consists Fe3+ ions. Thus,. the Example 12. (i) A black coloured compound (8) is formed
compound (A)is ferrous sulphate, FeS04·7H20. on passing hydrogen sulphide through the solution of a
Reactions compound (A) in NH40H.
Fe203 + S02 + S03 (ii) (B) on treatment with HCI and potassium chlorate gives
(8) (C) (D) A.
Blackish (iii) (A) on treatment with potassium cyanide gives a buff
brown powder
coloured precipitate which dissolves in excess of this reagent
Fe203 + 6HCI ~ 2FeCl3 + 3H20 forming a compound (C).
(8) (E)
Yellow solution (iv) The compound (C) is changed into a compound (D)
when its aqueous solution is boiled.
2FeCl3 + H2S ~ 2FeCl2 + 2HCI + S
(G) (F)
(v) The solution of (A) was treated with excess of sodium
Apple White bicarbonate and then with bromine water. On cooling and
green solution turbidity shakingfor sometime, a green coloured compound (E) isformed.
FeCl3 + 3CNS- Fe(CNS)3 + 3CI- No change is observed on heating. Identify (A) to (E) and give
(E) Blood red chemical equations at steps (i) to (v). [Roorkee 1996]
coloured solution
Solution:
Example 11. (i) A black mineral (A) on treatment with
The formation of a black coloured precipitate on passing
dilute sodium cyanide solution in presence of air gives a clear H2S in alkaline medium indicates that the salt is either of cobalt
solution of (B) and (C). "," OJ:' nickel. However, the reaction (iii) suggests that (A) is a
(li) The solution (8) on reaction with zinc gives precipitate cobalt salt (CoCl 2). This is confirmed by the following
of a metal (D). reactions:
(iii) (D) is dissolved in dilute HN03 and the resulting solution (i) CoCI2+H2S+2NH40H ~ CoS + 2NH4CI + 2H 20
gives a white precipitate (E) with dilute HCI. (A) (8)
(iv) (E) on fusion with sodium carbonate gives (D). (n) CoS + 2HCI + [0] ~ CoCl2 + H20
(8) From KCI03 (A)
(iii) CoCl 2 + 2KCN ----1- 2KCl + CO(CN)2 (li)La3+ has a stable configuration of an inert gas
(A) Buff coloured [(Xe)5do6so], i.e., xenon (54-2, 8, 18, 18, 8). To obtain +4
Co(CNh + 4KCN ----1- K4CO(CN)6 oxidation state, the stable configuration is to be disturbed which
(C) is not possible under ordinary conditions and hence La4+ does
(iv) 2K4CO(CN)6 + H20 + [0] ----1- 2K3Fe(CN)6 + 2KOH not exist.
(C) From air (D) (iii) This is because gadolinium in +3 state has half filled
Pot. cobaltocyanide Pot. cobalticyanide
4f-subshell (4/) and lutetium in +3 state has completely filled
(v) CoCl2 + 2NaHC03 ----1- CO(HC03)2 + 2NaCI 4f-subshell which are very stable configurations.
(A)
(iv) Due to lanthanide contraction, the atomic radi\ of both
Co(HC0 3h + 4NaHC03 ----1- N~CO(C03h + 3C02 + 3H20 Zr and Hf are same. Hence, their properties are similar.
Br2 + H 20 ----1- 2HBr + [0] Example 16. Why is dilute sulphuric acid and not dilute
2N~Co(C03h + H20 + [0] 2Na3CO(C03h + 2NaOH HCl or HN0 3 used to acidify a permanganate solution in
(E) volumetric analysis?
Green coloured solution
Solution:
(EUs stable tQwardsheat. ~Volumetrietitrations . involving~ potassium perrilanganate
~-=E!81!!PJ~~13. When the ore haematite is bumtinair with solution are c~arried· out only ~in presenceQf diluteH2S04,:but~~
coke around 2000°C along with lime, the process not only not in presence of dilute HCl or dilute HN0 3. This is because
produces steel but also produces a silicate slag that is useful oxygen produced from KMn0 4 + dil. H2S04 is used only for
in making building materials such as cement. Discuss the same oxidising the reducing agent. Moreover, H2S04 does not give
and show through balanced chemical equations. [I.I.T. 1998] any oxygen of its own to oxidise the reducing agent.
[Hint : Haematite (F~03) on burning with coke and lime at 2000"C 2KMn04 + 3H2S04·~ K2S04+ 2MnS04 + 3H20 +·5[61-
results in the following:
C + O2 ----+ CO 2
Reducing agent + [0] ----1- Oxidised product
CO2 + C ----+ 2CO In case HCl is used, the oxygen produced from KMn04 is
partly used upto oxidise HCl and C1 2 is produced.
F~03 + 3CO ----+ 2Fe + 3C02
Steel 2KMn04 ----1- K20 + 2Mnu + 5[0]
Si02 + Cao ----+ CaSi0 3 K20 + 2HG:'1 ----1- 2KCl + H 20
Lime Slag
(used as a building material)] [MnO + 2HCl MnCl2 + H20] x 2
Example 14. An aqueous solution containing 1 mole of [2HCl + [0] ----1- H20 + C12] x 5
Hglz and 2 moles of Nal is orange in colour. On addition of 2KMn04 + 16HCI----1- 2KC1+2MnCI2+ 8H20+ 5Cl2
excess of NaI the solution becomes colourless. The orange In case HN03 is used, it itself acts as an oxidising agent and
colour reappears on subsequent addition of NaOt;(l. Explain partly oxidises the reducing agent.
with equations. [U.T. 1999]
[Hint : Hgl2 is sparingly soluble in water and gives orange solution. On
Example 17. What is the equivalent mass of KMn04 when
addition of excess ofNal, the colourless soluble complex Na2Hg14 it acts as an oxidising agent in acidic medium~molecular mass
is formed. KMn04 = 158)?
HgI2 + 2Nal----+ NazHgI4 Solution:
The complex reacts with NaOCI with formation of again HgI2, Oxidising action of KMn04 acidic medium is represented
i.e., orange colour is restored. as:
3Na2HgJ \ + 2NaOCI + 2H zO - 7 3Hglz + 2NaCI + 4NaOH + 2Nal3] 2KMn04 + 3H2S04 K 2S04 + 2MnS04 + 3H20 + 5[0]
Example 15. Explain: 2 x 158 g 5 x 16 = 80 g
2 2x158
(i) Why are Sm +, Eu2+ and Yb2+ good reducing agents? Eq. mass of KMn04 ::;: gox8 = 31.6
(ii) Can lanthanum (2 = 57) exhibit +4 oxidation state? or Eq. mass of KMn04
(iii) Why are +3 oxidation state of gadolinium (2 =64) and Molecular mass
lutetium (2 = 91) especially stable? = Number of electrons gained per molecule
(tv) Why do 2r and Hf exhibit similar properties?
Solution: = 158 = 31.6
(i) The most stable oxidation state of lanthanides is +3.
Hence, ions in +2 state tend to change to +3 oxidation state by or Mn04
loss of electron and act as reducing agents. Oxidation state +7
TransitionElements or d-block Elements andf-block Elements
Eq. mass of KMn04 Example 20. Transition metals of 3d-series do not react
Molecular mass readily with dilute acids to liberate hydrogen although they
= Change in oxidation state per molecule have high negative reduction potential values. Explain.
158
=5 31.6 Solution:
Most of the transition metals have the tendency to form a
Example 18. Explain the following giving suitable reason: protective layer of their oxides on the surface. This oxide layer
(i) Yellow coloured aqueous solution of sodium chromate is somewhat inert and does not permit the metals to react with
changes to orange red when CO 2 under pressure is passed. dilute acids to liberate hydrogen.
(ii) Green solution of potassium manganate, K 2Mn04> turns
Example 21. The atomic radii of the eLements in a
purple when CO 2 is circulated.
transition series do not vary much while they do vary in the
Solution:
case of sand p-block elements. ExpLain.
(i) Yellow coloured aqueous solution of sodium chromate
Solution:
changes to orange red on passing CO2 as H+ ions are formed
There are operating two effects namely nuclear charge effect
which are responsible for conversion of chromate into and screening effect which oppose each other. Due to increase
dichromate. in nuclear charge from member to member in a transition
..... CQ2-l::.Hz...Q_~_:u+-l::.HCQ3 .series,· theatemicradiitentt.todecrease. Atth~sametime;th~
2CrO~~,+2H-+-~ Cr20~:- +. H20. addition of extraelectrons.one by one to{n,.,l)d-orbitalsprovides::. .... ~ .
Yellow Orange red the screening effect. As the number of d electrons increases,
(li) CO2 gives H+ ions which are responsible for conversion the screening effect increases and this tends to increase size.
of manganate (green) to permanganate (purple). Due to these opposing tendencies, there is a very small change
in the atomic radii in a transition series. In s and p-block
CO2 + H 20 ~ H+ + HC03
elements, the extra electron is added· tosamesor p-subshell.
3MnO~- + 4H+ ~ 2Mn04 + Mn02+ 2H20 which does not exert screening effect and hence, the atomic
Green . Purple
radii decreases considerably in a period due to increase in
Example 19. Assign reason for each of the following: nuclear charge.
(i) Ce 3+ can be easily oxidised to Ce4+. . Example 22. The second and third members in each group
(ii) EO for Mn 3+/ Mn2+ couple is more positive than for of the transition elements have similar atomic radii. Explain.
3 Solution:
Fe +/Fi+ couple.
This is due to lanthanide contraction by the members of
(iii) Lu(OHh is a weaker base than La(OHh.
4f-series which occupy a position between lanthanum (Z =57,
Solution:
a first member of third transition series) and hafnium (Z 72,
(i) Ce3+ has the configuration 4i5do6so. It can easily lose second member of 3rd transition series).
an electron to acquire more stable configuration (4fo5do6l,
i.e., configuration of an inert gas, xenon 2, 8, 18, 18, 8), i.e., 2nd transition series Y Zr Nb Mo
3rd transition series La-Lanthanides Hf Ta W
Ce3+ can be easily oxidised to Ce4+.
. (58 to 71)
Ce3+ ~ Ce4+ + e
The pairs of elements such as Zr-Hf, Nb-Ta, Mo-W,· etc., .
(ii) E' for Mn3+/Mn2+ couple is more positive than for possess nearly the same atomic radii and almost the same
Fe +lFe 2+ couple because Mn2+ state is more stable than Mn3+
3
properties.
state. Thus, the reduction is spontaneous. Example 23. (a) Chromium is a typical hard metaL while
Mn 3+(3d 4,4so) + e ~ Mn 2+(3d5 ,4so) mercury is a liquid. Explain.
For Fe3+lFe2+ couple, Fe 3+(3d5,4so} is more stable than (b) The melting and boiling points of Zn, Cd and Hg are
2
Fe +(3d 6,4so). Thus, the reduction is not spontaneous. low. Why?
(iii) In the lanthanide series, the size of the M 3+ ion (c) Though copper, silver and gold have completely filled
decreases from La3+ to Lu3+. Thus, the covalent nature of sets of d-orbitals, yet they are considered as transition metals.
Lu(OHh increases (Fajan's rule). Hence, Lu(OH)3 is weaker Why?
than La(OHh.
Solution: Solution:
(a) In chromium, the interatomic bonding is very stron~ due (i) In case a metal forms a number of oxides, the acidic
to presence of five unpaired electrons in 3d-subshell (3d 4s 1). strength increases with the increase in oxidation state of the
Therefore, it is a hard metal. In mercury, on the contrary, the metal, i.e., acidic strength increases with the increase in
3d-subshell is filled to maximum capacity (Si06i), i.e., these percentage of oxygen in the oxide. For example, MnO is a
electrons are not available for interatomic bonding and thus, basic oxide while Mn207 is an acidic oxide.
bonding is very weak in mercury. Therefore, mercury is a (ii) A metal exhibits higher oxidation states in oxides and
liquid at room temperature. fluorides as oxygen and fluorine are highly electronegative
(b) In Zn, Cd and Hg, the (n - 1) d-orbitals are filled to their elements and small in size, i.e., act as strong oxidising agents.
maximum capacity. These d-electrons do not take part in For example, chromium shows an oxidation state of +6 in
metallic bonding. Thus, metallic bonding is weak in Zn, Cd and CrF6 and osmium shows an oxidation state of +8 in OS04.
Hg. That is why, they have low melting and boiling points. (iii) This is also because of high electronegativity of oxygen.
(c) Copper, silver and gold in their common oxidation states For example, chromium shows oxidation state of +6 in Cr20~
have partially filled (n - 1) d-orbitals. and manganese shows oxidation state of +7 in MnO:!.
Cu 2\3d 9 ); Ag 2\4d 9 ); Au 3+(Sd 8 ) Example 26. (a) Actinide contraction is greater from
-7.+,£xample-24.--(a)OftheionsAg~,-Co2+-andTt-+ which elernenL to dement tban ZanthanldJLCQ1J,t[{],ction. _Why? _____
oneswiU be coloured in aqueous solution? (b) The outer electronic configuration offW.O membeDi-=ot_
(b) If each one of the above ionic species is in tum placed the lanthanide series are as follows:
in a magnetic field, how will it respond and why? 4/si6i and 4/Sdo6i
Solution: What are their atomic numbers? Predict the oxidation states
(a) The ionic species which possesses unpaired electron or exhibited by these elements in their compounds.
electrons in (n - 1) d-subshell will show colour. Of the ions Solution:
Ag \ 4d 10), C0 2\3d 7-three unpaired electrons) and Ti4\3do), (a) This is due to poor shielding by Sf electrons in the
C02+ will be coloured as it contains three unpaired electrons actinides than that of 4f electrons in the lanthanides.
and Ag+ and Ti4+ will be colourless. (b) Complete E.C. of 1st element: [Xe] 4/Sd 16i = S8,
(b) When placed ~n magnetic field, C0 2+ will be attracted i.e., the element is cerium.
because it is paramagnetic due to unpaired electrons. Ag+ apd Complete E.C. of 2nd element: [Xe] 4/Sdo6i = 63,
Ti 4+ ions will be repelled by the magnetic field as they are i.e., the element is europium.
diamagnetic due to presence of paired orbitals. The expected oxidation states of 1st element = +3, and +4
and of 2nd element = +2, +3.
Example 25. Give examples and suggest reasons for the
following features of the transition metal chemistry: Example 27. Which is the most common oxidation state
of lanthanides and how is it formed? Give its configuration.
(i) The lowest .oxide of transition metal is basic, the highest
Solution:
is amphoteric/acidic.
(ii) A transition metal exhibits highest oxidati~n state in The most common oxidation state of lanthanides is +3. This
oxidation state of the lanthanide ions arises due to the loss of
oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxoanions of two 6s electrons and the lone Sd electron, if present from the
atom of the elements. If no electron is presentin the Sd orbital,
a metal.
than one of electrons from 4f shell is lost. The lanthanides in
this state have the general configuration [Xe] 4/- 14 . .
b SUMMARY AND IMPORTANT POINTS TO REMEMBER' i

1. The elements belonging to groups' 3 to 12 of the extended 5. Generally, the atomic radii of d-block elements in a series
form of the periodic table are called d-block elements. They decrease with illcrease in atomic number but the decrease in
are present between s-block and p-block elements and belong atomic size is small after midway. In the flrst series, the atomic
to 4th, 5th, 6th and 7th periods of periodic table. They are radii decrease upto Cr but after that it remains almost the
also called transition elements (elements having incomplete same. The atomic radii of second and third transition series
(n l)d-orbitals in their atoms or in their simple ions). Their in the same vertical columns are almost the same. This is due
general electronic configuration is : to lanthanide contraction. The atomic radii of the pairs such '
(n l)d l - lOnsO, lor 2 as Zr-Hf, Nb-Ta, Mo-W, Ag-Au, etc., are almost same.
All transition elements are d-block elements but all d-block 6. The ionisation energy gradually increases with increase in
elements are not transition metals. For example, the elements atomic number along a given transition series. The ionisation
of group 12, namely Zn, Cd, Hg and Uub, though belong to energies of 3d and 4d elements are irregular. The frrstionisation
d-block but are not considered as transition metals because energy of 5d elements is higher than 3d and 4d elements
they contain completely filled (n - l)d-orbitals. belonging to same group due to lanthanide contraction.
2. Tl1ere are fourtranshion senes
'whIch Tnvolve
thc'fll11ng of". . 7.' Tfiilfsifi()nmehils sn()wvana6reoxiaationstate.s(excepfffrsr---'·~
(n - l)d-subsl1eJl.Each senes corislststenelements. Each . and lastmembef of the seriesFThe~ m()stc()mmonoxidation~
series starts from a member of third group and ends with a state of the first transition series is +2 except scandium. The
member of group 12. maximum oxidation state increases with atomic number upto
First series (3d-series) Sc (3d 1,4i) - Zn (3d lO ,4i) manganese in the first transition series. This is due to the
(21) (30) involvement of 4s electrons and unpaired electrons of
-Se2oIitherfes~(4d;~eries) ,'-:::':"Y'-2. 4ilJ.;S-:?)
t .. -, '-ed:":"-'-t4il~j;)- 3d-subshell. Manganese (3d 54i) shows maximum oxidation-
,- (39)'" (48) state of +7. Lower states are ionic while higher states are
Third series (5d~series) La (5d 1,6s2 )" - Hg (Sd lO ,6i) covalent.
{57) (8Q) The highest oxidation state shown by transition metal is +8
Fourth series (6d-series) Ac (6dI,7i) -- Uub (6i10,7s2) (by Ru and Os). Ions with the metal in a high oxidation state
(89) (112) tend to be good oxidising agents (Cr20?-, MnO;j) and ions
Certain elements show exceptional electronic configuration. with the metal in low oxidation state are good reducing agents
In the first transition series Cr (3d 5,4sl) and Cu ( 3dlO,4sl) 012+,C~+).
have exceptional configuration. 8. Most of the transition metals and their compounds exhibit
3. The elements of first transition series are : paramagnetism. Substances containing unpaired electrons are
Sc (21), Ti (22), V (23), Cr (24), Mn (25), Fe (26), paramagnetic. Those containing no unpaired electron are
Co (27), Ni (28), Cu (29) and Zn (30). diamagnetic. (Zn, Cd, Hg, Zn 2+, Cd2+, Hl+, Cu+, Sc 3+, Ti4+,
4. All the transition elements are metals. Iron is the most VS+, etc., are diamagnetic.) Magnetic moment is given as
abundant transition metal ill the earth's crust. Technetium and Jl .In(n + 2) B.M., where n = number of unpaired
all ·the members of fourth transition series are radioactive. electrons. In the first transition series Cr has maximum para-
Technetium is the first synthetic element. The elements after magnetism and amongst ions Mn2+ has maximum magnetic
uranium are termed transuranic elements. These elements moment.
have been obtained artificially by nuclear transmutation. 9. Most of the transition metal compounds (ionic as well as
Transition elements have high density, hardness, high tensile covalent) are coloured both in solid state and in aqueous
strength, malleability, ductility, high thermal and electrical solution. Colour is due to the presence of incomplete
conductivity, high energy of atomisation, high melting and d-subshell, i.e., there is d-d transition. The ions with (n - l)dO
boiling points. Larger the number of" unpaired electrons, or (n l)d lO configuration are colourless. Sc3+, Te4+, Cu+,
stronger is the metallic bond and hence higher is the energy Zn2+, etc., are colourless because they have either 3dO or
of atomisation and the melting point. That is why melting 3dlO configuration. The following colours are observed for
points increase in each series up to the fourth member, i.e., the common ions.
Cr, Mo and W (W-highest melting point 3410"C). However, Ti 3+ V3+ Mn 3+ Fe 3+ Fe 2+ Cu 2+ Co 2+ Ni 2+
the melting point of manganese in 3d-series is lower than its Purple Green Violet Yellow Green Blue Pink: Green
neighbours. This is due to stable configuration of manganese 10. Transition metals have the tendency to form complex
(3d s, 4i), Le., metallic bonding is less. Among the transition compounds, interstitial compounds and alloys. They and their
3
metals, the lightest is Sc (density 3.0 g cm- and heaviest i compounds act as good catalysts.
osmium (22.59 g cm- 3) and iridium (22.61 g cm- ). Hg is known 11. Iron, cobalt and nickel are termed ferrous metals. Copper,
in liquid form under ordinary conditions. silver and gold are called coinage metals. Zinc, cadmium and
mercury are called zinc metals. Principal ores of iron, copper, and is used for making utensils, cutlery and ornamental
silver, zinc and mercury are : pieces.
Iron Copper (ii) Invar (Fe, Ni). It has small coefficient of expansion and
Haematite Fe203 Copper glance CU2S is used for making metre rods, pendulum rods and
Magnetite Fe304 Copper pyrites CuFeS2 springs for watches.
or Chalcopyrites (iii) Manganese steel (Fe, Mn, C). It is very hard. It is used
Limonite Fe203·3H20 Malachite Cu(OHh·CuC0 3
Siderite Azurite Cu(OHh· 2CuC03
for making rock drills, almirah, etc.
FeC03
Iron pyrite FeS2 Cuprite CU20 (iv) Tungsten steel (Fe, W, C). It is hard and is used for
Silver Zinc making high speed cutting tools.
Argentite or Ag2S Zincblende ZnS (v) Alnico (Fe, AI, Ni, Co). It is highly magnetic and is used
silver glance for making permanent magnets.
Hom silver AgCl Calamine ZnC03 15. Copper is extracted from chalcopyrites. The ore is concen-
Zincite ZnO trated by froth floatation process, roasted in reverberatory
Mercury
furnace and then smelted in a blast furnace when molten
Cinnabar HgS
'matte' containing CU2S + FeS (little) is obtained. It is
12. There are three commercial varieties of iron : transferred to Bessemer converter and heated with a blast of
(i) Pig iron or cast iron: This is the most impure form.
hot air,. wh~I1b.U£t~"CqInU~J'_is()blilil1~d.~ ...
It contains~ab()uC2-S% cafooiC along With ~varying
amoUnts· ofMn,Si,S,P, etc. It is hatdand brittle. It .CU2S + 2Cu20~. 6Cu + S02
cannot be welded. It is used for casting purposes. Blister copper contains 96-98% copper along with small
(ii) Wronght iron: It is the purest form. It contains not amounts of Ag, Au, Ni, Zn, Pb, Sn, etc. It is further purified
more than 0.5% impurities including carbon. It is soft, by poling process and electrolytic process.
malleable and ductile. It can be welded. It can be easily Copper is used for making electrical wires, electroplating,
magnetised. coins and many useful alloys such. as bJ:a,ss (Cuand Zn)l
(iii) Steel: The carbon content is between 0.5 to 1.5%. It bronze (Cu and Sn), german silver (Cu, Zn and Ni), constantan
contains small amounts of other metals such as Cr, Ni, (Cu and Ni), rolled gold (Cu and AI), etc.
Mn, etc. 16. Silver is extracted from argentite. It is concentrated by froth
13. Cast iron or pig iron is usually extracted from the oxide ore. floatation process. The concentrated ore is ground to fine
It involves. the following steps : powder. This is treated with dilute solution (0.4 to 0.6%) of
(i) Concentration by gravity process; (ii) Calcination in sodium cyanide and a current of air is circulated. Silver present
reverberatory furnace ; (iii) Smelting in blast furnace. The in the ore dissolves.
calcined ore.is mixed with coke and limestone and smelted in' Ag2S + 4NaCN 2NaAg(CN}z + NazS
the blast furnace where CO produced as a result of 4Na2S + 502 + 2H20 ----t 2Na2S04 + 4NaOH + 2S
combustion of coke reduces Fe203 into Fe. Silver is precipitated from the solution by addition of zinc
Fe~03+ CO ----t 2FeO + C02 powder.
FeO + CO ----t Fe + CO 2 2NaAg(CN)z + Zn ----t Na2Zn(CN)4 + 2Ag
cac03 ----t CaO + CO 2 The precipitated silver is dried and fused with KN03 in a
CaO+ Si02 CaSi03 crucible. Liquid silver on cooling appears as a compact mass.
Slag The main impurities are lead, copper and gold. These are
14. Steel is manufactured from cast iron or pig iron by Bessemer removed by cupellation and electrolytic processes. Silver is
process, open hearth process or electric process. used, for making coins, ornaments, silverware and in
SpiegeJeisen-an alloy of Fe, Mn and C is added during electroplating. Silver salts are used in photography, silvering
manufacture. Steel is given heat treatment in order to impart of mirrors and for making marking inks and medicine.
special properties. 17. Zinc is extracted either from zinc blende or calamine. When
(i) Annealing: It involves heating of steel much below zinc blende is used the powdered ore is concentrated by froth
red heat and then cooled slowly. It makes steel soft. floatation process. In case of calamine, the ore is concentrated
(ii) Quenching: It involves heating of steel to red heat by gravity process. The concentrated ore is heated in excess
followed by sudden cooling by plunging into water or of oxygen at about 900°C. Zinc sulphide is oxidised to zinc
oil. It makes steel hard and brittle. oxide.
(iii) Tempering: It involves heating of steel which has 2ZnS + 302----t 2ZnO + 2S02
already been quenched to a temperature 230-300"C and Reduction of oxide is done by carbon.
then allowed to cool slowly. It makes steel hard but ZnO + C ----t Zn + CO, ZnO + CO ----t Zn + CO 2
brittleness disappears.
Zinc is also recovered by electrolytic process. The roasted
Some special steels are :
ore is dissolved in dilute sulphuric acid. The solution is freed
(i) Stainless steel (Fe, Cr, Ni, C). It is resistant to corrosion
from iron, aluminium and silica, etc. The solution is then
Transition Elements or d-block Elements and f-block Elements 72-1~
electrolysed by using a sheet of pure AI as cathode and pure the white of an egg. It is less soluble in cold water but
lead plate as anode. The zinc is removed from cathode by soluble in hot water and in organic solvents. It is a
melting. The zinc obtained is 99.95% pure. covalent compound. It is reduced by SnCl2 and copper.
The impure zinc obtained by reduction process is known as Its very dilute solution (0.1 %) is used as antiseptic.
spelter. Granulated zinc is made by melting the metal in a (v) HgI2 dissolves in excess of KI to form K2Hg4. An
crucible and pouring the drops in water. Zinc dust is made alkaline solution of K2HgI4 is called Nessler's reagent.
by melting zinc and then atomising it with a blast of air. Zinc It is used for the test of NH3 or NHS ion.
is used in the manufacture of various important alloys such (vi) K2Cr207 is prepared from the chromite ore (FeO·Cr203)'
as brass, german silver, etc. The most important use of zinc The fmely powdered ore is mixed with sodium carbonate
is for galvanising iron. It is also used for extraction of Ag and the mixture is fused in reverberatory furnace in
and Au, as a reducing agent in laboratory and zinc rods in excess of air. The roasted mass is extracted with water
making electric batteries. and the solution is treated with conc. H2S04·Na2S04·
18. Mercury is extracted from cinnabar. It is concentrated by froth lOH20 being less soluble crystallises our and is ftltered.
floatation process. The concentrated ore is then roasted in Hot solution of Na2Cr207 is treated with calculated
excess of air when mercury is obtained. amount of KCI when K2Cr207 crystals are obtained.
HgS + 02 ~ Hg + S02 4FeO·Cr203 + SNa2C03 + 702~
The menmryisrefllled byfustpassingit threughdiluteHN0 3 SNa:2Cf04+2FeiOi+-SC02
and. then distilled. Mercury forms alloys (amalgams) with all .S.olu.bleInsolltble • ==~-
metals except Fe and Pt. Hg is used in thermometers, mano- 2Na2Cr04 + H 2S04 ~ Na2Cr207 + Na2S04 + H20
meters and barometers.
19. (i) Copper sulphate (CuS04·5H20) is called blue vitriol. It It is an orange crystalline compound. It decomposes
is prepared by dissolving cupric oxide, cupric hydroxide on heating to give K2Cr04, Cr203 and O 2, Its acidic
or copper carbonate ill dilute H 2S04, solution contains dichromate ions while alkaline solution
In CuS04·5H20, the four· water molecules are contains chromate ions. It is a strong oxidising agent. .
2
coordinated to control Cu + ion while fIfth one is AcidifIed solution is used as a primary standard in
attached to SO~- ion by H-bonding. volumetric analysis for the estimation of reducing agents
With KI, it gives white CU2I2 and free iodine. such as ferrous sulphate, oxalic acid, etc. On heating
[2CuS04 + 4KI ~ CU2I2 + 2K2S04 + Iil with a chloride (NaCl) and conc. H 2S04, red vapours of
With excess ofNH40H, CUS04 gives deep blue solution Cr0 2Clz (chromyl chloride) are evolved. Its equivaJent
due to complex formation. mass in acidic medium is mol. mass/6 :;; 49.
CUS04 + 4NH40H ~ CU(NH3)4S04 + 4H20 (vii) KMn04 is. prepared from pyrolusite ore (Mn02)' The
fInely powdered ore is fused with KOH or K 2C03 in
A mixture of CuS04 and Ca(OH}z is used as a fungicide
presence of air or oxidising agent when K2Mn04
under the name of Bordeaux mixture.
(manganate) is formed. It is oxidised chemically by using
(li) Silver nitrate (AgN03) is called lunar caustic. It is
H2S04, CO 2 or C12 or electrolytically.
obtained by dissolving silver in dilute nitric acid. On
It is a deep purple crystalline compound, moderately
coming in contact with organic matter like skin or cloth
soluble in water. It decomposes when heated giving O2,
it is reduced to silver giving a black stain. It gives
It acts as a strong oxidising agent in neutral, alkaline
different coloured precipitates with acidic radicals such
as CC Br-, C crO~-, S2-, S20r, pot etc. and acidic media: The acidified KMn04 (dil. H 2S04) is
It is used for making silver halides, as a laboratory used as a volumetric reagent. It is not a primary
reagent, silvering mirrors and for making marking ink. standard, i.e., it is fIrst standardised and then used. Its
(iii) Out of AgCl, AgBr and AgI, AgBr is most sensitive to
equivalent mass in acidic medium is mol. massl5 31.6.
light and is used in photography. Alkaline KMn04 solution is called Baeyer's reagent
(iv) Hg. forms two chlorides. Mercury (I) chloride, i.e., used in organic analysis. It has tetrahedral structure.
mercurous chloride (Hg 2CI2) is also called calomel.
20. The f-block elements (inner transition elements) are placed
outside the periodic table. Their general configuration is :
It is nonpoisonous. It turns black when treated
with ammonia due to deposition of Hg. The oxidation (n ~ 2)/-14 (n l)do,lni
state of Hg is +1 but valency is 2, e.g., in Hg~+ There are two series :
(-Hg-Hg-) two atoms are joined together by a <a) 4f-series: 4f-orbitals are gradually ftlled up. These are
covalent bond. It is used for making calomel electrode 14 elements from Ce (58) to Lu(71) and are called
and as a purgative in medicine. lanthanides as these show similarities with La(S7).
Mercury(JI) chloride, i.e., mercuric chloride (HgCI2) is (b) ~-serieS: Sf-orbitals are gradually fIlled up. These are
also called corrosive sublimate. It is highly poisonous also 14 elements from Th (90) to Lr (103) and are called
(corrosive) and undergoes sublimation. Its antidote is actinides as these show similarities with actinium'.
Ac (89). These are radioactive elements. Most of these Paris green - Cu(CH3COOh·3Cu(As02h
are man-made. Rinnmann's green - ZnO·CoO or CoZno2 (Cobalt zincate)
21. There is gradual decrease in the atomic and ionic sizes of Verdigris - Cu(CH3COOh·Cu(OHh
these metals along the series. These are called hlnthanide
contraction and actinide contractions. Lanthanide contrac- NH
tion is responsible for various changes in chemical properties Fulminating gold AUI'
of the elements succeeding them. NH
22. All the lanthani~es are rather soft white metals. Tiley react "" 2
easily with water to give solutions giving +3 ions. The Calomel
principal oxidation state is +3 although +4, + 2 o~xidation states Corrosive sublimate - Hg02
2 2 2 Lunar caustic - AgN0 3
are also exhibited. Those having +2 (i.e., Sm +,Eu + and Yb +)
change to +3, and act as reducing agents. Those having +4 Philospher's wool - ZnO
tend to change to +3 and act as oxidising agents. The or pompholyx
maximum oxidation state shown by actinides is +7. U, Np and Blue vitriol '- CuS04·5H20 (Nila Thotha)
Pu show oxidation state of +6. However, all the actinides als~ Green vitriol - FeS04·7H20 EHara kasis)
show +3 oxidation state. Hom silver - AgCI
:~3. Paramagnetism is shown by the positive ions of lanthanides
MQl1I"'.~_~alt _ .. ____ ==-EeSQ4".~~QAJi!l-2Q_.~ __ ._~ _ __
exceptCi+(4y Or anQ-Lti3+(4f14r~Mostof the· fl1.vaIerif
~IpIssian -':>lu!!_ __-=-_Fe4lJ:e~6h ___ .~~_~ __~ _ _ _
laniliaiiiCle· ions are coloured. This is due to f {transition.
Actinide cations are also generally coloured. The cations
White vimor - znS04·7HiO
Vermilion - HgS
having 5/ or 5/ or 5/,4 configuration are colourless.
Purple of cassius - Colloidal gold solution
24. La(OHh is most basic while Lu(OHh is least basic.
25. The inertness exhibited by certain metals under conditions Fool's .gold - FeS2 or CuFeS2
when chemical activity is to be expected is called passivity. Titanox . ~ riQ2 i-Ba,S04
Iron is rendered passive by oxidising agents like conc. HN03, Lithophone - ZnS + BaS04
conc. H2S04, KMn04, chromic acid, etc. The passivity of iron Vaska's compound - Trans IrCI (CO) (PPh 3h
is believed to be due to formation of an extremely thin film of 29. Finely reduced form of platinum in the form of velvety black
oxide on the surface. Passive iron can be made active by powder is called platinum black.
scratching or removing oxide film chemically. 30. Titanium has been called 'The wonder metal'·because ofits
26. There are many compounds of transition metals which are useful properties. It is very hard; very light and has high
used as catalysts. For example: melting point.
Adam's catalyst PtJPtO 31. Mischmetal, an alloy which contains rare earth elements (94-
Brown's catalyst Nickel boride 95%), iron (5%) and traces of sulphur, carbon, silicon, calcium
Zeigler-Natta catalyst TiCl4 + (C 2H 5hAI and aluminium. It is pyrophoric and is used in cigarette and
Wilkinson's catalyst [Ph3P]RhCI gas lighters, tracer bullets and shells. The main rare earth
27. There are many compounds of transition elements which are elements present in this alloy are cerium ('" 40%), lanthanum
used as reagents in laboratory or industry. For example, and neodymium ('" 44%).
Baeyer's reagent Dilute alkaline soln. of KMn04 An alloy containing magnesium and about 3% mischmetal is
Tollen's reagent AgN0 3 soIn. + NaOH soln. used in jet engine parts.
+ NH40H 32. Technitium (Z = 43) does not occur in nature. It is a synthetic
Schweitzer's reagent - [Cu(NH3)4]S04 element. It was discovered, in 1937, by Segre.
Nessler's reagent Alk. soIn. of K2HgI4 =
Promethium (Z 61) does not occur in nature also.
Benedict's solution CUS04 soIn. + sod. citrate 33. (a) Rolled. geld is an alloy of Cu (95%) and Al (5%) and is
+ Na2C03 used for artificial jewellery.
Fehling's solution CUS04 soIn. + sodium potassium (b) Impure zinc is called spelter.
tartrate (c) German silver does not contain silver. It is an alloy of
Fenton's reagent FeS04 + H 20 2 Cu (56%), Zn (24%) and Ni (20%).
Etard's reagent CrD20 2 (d) Iron does not form amalgam with mercury.
Bordeaux mixture CUS04 soln. + lime (e) Sterling silver is an alloy of Ag (80%) and Cu (20%).
Lucas reagent Conc. HCI + anhydrous ZnCl2 (f) Permalloy (Fe 21 %, Ni 78% + C) is strongly magnetised
Barfoed's reagent Cu(CH3COOh+CH3COOH by electric current but loses magnetism when electric.
28. Some of the substances having compounds of transition current is cut off.
metals are given special names. (g) Alnico (Fe = 60%, AI = 12%, Ni = 20% and Co = 8%) is
highly magnetic and is used for permanent magnets.
Transition Elements or d-block Elements and i-block Elements 123--
~~*~--;-:J PRACTICE PROBLEMS - ••• -

,~~ > ::.... ' -.
• Subjective Type Questions (iv) Mercurous chloride is treated with ~OH.

(v) Potassium iodide is added iri excess to the solution of
1. How do the following properties vary in the transition ferric sulphate.
elements? (vi) Potassium permanganate solution is added to ferroUS
(a) Atomic size <.
sulphate solution in presence of sulphuric acid.
(b) Stability of various oxidation states (vii) Potassium nitrite reacts with cobalt chloride in presence
(c) Ionisation energy of acetic acid.
2. Explain the following: (viii) H2S is circulated through acidic solution of ferric
(a) Mercury is a liquid. chloride.
(b) Why CUS04 is blue while Zns04 is white. 8. What happens when the following chemical compounds are
(c) Why zinc and cadmium are soft metals. heated?
3. (a) Which one out of the each of following pairs is more (i) Silver nitrate (ii) Blue vitriol
stable? (iii) White vitriol (iv) Green vitriol
(i)-G;-t:, Cr3+ (ii)Fe3+,Fe~:t ··(ili)Mn2.+,MnOii' (v) Hyorafediinc chloride (vi) Mercurous chl()ride~--'
(b) Wh!ch one. of the following~tend to be an oxidising or (vii) Zinc carl?ollate (viii) Mercuncnitrate
reducing agent? , (lX) Zinc nitrate (x) Mercuric oxide
(i) C?+ (ti) Cr2~- (iii) MnOii' (iv) Ti2+ (Xl) Hydrated ferric chloride (xit) Cupric nitrate
4. Predict the spin only megnetic moment for: 9. Complete and balance the following equations :
(a) Fe2+ (b) Mn2+ (<:) Cr6+ (d) Cu+
(i) CUS04 + Na2C03+H20~ ... + Na2S04 + .~ ..
5. Answer the foUowing: [I.I.T.19921
(i) Name the lightest and heaviest elements in terms of
(n) CuS04 + ~OH ~ ... + ...
density among the transition elements.
(Ii) Name the transition,~lement which does not show (iii) AgBr + Na2S203 ~ ... + . . . rUT. 1993]
variable oxidation stares. (iv) CUS04 + KI ~ .. .
(iii) Name the member of lanthanide series which is well (v) CUS04 + KCN ~ .. .
known to exhibit +4 oxidation state. (vi) Ag+ + AsH3 + ...~H3As03 + W + ...
(iv) The +3 oxidation state of lanthanum (Z =57), gadolinium +
(vii) Ag CN- + 02 + ... ~ OH- + . .. [Roorkee 1996]
(Z = 64) and lutetium (Z= 71) are especially stable.
(viii) HgCl2 + SnCl2 ~ .. .
(v) Why lanthanides are paramagnetic in nature? '
6. What happens when? (lX) CdS04 + ~OH ~ .. .
(i) Hot and concentrated nitric acid reacts with copper. (x) HgCI2+ S02+"'~'" ',',
(li) Copper sulphate reacts with potassium iodide. (xi) [Fe(H20)6]2+ + NO'3 + ... + [Fe(H20)6P++H20
(iii) Ammonia solution is added to copper sulphate solution. [Fe(H20)6]2+ + ... ~ ... + H20 rUT. 1993]
[M.L.N.R. 1991] (xii) FeCl3 + H2S ~ ...
(iv) Cupric chloride is heated with concentrated HCI and
(xiii) Mn04 + Fe2+ --=---t Mn2+ + Fe3+ + H20
copper turnings.
(v) Copper is heated with concentrated H2S04. (Acidic medium) [Roorkee 1996]
(vi) Potassium iodide is added fIrst and then sodium (xiv) Fe2+ + NO'3 + H+ ~ Fe3+ + ... + H20 IRoorkee 1996]
thiosulphate to a solution of copper sulphate. (xv) FeCl3 + KI ~ .. "
(vii) Sulphur dioxide is circulated through a solution of copper (xvi) Ag2S + 2CuCl2 + 2Hg ~ ... + ... + S + 2Ag
sulphate containing sodium chloride. . [Roorkee 1998]
(viii) Silver chloride is treated with excess of ammonium (xvii) Au + HCI + HN03 ~ ... + ... + H 20 [Roorkee 1999]
hydroxide. (xviii) Cu(OHh + NH 4N03 + ~OH ~ ... + H20
(lX) Gold is dissolved in aqua-regia. [Roorkee 19991
(x) Sodium thiosulphate solution is added to silver
to. How will you obtain the following?
bromide.
(i) Cuprous chloride from copper sulphate.
7. What happens when?
(ii) Silver nitrate from silver.
(i) Excess. of caustic soda solution is added slowly to zinc
(iii) Silver from silver nitrate.
chloride solution.
(iv) Mercury from corrosive sublimate.
(li) Excess of ammoQium hydroxide solution is added to zinc
(v) Zinc chloride from zinc sulphate.
chloritJe solution. .
(vi) Allhydrous ferric chloride from iron.
(Iii) MercuJic chloride is treated willi ~OH.
(vii) Ferric chloride from ferrous sulphate.
11. Give the balanced equations for the: (iv) Hydrated zinc chloride cannot be dehydrated on heating?,
(i) Reaction of argentite with KCN. Name the products in [Hint: On heating it reacts with water of crystallisation and
solution. [U.T.l996} forms zinc oxychloride.
(li) Recovery of silver from silver coin. 2ZnC12·2H20 ---t Zn20Ch + 2HCl +'3H20]
(iii) Extraction of copper from copper pyrites by self (v) Zinc is used in the galvanisation of iron.
reduction. [I.I.T. 1990] [Hint: Zinc coating protects the iron from corrosion as zinc
(iv) Extraction of zinc from zinc blende. is not affected by oxygen and water.]
(v) Reactions occurring in blast furnace in the extraction of (vi) Poling process is used in the purification of copper.
iron. [Hint: The oxide of copper which remains in the copper
12. Name two principal ores of each of the following metals: (blister) is reduced by introducing poles of green
(i) Copper (li; Silver (iii) Zinc (iv) Mercury (v) kon wood. The gas (hydrocarbons, CO, Hz, etc.) bubbles
13. Give the constituents of following alloys: originating .from the wood act as reducing agents. The
(i) Brass (ii) German silver (iii) Bronze (iv) Rolled gold mass is stirred with these green poles vigorously.J
(v) Constantan (vi) Invar (vii) Stainless steel (viii) Gun (vii) A solution of ferric chloride gives a brown precipitate on
metal standing.
14. Answer the following: [Hint: Hydrolysis of ferric chloride occurs giving finally
(i) What are d-block elements? brown precipitate.
(ii)Whafisflie generid electronic configuratioDofd:block ··FeeI3 T 3H2fr~Fe(OH)3 ,..-3HCI
elements? 2Fe(OHh- Fez0T+ -3Hz0]
n
)
Brown
(iii) Name three characteristic properties of d-block elements.
(iv) Name the first and last element of 3d-series. (viii) Transition metals and their compounds act as catalysts.
(v) Name the two elements of 3d-series which show [Hint: Because of the availability of d-orbitals they can easily
form intermediate products which are activated. The
anomalous electronic configuration.
sizes of transition metal atoms and ions are also
(vi) Transition. elements form alloys easily. What is the favourable for transitory complex formation with the .
reason? reactants. ]
(vii) Which ions of flIst transition series show highest
paramagnetism? (Ix) In moist air copper corrodes to produce a green layer on
(viii) Why the compounds of transition elements are
the surface. [I.l.T. 1998J
[Hint: Copper in presence of moisture oxygen and carbon
coloured?
3 dioxide of atmosphere is converted into basic carbonate
(ix) Why Fe + compounds are more stable?
which is deposited as green layer on surface.
(x) Why most of the compounds of transition elements are 2Cu + CO2 + H 20 + O2 ---t Cu(OH)zCuC031
paramagnetic ?
17. Due to lanthanide contraction which properties are expected
(xi) What is the maximum oxidation state of manganese?
to be similar in the same vertical columns of the second and
(xii) What is the maximum oxidation state of chromium?
third row transition elements besides atomic radii?
15. Write short notes on the following:
(i) Refining of blister copper (ii) Silver plating 18. Calculate magnetic moments of M2+ ions· of Ti(Z=22),
(iii) Silvering of mirrors (iv) Poling process Cr(Z=24), Mn(Z=25) and Cu(Z=29) and arrange them in
(v) Cupellation process (vi) Galvanisation increasing order.
(vii) Lithopone (viii) Nessler's reagent H. Explain by giving suitable reason.
(ix) Passivity (x) Heat treatment of steel (i) Yellow coloured aqueous solution of sodium chromate
(xi) Corrosion of iron (xii) .Types of iron changes to orange-red when CO 2 under pressure is
16. Explain the following giving proper reason. passed.
(i) Anhydrous ferric chloride cannot be obtained by heating [Hint : CO2 gives It' ions which are responsible for the
conversion of chromate into dichromate (orange-red).
hydrated ferric chloride.
[Hint: On heating, it reacts with water of crystallisation and CO 2+HzO ~ HCO'3+H+
converted into FeZ03 with evolution of HCl. 2CrO;- + 2H+ Cr20?-+HzO]
(li) COz is evolved when NaHC0 3 is added to FeC13
(li) ZnO is used as a white paint inspite of the fact that it solution.
[Hint: FeCl 3 undergoes hydrolysis giving HCI which reacts
has less covering power than· white lead.
with NaHC0 3 to form CO 2,
[Hint: ZnO is not blackened in atmosphere of hydrogen
sulphide. It can be tilled both as oil and water paint. FeCl3 + 3H20 Fe(OHh + 3HCI
It is non-poisonous in nature.] NaHC0 3 + HCl NaCI + H20 + COz]
(iii) CuS04 is paramagnetic while ZnS04 is diamagnetic. (iii) Green solution of potassium manganate, KzMn04, turns
[Hint: .Cu2+ ion has configuration, i.e., one unpaired purple when C02 is circulated.
orbital while ion has 3dlO configuration, i.e., all [Hint: COz gives H+ ions which are responsiblf' for
. orbitals doubly occupied.] conversion of MnOl- into MnO; (purple),
CO 2+H20 ~ H++ HCO'3 (iv) Lithopone (d) Cobalt zincate
3MllOl- + 4W ---? 2Mn04 + Mn02 + 2H20] (v) Zinc oxide (e) Hg(CNSh
Green Purple (vi) White vitriol (f) An ore of mercury
(iv) Hg2+ and Hg~+ salts are colourless. (vii) Spelter (g) An ore of zinc
[Hint : Hg2+ and Hgi+ salts have 5dlO configuration, i.e., there (viii) Rinmann's green (b) HgCl2
is <no d-d transition, hence colourless.] Ox) Nessler's reagent (i) Zinc sulphate
2 (x) Phl!fash'sserpent (j) (BaS04+ZnS)
(v) Cu + salts are paramagnetic while Cu+ salts are diamag-
(xi) Calamine (1;.) Red form of HgS
netic in nature,
[Hint: Cu z+ configuration is 3d 9(one orbital is singly
(xii) Cinnabar (1) A white pigment
occupied)-Paramagnetic; Cu+ configuration is 3d 10 [B) (i) Lunar caustic (a) Basic copper acetate
(all orbitals are doubly occupied)-Diamagnetic.] (ii) Blue vitriol (b) Impure copper
20. Explain: (iii) Malachite (c) Black oxide of copper
(a) Why is K2Cr207 generally preferred to Na2Cr207 in (iv) Argentite (d) Mixture of copper
volumetric analysis? sulphide and iron
[Hint : K2CrZ~ is not hygroscopic and can be used as slllJ:>hi~e
primary-standarirT (v) Blister copper (e) Silver nitrate
(b) Whlchdivruenfmetal ion -has maillnurn paramagnetic (vi) Brass (f) Anorebf silver <
character among the first transition metals? Why? (vii) Light sensitive (g) An ore of copper
[Hint: Mn2+, It has maximum number of unpaired electrons,] (viii) Matte (h) An alloy of copper
(c) HgC12 and SnCl2 cannot exist together in an aqueous (ix) Verdigris (i) Copper sulphate
solution, Why? (x) Tenorite _CD Silver_bromide
[Hint : SnClz is a strong reducing agent. Itreduces HgCi to z [C] (i) Green vitriol (a) Fe4[Fe(CN)6h
(ii) Haematite (b) Impure iron
2HgClz + SnClz ---? HgzClz + SnCl4
HgzClz + SnCl2 ---? 2Hg + SnC4] (iii) Siderite (c) FeS04(Nl4hS04,6H20,
(iv) Prussian blue (d) An alloy of iron
(d) Why does AgN0 3 produce a black stain on the skin?
(v) Mohr's salt (e) Pure iron
[Hint : In the presence of organic matter and light, AgN03
decomposes to give a black stain of metallic silver. (vi) Pig iron (1) Mixed oxide
(vii) Wrought iron (g) An ore of iron
2AgN03 ---? 2Ag + 2NOz + Oz]
(viii) Steel (stainless) (h) Galvanised iron
(e) How the colour ofK2Cr2~ solution does depend on pH
(ix) Resistant of corrosion (i) Ferrous sulphate
of the solution?
(FeS°4 ·7H20)
[Hint : In the solution, the following equilibria exists:
(x) Magnetic oxide (j) FeC03
CrzO;- + H 20 ~ 2CrO~- + 2W
[D] (i) Standard electrode (a) Open hearth furnace
In acidic medium (pH < 7), it exists as Cr20~- ions
(ii) Silvering of mirrors (b) Blast furnace
and has orange colour while in basic medium (pH>7),
CrOl-
it exfsts as' ions and has yellow colour.] (iii) Electric wiring (c) ZnS04,7H20
(iv) Steel manufacturing (d) Silver
(v) Pig iron (e) Cupric chloride
• Matchin~ Type Questions
(vi) Parkes process (1) Hg 20 2
Match the foUowing: (vii) White vitriol (g) Copper metal
[A] (i) Corrosive sublimate (a) Hg20 2
(viii) Deacon's process (h) AgN03
(ii) Vermilion (b) Impure zinc
(iii) Calomel (c) KzHg4+KOH
Answers : Subjective Type Questions (iii) HgClz + 2Nl:140H ---4 Hg(NHz)CI + Nl:I4CI + 2HzO
1. See the trends in properties.
(iv) Hg2Clz+2Nl:140H ---4 !lg(NHz )CI+ H~ +NH4CI + 2HzO
2. (a) No metallic bond fonnation is Rresent.
(b) Cu z+ in CUS04 has [Ar] 3d94s configuration. It can undergo Greyish black
d-d transition. It absorbs red region of the visible light and hence (v) FC2(S04h + 2Kl ---4 2FeS04 + K2S04 + 12
CUS04 ~ blue as blue is complime~tary colour of red.
(vi) 2KMn04 + 3HzS04 ---4 KZS04 + 2MnS04+ 3H20 + 5[0]
In ZnS04. Zn 2+ has 3io4i configUration. It cannot undergo
d-d transition, hence it appears colourles~. [2FeS04 + HZS04 + [0] ---4 Fe2(S04)3 + HzO] x 5
(~j Zn \Uld Cd have no unpaired electr~n and thus there is no metallic 2KMn04+8H2S04+10FeS04~5Fe2(S04h+KzS04+2MnS04+8H20
. bonding. Hence, they are soft in nature.
3. (a) (i). Cr3+ (ii) Fe3+ (iii) Mn2+ (vii) [CoQ2 + 2KNOz ---4 Co(N02h + 2KCI] x 2
\
(b) (i).reducing agent (ii) oxidising agent (iii) oxidisingllgent [Co(NOzh + 4KNOz ---4 K4Co(N02)61 x 2
(iv) reducing agent. '
[KN02 + CH3COOH ---4 CH3COOK + HNOz] x 2
4. Ion Electronic No. of unpaired Magnetic
~O~~~N'Q±J!2Q+JQ]
~eonfigurationc -electrons-~~- -moment
--4 2K4CO(NOZ)6 +c-HzO +. [QJ .~. 2K:lCo(N~2)6+ 2KOH.
(a) Fe?+, [Ar]3d 64s0 4;roBM
(b) Mnz+ [Ar] 3d s4s0 5 5.96 BM [KOH + CH3COOH ---4 CH3COOK + H20] x 2
(c) Cr6+ [Ar] 3do4:P 0 o BM 2COC12+ 14KN02+4CH3COOH ---4 2K3Co(N02)6 + 4CH3COOK
(d) Cu+ [Ar] 3d 104so 0 o B-M Pot. cobaltinilrlte
5. (i) Scandium (density 3.43 g cm-3) and osmium or iridium (density + 4KCI + 2NO + 2H20
22.59 and 22.61 g cm-3 resp.) or CoCI2 + 7KNOz + 2CH3COOH ---4 K3Co(N0z)6 + 2CH3COOK
(ii) Scandium. It shows only +3 oxidation state. + 2KCI + NO +H20
(iii) Cerium (Z = 58). It has configuration [Xe] 415d16sz. After
(viii) 2FeCl3 + H~ ---4 2FeCh + 2HCl + S
losing 4 electrons, it acquires inert gas configuration.
8. (i) On heating above its melting point, it decomposes to silver
(iv) This is because they have 4fo, 4/ (half-filled) and 414 (fully
nitrite and oxygen.
. filled) subshell respectively.
(v) All the lanthanides except La3+ and Lu3+ contain unpaired 2AgN03 ---4 2AgNOz + O2
electrons. When heated at red heat, it further decomposes to metallic silver.
6. (i) Cu + 4HN03(Conc.) Heat) Cu(N03h + 2N02 +2H20 AgN02 ---4 Ag + N02
(ii) 2CUS04 + 4KI ---4 Cu212+2K~04 + Iz or 2AgN0J ---4 2Ag + 2NOz + 02
(iii) CUS04 + 4Nl:140H ---4 [Cu(NH3)4]S04 + 4HzO (li) CuS04·5H20 lOO"C) CUS04.H20 230"C) CUS04 72O"C)
Tetrammine cupric sulphate
Blue
(iv) CuClz + Cu HCI) CU2Ch
(V) Cu + 2HzS04 ~ CUS04 + SOz + 2HzO
(vi)2CuS04 + 4KI ---4 CuZl2 + 2KzS04 + Iz (iii) ZnS04'7H20
White
Iz.+ 2NazSZ03 ---4 2NaI + NaZS406
----------~----~~
2CuS04 + 4KI + 2NazSz0J ---4CuZI2 + 2K~04 + 2NaI + NaZS406
(iv) 2FeS04·7H20
(vii)2CuS04+2NaCI+SOz+2HzO ---4 CuzClz+Na~04+2HZS04 Green
(viii) AgCI + 2NH40H ---4 Ag(NH3hCI + 2HzO (v) ZnClz·2HzO ---4 Zn(OH)CI + HCI + H20
(ix)2Au + 3HN03 + llHCI---42HAuC4 + 3NOCI + 6HzO or 2ZnClz·2HzO ---4 Zn2OCl2 + 2HCl + 3H20
Zinc oxychloride
Chloroauric chloride
(x)
(vi) HgzCl2 ---4 HgCl2 + Hg
AgBr + 2NazSZ03 ---4 Na3[Ag(S20Jh] + NaBr
Sodium argentothiosulphate (vii) ZnC03 ---4 ZnO + CO2
7. (i) ZnC1 2 + 2NaOH ---4 Zn(OHh + 2NaCI (viii) 2Hg(N03h ---4 2HgO + 4NOz + 02
Zn(OH)z + 2NaOH ---4 NaZZn02 + 2H20 or 2Hg(N03h ---4 2Hg + 4N02 + 202
(ix) 2Zn(N03h ---4 2Zn0 + 4NOz + Oz
ZnClz + 4NaOH ---4 Na2Zn02 + 2NaCI + 2H20
Sodium zincate (x) 2HgO ---4 2Hg + Oz
(li) (xi) 2[FeCI3·6H20] ---4 FC203 + 6HCI + 9HzO
Zn(0H)2 + 2NH4CI + 2Nl:140H ---4 [Zn(NH3)4]Clz + 4H20 • (xii) 2Cu(N03h ---4 2CuO + 4N02 + Oz
Tetrammine zinc chloride 9. (i) 2CUS04 + 2NazC03 + H20 ---4 CuC03,Cu(OH}z
+ 2Na2S04 + C02
(ii) CUS04 + 4NH40H~ Cu(NH3)4S04 + 4HzO FeO + Si02 ----7 FeSi03(Slag) Smelting
(iii) AgCl + 2NazSZ03 ----7 Na~g(SZ03h + NaCI CU20 + FeS ~ CuzS + FeO
(iv) 2CUS04 + 4KI ----7 Cuzlz + 2K~S04 + 12 CU2S + 2CU20 ----7 6Cu + S02 Bessemerisation
(v) 2CUS04 + IOKCN ----7 2K3Cu(CN)4 + (CNh + 2KzS04 (iv) 2ZnS + 302 900"C) 2Z:q,0+2S02
(vi) 6Ag+ +AsH3 +3Hz0----7 6Ag + 6H+ + H3As03
Roasting in reverberatory furnace
\ (vii) 4Ag + 8CN- + 02 + 2HzO ----7 40U- + 4[Ag(CN)2r ZnO + C ----7 Zn + CO Reduction
\(viii) HgClz + SnClz ----7 Hg + SnCl4 (v) Combustion zone
(ix) CdS0 4 + 4NH40H ----7 Cd(NH3)4S04 + 4H20 C + O2 ----7 COz:" 97:0 kcal
(x) 2HgCl2 + SOz + 2HzO ----7 HgzCl2 + 2HCl + H2S04 CO2 + C lS00·C) 2CO
(xi) 3[Fe(HzO)6]z+ + NO"3+4H;I- ----7 NO + 3[Fe(HzO)6]3+ + 2H20 Reduction zone
[Fe(HzO)6f+ + NO ----7 [Fe(HzO)sNOf+ + H20 300-400·C
3Fez03 + CO . ) 2Fe304 + COz
(xii) 2FeCl3 + HzS ----7 2FeCIz + 2HCl + S Fe304 + CO SOo-600·C) 3FeO + COz
(xiii)Mn04 +5FJ+ + 8H+ ----7Mnz+ +5Fe~++4HzO- '- -~-- ~- ~ -700"C _..... .~
FeO + CO~ Fe + C02

~(xi\i) 3
NO"3 + 4H+ ----7 3Fe ++ NO + 2HzO Slag formation zone
(xv) 2FeCl3 + 2KI ----7 2FeC12 + 2KCI + 12 CaC03 ~ CaO + COz
(xvi) AgzS + 2Hg + 2CuCIz ----7 CU2Cl2 + Hg2Cl2 + 2Ag + S CaO + Si0 2 ----7 CaSi0 3(Slag)
(xvii) Au + 4HCI + HN03 HAuC4 + NO + 2HzO P40 lO + lOC ----7 4P + lOCO
(xviii) Cu(OHh + 2NH4N03 + 2NH40H ~ Cu(NH 3MN0 3h + 4HzO SiOz + 2C ----7 Si + 2CO
Mn02 + 2C ----7 Mn + 2CO
10. (i) 2CUS04 + 2NaCI + S02 + 2H20 ---:--?Cu2Clz + Na2S04.
Cuprous chloride
These are partly absorbed by iron.
12. (i) Copper pyrites, CuFeSz; Copper glance; CuzS
(ti) Argentite Ag2S; Argentiferous lead
(ti) Ag + 2HN03(conc.) ----7 AgN0 3 + N02 + H20 (iii) Zinc blende ZnS; Calamine ZnC03
(iii) 2AgN03 + Zn ----7 2Ag + Zn(N03)z (iv) Cinnabar HgS; Small quantities of Hg
occur in free condition
(iv) HgCl 2 + SnClz ----7 Hg + SnCl4 (v) Haematite Fe203; Magnetic Fe304
(v) ZnS04 + NaHC0 3 ----7 ZnC03 + NaHS04 llroCu~Zn~~Zn~M~Cu~~~Cu~N
(v) Cu and Ni (vi) Fe and Ni (vii) Fe, Cr and Ni (viii) Cu, Sn
ZnC0 3 + 2HCI(dil.) ----7 ZnClz + H20 + CO2
and Zn
(vi) 2Fe + 3Cl2 ----7 2FeCl 3
14. (i) The elements in which differentiating electron is accommodated
(By passing chlorine over heated iron fillings.) in the d-subshell are called d-block elements. (ii) (n-l)i-lOni
(iii) (a) Formation of coloured compounds (b) Formation of complex
(vii) 2FeS04 Healed)
strongly
Fe2'-'j
rI_ + SO + SO
2 3 compounds (c) Paramagnetic in nature (iv) Scandium, Zinc
FeZ03 + 6HCI ----7 2FeCl3 + 3HzO (v) Chromium, Copper (vi) Nearly same atomic radii (vii) Fe3+ and
Mnz+ (viii) d-d transition by absorbing part of visible light
11. (i) AgzS + 4KCN ~ 2KAg(CNh + K2S
Pot. argentocyanide
(ix) 3d s configuration, i.e., all the five orbitals are singly occupied
The above reaction is reversible. To dissolve Ag2S in KCN, air (x) Presence of unpaired electrons (xi) +7 (xii) +6.
is blown through solution. 15. See text.
17. Lattice energies, solution energies and ionisation energies.
4K2S + 502 + 2H20 ----7 2K2S04 + 4KOH + 2S . 18. Tiz+=J8; Cr2+ =..fi4 ; Mnz+=.J35 ; J3
(ti) Coin is dissolved il). nitric acid. Silver nitrate is present in the z
Cu +< Tiz+ < Cr2+ < Mnz+.
solution. HCI is added to precipitate AgCI which is fused with
NaZC0 3 to recover Ag. Answers : Matching Type Questions
AgN03 + HCI ----7 AgCl + HN0 3 [A] (i-h); (ii-k); (iii-a); (iv-j); (v-I); (vi-i); (vii-b);
2AgCI + NaZC0 3 ----7 Ag ZC03 + 2NaCI (viii-d); (ix---c); (x-e); (xi-g); (xii-f).
1 [B] (i-e); (ii-i); (iii-g); (iv-f); (v-b); (vi-h); (vii-j);
Ag2C0 3 ----7 2Ag + CO 2 + 2 O2
Heat
(viii-d); (ix-a); (X;---c).
(iii) 2CuFeS2 + O2 ----7 CU2S + 2FeS + S02 [C] (i-i); (ii-g); (iii-j); (iv-a); (vi-b); (vii-e);
Copper pyrites
(viii-d); (ix-h); (x-f).
2Cu zS + 302 ----7 2CU20 + 2S02 Roasting [D1 (i-f); (ii-h); (iii-g); (iv-a); (v-b); (vi-d); (vii---c);
2FeS + 302 ~ 2FeO + 2S02 (viii-e).
QUESTIONS BASED ON THE PROPERTIES

1. An unknown inorganic compound (A) gave the following [Hint: The compound (X) is CuS04·5HzO
reactions: (a) CUS04 + BaClz ~ BaS04 + CuCl2
Insoluble
(a) The compound (A) on heating gave a residue and a
(b) 2CuS04 + 4KI ~ Cuzlz + 2KzS04 + Iz
gaseous mixture of N0 2 and oxygen. White
(b) The compound (A) with tap water gave a turbidity which 12 + 2NazSZ03 ~ 2Nal + Na2S406
'did not dissolve in conc. HN0 3 . (C) 2CuS04 + ~Fe(CN)6 ~Cu2Fe(CN)6 + 2K2 S04 ]
. (c) The aqueous solution of (A) gave a white precipitate with Chocolate ppt.
sodium chloride solution. The precipitate dissolves in 4. A certain metal (A) is boiled in dilute nitric acid to give a salt
excess of ammonium hydroxide. (B) and an oxide of nitrogen (C). An aqueous solution of (B)
Identify the compound (A) and give the balanced equations. with brine solution gives a precipitate (D) which is soluble
[Ans. The compound (A) is AgN03 in ammonium hydroxide. On adding aqueous solution of (B)
(a) 2AgN0 3 ~ 2Ag + 2N02 + O2 to hypo solution, a white precipitate (E) is obtained. (E) on
. (b) ._AgNQ3.+~cr. _ .. _....).AgCl +NO"3 standingturnstoltblackcompound tF);Identify(Atto(F): . . - - - -
(Tap water)
·--iRoorkee· ·199Oj=c-
(c) AgN03 + NaCl ~. AgCl+NaNO:3
[Ans. (A) = Silver; (B) = AgN03; (C) NO; (D) AgCl;
AgCl + 2NH40H ~ Ag(NH3)zCl + 2H20]
(E) AgzSZ0 3; (F) = AgzS.
2. A black coloured compound (A) on reaction with dilute H2S04 Reactions: 3Ag + 4HN0 3 ~ 3AgN03 + NO + 2HzO
gives a gas (B) which on passing in a solution of acid (C) (Al (Bl (c)
gives a white turbidity (D). Gas (B) when passed in an AgN03 + Na9 ~ AgCI + NaN0 3
acidified solution of compound (E) gives a precipitate (F) (D)
soluble in di!. HN0 3. After boiling this solution when an AgCl + 2NH40H ~ Ag(NH3)zCl + 2H20
excess ofNH40H is added, a blue coloured compound (G) is Soluble
formed. To this solution on addition of acetic acid and 2AgN0 3 + NaZSZ03 ~ Ag 2S20 3 + 2NaN03
(E) White ppt.
aqueous potassium ferrocyanide a chocolate precipitate (8)
is obtained. On addition of an aqueous solution of barium Ag2S Z03 + H 20 ~ Ag 2S + H2S04]
(F) Black
chloride to an aqueous solution of (E), a white precipitate
insoluble in HN0 3 is obtained. Identify from (A) to (8). 5. A pale blue crystalline substance (X) when heated upto 300°C
[Hint: FeS + H 2S04 ~ FeS04 + HzS gives a white solid (Y) which can restore blue colour with
(A) (B) moisture. Solution of either (X) or (Y) forms (2) with excess
H 2S + [0] ~ H 20 + S of ammonia which imparts deep blue colour to solution. Write
From acid (D) formulae for (X), (Y) and (2).
(HN0 3 )
HzS + CUS04 ~ CuS + H ZS04
[Ans. (X) CuS04·5H20; (y) = CUS04; (Z) = Cu(NH3)4S04]
(E) (F) 6. (i) A white amorphous powder (A) on stroqg heating gives
Soluble in HNG.J a colourless non-combustible gas (B) and solid (C).
2HN03 ~ H20 + 2NOz + [0] (ii) The gas (B) turns lime water milky and turbidity
CuS + 2HN03 + [0] ~ Cu(N03h + H20 + S disappears with the passage of excess of gas.
Cu(N03h + 41':~OH ~ Cu(NH3MN03h + 4H20 (iii) The solution of (C) in dil. HCI gives a white precipitate
(0)
with an aqueous solution of ~Fe(CN)6'
Cu(NH3)4(N03)z + 4CH3COOH Cu(N03)z + 4CH3COONH4
(iv) The solution (A) in dilute HCI gives a white precipitate
2Cu(N03h + K4Fe(CN)6 ~ Cuz[Fe(CN)6] + 4KN0 3
(lI)
(D) on passing H2S in presence of excess of NH4 0H.
Identify (A) to (D) and give chemical equations for the
CUS04 + BaCh ~ CuCh + BaS04 ]
(E) Insoluble in HN03 reactions. [Roorkee 1993]
[Hint : ZnC0 3 --'---4 COz + ZnO
3. An aqueous solution of an inorganic compound (X) gives (A) (B) (e)
the following reactions: CO 2
CO2 + Ca(OHh ~ CaC03 --"7 Ca(HC0 3h
(a) When an aqueous solution of barium chloride is added, Milky Soluble
a precipitate insoluble in dil. HCI is obtained. ZnO + HCl ~ ZnCl z K.Fe(CN)6) Zn2Fe(CN)6
(b) Addition of excess of KI gives a brown precipitate which White ppt.
turns white on addition of excess of hypo. Znc0 3 + HCl ~ ZnC12
(c) With an aqueous solution of potassium ferrocyanide a Solution
chocolate coloured precipitate is formed. ZnCl2 + NH40H + HzS ~ ZnS

Identify (X) and give equations for the above reactions. White ppt.
(D)
7. A white substance when heated in a test tube, produced a (ii) CuO + Hz ---7 Cu + H20
colourless, odourless gas leaving a residue, yellow when hot (D)
and white on cooling. The residue was dissolved in dil. HCI, (iii) CuO + 2HCl ---7 CuCl 2 + H20
made alkaline with ammonium chloride and ammonium 2CuCl2 + KJ'e(CN)6 ---7 CU2Fe(CN)6 + 4KCl
hydroxide and H2S gas passed through it. A white precipitate (E)
was obtained. (iv) CO2 + Ca(OHh ---7 CaC03 + H20

(i) What was the original substance? CaC03 + CO2 + H 20 ---7 Ca(HC03h ]
(ii) Write the equation for the action of heat. (F)
(iii) What was the white precipitate formed with H2S? 10. (i) A black mineral (A) on heating in presence of air gives a
[Ans. (i) ZnC03; (ii) ZnC03 ---7 ZnO + CO2; (iii) ZnS] gas (B),
8. (i) An aqueous solution of a white coloured compound (A) (ii) The mineral (A) on reaction with dilute H 2S04 gives a
on reaction with HCI gives a white precipitate of gas (C) and the solution of a compound (D).
compound (B). (iii) On passing gas (C) into an aqueous solution of (B), a
(ii) (B) becomes soluble in chlorine water with formation of white turbidity is obtained.
(C). (iv) The aqueous solution of compound (D) on reaction with
(iii) . ~C)reacts.with-Kl togiveapf{~cipitatewhlchbeoomes potassium' ferricyanide .gives a blue' compound (E). ...._-_.
soluble in excess of. it forroinga ·compound(D). The Identify (A) to (mand give chemical equation for reactions .-- .
compound (D) is used for detecting am.n:lOnium salts. at steps (i) to (iv). [Roorkee 1994]
(iv) (B) and (C) both on treatment with SnCl2 gives a grey [Hint : (A) = FeS; (B) :::: S02; (C) :::: H2S; (D) :::: FeS04;
precipitate of CE), (E) = K+Fen [Feill(CN)6]
(v) When conc. H2S04 is added slowly into a mixture of cold (i) 2FeS + 302 ---7 2FeO + 2S02
solution of (A) and FeS04, a brown ring compound (F) (A) (8)
is formed. (ii) FeS + H2S04 ---7 FeS04 + H2S
Identify (A) to (F) and give chemical equations for the (D) (C)
reactions at steps (i) to (v). [Roorkee 1997) (iii) 2H2S + S02 ---7 2H20 + 3S
[ADS. (A) = Hg2(N03h; (B) :::: Hg 2C1 2 ; (C) :::: HgCI2; (D):::: K2HgL;; (C) (8) Turbidity
. (E) :::: Hg; (F) FeS04 ,NO. (iv) FeS04 + K3Fe(CN)6 ---7 KFe[Fe(CN)6] + K2S04]
(E) Blue
Reactions : (i) Hg2(N03h + 2HCl ---7 Hg2Clz + 2HN03
(A) (8) 11; A certain inorganic compound (A) on heating loses its water
(ii) Hg2Cl2 + 2Cl(Chlorine water) ---7 2HgCl2 of ~rysta1lization. On further heating a blackish brown powder
(C)
(B) and two oxides of sulphur, (C) and (D) are obtained, The
(iii) HgCl2 + 4Kl---7 K2HgL; + 2KCI
(D)
powder (B) on boiling with hydrochloric acid gives a yellow
(iv) Hg2Cl2 + SnClz ---7 2Hg + SnC4 solution (E). When H2S is passed in (E) a white turbidity (F)
(8) (E) and a apple green colour (G) are obtained. Th~ solution (E)
HgCl2 + SnCl2 ---7 Hg + SnCl4 on treatment with thiocyanate ions gives a blood red coloured
(C) (E) compound (H). Identify from (A) to (H).
(v) Hg 2(N03)2 + H2S04 ---7 Hg2S04 + 2HN03 = =
[Ans. (A) :::: FeS04,7H 20; (B) Fe203; . (C) S02; (D) = S03;
2HN03 ---7 H20 + 2NO + 3[0] (E)=FeCI3; (F):::: S; (G) =HiCI2; (ll) = Fe(SCNh
2FeS04 + [0] + H 2S04 ---7 Fe2(S04h + H20 Reaction:
FeS04 + NO ---7 FeS04,NO (Brown ring)] Heat Heat S
FeSO4.7H20 -7H 0) FeS04 ~ Fe203 + 02 + S03
(F) (A) 2 (8) (C) (D)
9. (i) A blue coloured compound (A) on heating gives two F~03 + 6HCl ---7 2FeCh + 3H20
products, (B) and (C), (E)
(ii) A metal (D) is deposited on passing hydrogen through 2FeCh + H2S 2FeCl2 + 2HCI + S
(G) (F)
heated (B),
(iii) The solution of (B) in HCI on treatment with ~Fe(CN)6 FeCl3 + 3SCN- ---7 Fe(SCN)3 + 3Cr]
(ll)
gives a chocolate brown coloured precipitate of
compound (E). 12. Compound (A) is a light green solid. It gives following tests:
(iv) (C) turns lime water milky which disappears on (a) It dissolves in dilute H 2S04.No gas is evolved.
continuous passage of (C) forming a compound (F). (b) A drop of KMn04 is added to the above solution. The
Identify (A) to (F) and give chemical equations for the pink colour is decolourised.
reactions at steps (i) to (iv). [Roorkee 1997] (c) Compound (A) is heated strongly. Gases (B) and (C) with
[ADS. (A) = CuC03; (B) CuO; (C) CO2 ; (D) Cu; pungent smell come out and a brown residue (D) is left.
(E)= Cu2Fe(CN)6;(F) = Ca(HC03)z. (d) The gaseous mixture is passed into a dichromate
Reactions : (i) CuC03 ---7 CuO + CO2 solution, it turns green.
(A) (8) (C)
(e) The green solution from reaction 'd' gives a white Identify (A) to (E) and give chemical equations for the
precipitate (E) with a solution of barium nitrate. reactions at steps (i) and (iii) to (vi). [Roorkee 1998]
(f) The residue (D) from reaction 'c' on heating with [Hint: (B) is CdS04 which gives a yellow compound by passing
charcoal in a reducing flame, gave a magnetic substance. H2S through its solution. It gives a white ppt. with BaCl2
Nanie the compounds (A), (B), (C), (D) and ({). soln. The ppt. is insoluble in conc. HN0 3. It suggests that
= = =
[Ans. (A) FeS04·7H20; (B) S02; (C) S03; (D) Fe203; = SO~- ion is present in the salt.
(E) == BaS04 (i) CdS04 + H 2S ~ CdS + H2S0 4
(a) (A) dissolves in dilute H 2S04. No gas is evolved. (B) (A)
(b) lOFeS04 + 2KMn04 + 8H 2S04 ~ 5Fe2(S04h + K2S04 (ii) CdS04 + BaCl2 ~ BaS04 + CdCl2
+ 2MriS04 + 8H20 (B) (El
(c) 2FeS04·7H20 ~ Fe203 + 2S0 2 + 2S03 + 14H20 Insoluble in
(A) (D) (B) (C) water
(d) S02 reduces acidified K2Cr207' CdS + 2HN0 3 ~ Cd(N03h T, H2S
K2Cr2~ + H2S0 4 + 3S02 ~ K2S04 + Cr2(S04h + H 20 Soluble \
Green CdS +
(e) SO~- + Ba(N0 3h ~ BaS04 + 2NO] Yellow anunonium
Sulphide
(f)_F~03_+3c: ~2I<e:+:~c:9L
(iii),€dSO'l+2;NI40H ~. €d(OHJ2+(NH4hSOc- - - - - -
13. Compound (A). _.'_ ___ ._ Cd(OHh-+4NH40H ~Cd(NH3M0H}2+ 4H20-~-
(i) .On strong heating gives two oxides of sulphur. (C) Soluble
(ii) On adding aqueous NaOH solution to its aqueous (iv) CdS04 + 2KCN ~ Cd(CNh + K2S04
solution, a dirty green precipitate is obtained which starts White PP],
turning brown on exposure to air. , Cd(CNh + 2KCN ~ K2Cd(CN)4

(D) Soluble
Identify (A) and give chemical equations. [Roorkee 1993]
(v) K2Cd(CNk+ H2S~ CdS + 2KCN + 2HCN]
[Hint : (A) = FeS04 (A)
Heat
2FeS04 ------? Fe203 + S02 + SO3 16. (i) An aqueous solution of a compound (A) is acidic towards
FeS04 + 2NaOH ~ Fe(OHh + Na2S04 litmus and (A) is sublimed at about 300°C.
[0] (ii) (A) on treatment with an excess of NH4CNS gives a red
Fe(OHh ~ Fe(OHh]
coloured compound (B) and on treatment with a solution
14. A light bluish green crystalline compound corresponds to the
of ~Fe(CN)6 gives a blue coloured compound (C).
following tests: (iii) (A) on heating with excess of K2Cr207 in presence of
(i) Its aqueous solution gives a brown precipitate or
conc. H2S04 gives deep red vapours of (D).
colouration with alkaline K2[Hg4]. (iv) On passing vapours of (D) into a solution of NaOH and
(ii) Its aqueous solution gives a blue colour with K 3Fe(CN)6
then adding the solution of acetic acid and lead acetate,
solution.
a yellow precipit.ate of compound (E) is obtained.
(iii) Its solution in HCI gives a white precipitate with BaCl2
Identify (A) to (E) and give chemical equations for the
solution. reactions at steps (ii) to (iv). [Roorkee 1998]
Identify the ions present and suggest the formula of the
[Hint: (A) is FeCI3' It gives red colour of Fe(CNSh with NH4CNS
compound. .' , [I.I.T. 1992} and chromyl chloride test for CI- ion. The reactions are:
[Ans. The ions'present are NH~, Fe2+ and SO~-. The formula of
(i) FeCl3 + 3H20 ~ Fe(OHh + 3HCI
the compound is (~hS04·FeS04·6H20] (A) (Acidic)
15. (i) The yellow coloured precipitate of compound (A) is (A) sublimes at 300°C
formed on passing H2S through a neutral solution of a (ii) FeCl 3 + 3~CNS ~ Fe(CNSh + 3~CI
salt (B). (B) Red
(ii) (A) is soluble in hot dilute HN0 3, but insoluble:in yellow 4FeCl3 + 3~Fe(CN)6 ~ Fe4[Fe(CN)6h + 12KCI
(C) Blue
ammonium sulphide.
(iii) 4FeCl3 + 9H2S04 + 3K2Cr207 ~
(iii) The solution of (B) on treatment with small quantity of
6Cr02Cl2 + 2Fez(S04h + 3K2S0 4 + 9HzO
NH3 gives white precipitate which becomes soluble in (D) Red vapours
excess of it forming a compound (C). (iv) Cr0 2Ci2 + 4NaOH ~ 4Na2Cr04 + 2NaCI + 2H 20
(iv) The solution of (B) gives white precipitate with small Na2Cr04 + (CH 3COOhPb ~ PbCr04 + 2CH3COONa]
concentration of KCN which becomes soluble in excess (El Yellow ppt.
of this reagent forming a compound (D). 17. Pyrolusite on heating with KOH in the presence of air gives
(v) The solution of (D) on treatment with H2S gives (A). a dark green compound (A). The solution of (A) on treatment
(vi) The solution of (B) in dilute HCI on treatment with a with H 2S04 gives a purple coloured compound (B), which
solution of BaCl2 gives white precipitate of compound gives following reactions.
(E) which is insoluble in conc. HN0 3. (i) KI on reaction with alkaline solution of (B) changes into
a compound (C).
(ii) The colour of the compound (B) disappears on treatment 4FeCl3 + 3~e(CN)6 ~ Fe4[Fe(CN)6h + 12KO
(D)
with the acidic solution of FeS04. Prussian blue
(iii) With conc. H2S04 compound (8) gives (D) which can
(ill) 2Na2Cr04 + H2S04 ~ Na2Cr207 + Na2S04 + H20'
decompose to yield (E) and oxygen. (C) (E)
Identify (A) to (E) and write balanced chemical equations for Yellow colour!ld
the formation of (A) and (8) and for steps (i) to (iii). (iv) Na2Cr2~ + 2KCl ~ K2Cr2~ + 2NaCl
(F)
[Roorkee 19'991
Orange-red
[Hint: 2MnO z + 4KOH + O2 ~ 2K2Mn04 + 2H20
(v) K2Cr2~ + 4H2S04 + 3H2C204 ~
K2S04 +. Cr2(S04h
(Air) (A) Dark green
3K2Mn04 + 2H2S04 ~ 2KMn04 + MnOz + 2K2S04 + 2H20 + 6C02 + 7HzO
(8) Purple Cr2(S04h + 6KzC204 ~2K3[Cr2(CZ04)3] + 3K2S041
(i) 2KMn04 + H20 + KI ~ KI03 + 2Mn02 + 2KOH (G)
(C) Blue crystals
(ii) 2KMn04 + SH2S04 + lOFeS04 ~

K2S04 + '2MnS0 4 20. Complete the following by identifying (A) to (F).
+ 5Fe2(S04h + SH20 (i) CUS04 ·5H20~(A) 230"C) (8)' 800"C >(C) +(D)
(iii) 2KMn04 + H2S04 ~ Mn2<h + K2S04 + H20
. (D) (ii)AgN03 u_~edhot_)(E) +(F) +Dz.. lRoorkee2000.!.____
2Mn207 ~4Mn6; +30 z1 [Hint: (i)(A)CuS04·H20;{B)CuS04;{C)CuO~-ED)S03
XE)
18. An aqueous blue coloured solution of a transition metal (ii) (E) Ag; (F) N02
sulphate reacts with H2S in acidic medium to give a black 2AgN03 ~ 2Ag + 2N02 + 021
precipitate (A) which is insoluble in warm aqueous solution 21. (i) A powdered substance (A) on .treatment with fusion
of KOH. The blue solution on treatment with KI in weakly mixture gives a green coloured compound (8).
acidic medium turns yellow and produces a white precipitate (ii) The solution of (8) in boiling water on acidification with
(8). Identify the transition metal ion. Write the· chemical dilute H2S04 gives a pink coloured compound (C).
reactions involved in the formation of (A) and (8). (iii) The aqueous solution of (A) on treatment with NaOH and
[(J.T. 20001 Br2-water gives a compound (D).
[Hint: The transition metal ion is Cu2+. (iv) A solution of (D) in conc. HN0 3 on treatment with lead
CUS04 + H2S ~ CuS + HZS04 peroxide at boiling temperature produced a compound
Blue coloured (A)
solution . Black ppt. (E) which was of the same colour as that of (C).
CuS0 4 + 2KI ~ CUl2 + K2S04 (v) A solution of (A) in dilute HCI on treatment with a
2CuI2 ~ Cu212 + 12 1 solution of barium chloride gave a white precipitate of
(8) compound (F) which was insoluble in conc. HN03 and
White ppt.
conc. Hei.
19. (i) An ore (A) on roasting with sodium carbonate and lime Identify (A) to (F) and give balanced chemical equations for
in the presence of air gives two compounds, (8) and (C). th~ reactions at steps (i) to (v). LRoorkee 2001]
(ii) The solution of (B) in conc. HCI on treatment with [Hint: (A) is MnS04.
potassium ferrocyanide gives a blue colour or precipitate (i) MnS04 + Na2C03 + 2KN03 ~ Na2Mn04 + 2KN02
of compound (D). (A) (B)
(iii) The aqueous solution of (C) on treatment with conc. Green coloured'
H2S04 gives a yellow colo1,1I'ed compound (E). +~a2S04 + 2C02
(iv) Compound (E) when treated with KCI gives an orange- (ii) 3Na2Mn04 + 2H2S04 ~ 2NaMn04 + MnOz + 2Na2S04 + 2H20
(C)
red compound (F) which is used as an oxidising reagent. Pink coloured
(v) The solution of (F) on treatment with oxalic acid and then (ill) MnS04 + 4NaOH + Br2 ~ Mn02 + Na2S04 ~ 2NaBr + 2H20
with an excess of potassium oxalate gives blue crystals (D)
of compound (0). . (iv) 2Mn02 + lOHN03 + 5PbOz ~ 2HMn04 + 5Pb(N03h
(E)
Identify (A) to (G) and give balanced chemical equations for Pink solution
reactions at steps (i) to (v). [Roorkee 2000} + 4H20 + 02
[Hint: The ore is chromite, FeOCrZ03' (v) MnS04 + BaCl2 ~. BaS04 + MnQ21
(F)
(i) 4FeO·Cr203 + SNazC03 + 702 2Fez~ +SNa2Cr04 (Insoluble in cone. HN03
(A) (8) (C)
+ SC02 and cone. Hel)
(li) Fez03 + 6HO ~ 2FeC13 + 3H20

(8)
fUlISTRA1fONS OF OBJECTIVE QUESTIONS

1. Among a-block elements, the most abundant element [Hint : K2Cr2~ + 7HzS04 + 6KI ~
belongs to the : 4K2S04 + Cr2(S04h + 7H 20 + 312]
(a) fIrst transition series (b) second transition series -1
(c) third transition series (d) fourth transition series +3
Ans. (a) 8. Calomel (Hg 2CI2) on reaction with NH40H gives:
[Hint : Iron is the most abundant d-block metal which belongs to [A.I.E.E.K 2005]
first transition series.] (a) HgNH20 (b) NH2-Hg-Hg-CI
2. The 3d metal ions are generally paramagnetic in nature (c) Hg 20 (d) HgO
because : Ans. (a)
(a) they form coloured salts [Hint : Hg 2Cl2 + 2N1140H ~
(b) they have one or more unpaired d electrons
<
NH 2 - .
(c) th~yh~ve .oll~Qr lllo!e. paired s electroIl§. Hg . . .+ Hg+ NH4 Cl+ 2HzO}-
(<i) th~Yare redllcltlgllgents . ___ .. _ . CI - --..~
...~
.....- - .
ADs. (b) '-,,-------'
[Hint: Paramagnetic nature is due to unpaired d electrons.] Black
3. The number of moles of acidified KMn04 required to convert 9. Which of the following is not an actinide ?
one mole of sulphite ion into sulphate ion is :
[D.P.M.T. 2005]
(a) Curium (b) Califomium
(a) 2/5 (b)" 3/5 (c) 4/5 (d) I .
Ans. (a) (c) Uranium (d) Terbium
[Hint: 2Mn04 + 6H+ + 5S0~- ______ 2Mn2+ + 5S0~- + 3H 20 Ans. (d)
2 moles 5 moles [Hint: Terbium is a lanthanide.]
5 moles of SO~- '" 2 moles of Mn04 10. Brass, bronze and german silver have one metal in common.
1 mole of SO~- ~ 215 moles of Mn04 This is:
2/5 moles of KMn04] (a) Zn (b) Fe
(c) Cu (d) AI
4. Which of the following ores contains both Cu and Fe ? Ans. (c)
[LLT.2005] [Hint: Brass Cu 60-80%, Zn 40-20%
(a) Cuprite (b) Azurite Bronze Cu 75-90%, Sn 25-10%
(c) Chalcopyrite (d) Malachite German silver Cu 56%, Zn 24%, Ni 20%
Ans. (c) Common metal is copper.]
[Hint : Chalcopyrite-CuFeS2] 11. Which of the following pairs of ions is colourless ?
5. The correct order of ionic radii of Ce, La, Pm and Yb in +3 [E.A.M.C.KT. (Engg.) 2004]
oxidation state is : (a) Te+, Cu2+ (b) Sc 3+, Zn2+
(a) La3+ < Pm3+ < Ce3+ < Yb3+ (c) C02+, Fe3+ (d) Ni2+, V3+
(b) La3+ < Ce3+ < Pm3+ < Yb3+ Ans. (b)
(c) Yb3+ < Ce3+ < Pm3+ < La3+ [Hint: Sc3+ has 3d o confignration while Znz+ has 3d 10 confi-
(d) Yb3+ < Pm3+ < Ce3+< La3+ guration. Hence, these ions are colourless.]
Ans. (d)
12. The lanthanide contraction relates to :
[Hint: Lanthanide contraction decreases atomic sizes from La3+
to Lu3+. Hence, the correct order will be (d) for the given (a) atomic radii (b) atomic as well as M3+ radii
ions.] (c) valence electrons (d) oxidation states
6. Heating mixture of Cu20 and CU2S will give: [A.LKRE.2005] Ans. (b)
(a) Cu + S02 (b) Cu + S03 13. For successive members of the fITst row transition elements
are listed below with their atomic numbers. Which one of
(c) CuO + CuS (d) CU2S03
them is expected to have the highest third ionisation
Ans. (a)
enthalpy? [C.BoS.E. 2005]
[Hint : 2CU20 + CU2S ______ 6Cu + S02]
(a) Vanadium (Z 23) = (b) Manganese (Z = 25)
7. The oxidation state of chromium in the final product formed (c) Chromium(Z=24) (d) Iron (Z=26)
by the reaction between KI and acidifIed K2Cr207 solution Ans. (b)
is: [A.LE.KE.2(05)
(a) +4 (b) + 6 [Hint : M2+ e i,~,) M 3+
(c) +2 (d) + 3 Mn 2+ has the most stable configuration, i.e., 3d 5 (all the
Ans. (d) five d-orbitals are singly occupied). Hence, to remove
Transition Elements or d-block Elements and f-block Elements 733~
electron from Mn2+ ion requires more energy, i.e., the third ' (c) the same effective nuclear charge from Ce to Lu.
ionisation enthalpy of manganese is highest.] (d) the imperfect shielding on outer electrons by 4f electrons
14. Green vitriol is formed by: from the nuclear charge
(a) FeS z + CO (b) FeSz + H20 + COz Ans. (d)
(c) FeS z + HzO + 0z (d) FeSz + CO + CO2 20. The spin only magnetic moment [in units of Bohr magneton]
AIlS. (c)
of Nlt in aqueous solution would be (At. No. 28) :
[Hint : 2FeS z + 70 z + 2HzO ----7 2FeS04 + 2HzS04]
[A.I.E.E.E.2006]
15. Stainless steel does not rust because :
(a) 2.84 (b) 4.90
(a) nickel present in it does not rust
(c) 0 (d) 1.73
(b) chromium and nickel combine with iron AIlS. (a)
(c) chromium forms an oxide layer and protects iron from 2 8
[Hint: Ni + has 3d configuration, i.e" 2 unpaired electrons are
rusting present. Thus, magnetic moment = .In(n + 2) =
(d) iron forms a hard chemical compound with chromium = J8 = 2.84 B.M.] ..
present in it 21. In which of the following pairs are both the ions coloured in
AIlS. (c) aqueous solution? [C.B.S.E. 2006]
16. Which of the following forms with an excess of CN-, a (a) Sc3+, Coz+ (b) Niz+, Cu+
compl~JLhaving. CQordination number two? [A.I.I.MS.20041 (c) Ni2+, Ti3+ Cd) Sc3+,1'i3+ - - - - -
( a ) C u z + ( b l Ag+ [At. Nos. Sc =21, Ti = 22,-Ni-=28-and Gu-=-29J-
(c) Niz+ (d) Fe2+ Ans. (c)
[Hint : Unpaired electrons are present in Ni 2+ and Ti 3+
AIlS. (b)
[Hint: AgCN + CN- ----7 [Ag(CN)zn .3d
17. Of the following outer electronic configurations of atoms, the
highest oxidation state is achieved by which one of them ? Ti 3+,," 3d ,
(a) (n - 1)d 8ns2 (b) (n 1)d 5ns 1
3 z
(c) (n - l)d ns (d) (n l)d 5ns 2 22. Arrange the following ions in their magnetic moment :
AIlS. Cd) (i) V4+(ii) Mn4+ (ill) Fe3+ (iv) Ni 2+
18. The compound used in enrichment of uranium for nuclear [At. Nos. V 23, Mn =25, Fe = 26, Ni 28]
power plant is : [A.I.I.MS. 2006} (a) (ii) > (ill) > (i) > (iv)
(a) U 30 S (b) UF6 (b) (iii) > (iv) > (n) > (i)
(c) UOz(N03)2 (d) UCl4 (c) (iii) > (ii) > (iv) > (i)
Ans. (b) (d) (i) < (iv) < (ill) < (ii)
19. Lanthanide contraction is caused due to: [A.I.E.E.E.2006] Ans. (c)
(a) the appreciable shielding on outer electrons by 4f [Hint: y4+[Ar]3d 1, Mn 4+[Ar]3d 3, Fe3+[Ar]3d5 , Ni z+[Ar]3d 8 ]
electrons from the nuclear charge
(b) the appreciable shielding on outer 'electrons by 5d
electrons from the nuclear charge
•
734
...' -
GR.B. Inorganic Chemistry for Competitions
I
Set I
, OBJECTIVE QUESTIONS
This set contains questions with one answer.
-
1. Among d-block elements, the most abundant element 11. Among the following outennost configurations of transition
belongs to: metals, which shows the highest oxidation state:
(a) fIrst transition series 0 (C.B.S.E. (p.M.T.) 2009]
1
(b) second transition series 0 (a) 3d 3 ,4i 0 (b) 3d 5,4s 0
(c) third transition series 0 5
(c) 3d ,4i 6
0 (d) 3d ,4i 0
(d) fourth transition series 0 12 In the fIrst transition series, the highest oxidation state is
2 Which of the following is not the characteristic of transition exhibited by:
metals? (a) Mn 0 (b) Ni 0
(a) They are all metals 0 (c) Fe 0 (d) Cr 0
(b) They show variable oxidation states which always differ 13. Which of the following ions is coloured in solution?
by two units 0 (a) Zn2+ 0 (b) Ti4+ 0
(c) They are paramagnetic 0 (c) Cu+ 0 (d) V~
(d) Theyeasilyforni~omplexes 0 14. Row many ~~airedelectrons are present in the centralmetaJ:--
3. The correct order of ionisation energy is : ion of [COC4] -?
(a) Cu > Ag > Au 0 (b) Cu >Au >Ag 0 (a) 5 0 (b) 4 0
(c) Au> Cu >Ag 0 (d) Ag >Au > Cu 0 , (c) 3 0 (d) 2 0
4. The fIrst transition element is:
(a) scandium 0 (b) chromium 0 [Hint: Co2+ E.C. = 2,8,8 + 7 11''\',1 i,\,ltlil iJ ]
3d
(c) nickel 0 (d) copper 0
5. The general electronic confIguration of transition elements 15. ' Which ofthe following has the maximum number of unpaired
is: d electrons?
(a) (n - l)i-5 0 (b) (n l)i- lO ns 1 0 (a) Zn 0 (b) Fe2+ 0
lO 1
(c) (n _ l)i- ns or 2 0 (d) none 0 (c) Ni3+ 0 (d) Cu+ 0
6. The property, which is not characteristic of transition metals, 16. Colour in transition metal compounds is attributed to :
is: (V.I.T.E.E.E. 2008] (a) small size of metal ions 0
(a) variable oxidation states 0 (b) absorption of light in UV region 0
(b) tendency to fonn complexes I] (c) moderate ionisation energy 0
(c) fonnation of coloured compounds 0 (d) incomplete (n - 1) d subshell 0
(d) natural-radioactivity 0 17. Europium is a: [D.P.M.T.2005]
7. The electronic configuration of the element which is just '(a) j-block element 0 (b) d-block element 0
above the element with atomic number 43 in the same (c) p-block element 0 (d) s-block element 0
periodic group is: 18. The electronic confIguration of copper is:
(a) li,2i2p6,3i3p63J,4i 0 (a) [Ar]3d 9 ,4i 0 (b) [Ar]3d lO ,4s1 0
8 lO
(b) Is2, 2i2p6, 3i3p63dlO, 4i4p5 0 (c) [Ar]3d ,4i 0 (d) [Ar]3d ,4i D
(c) Ii, 2i2p6, 3i3p63d 6, 4i 0 19. Which metal has the highest melting point ?
1 (a) Platinum 0 (b) Gold D
(d) li,2i2p6,3i3i3d lO ,4s 4i 0
(c) Tungsten 0 (d) Iridium D
8. Chromium has the electronic confIguration: 20. Transition metals show paramagnetism: (B.H.U.2005]
(a) 3i3p63d 4,4i 0 (b) 3i3p63dS,4s1 0 (a) due to characteristic configuration D
(c) 3s~i3d6 0 (d) none of these 0 (b) high lattice energy D
2
9. The number of d electrons in Fe + (at. no. of iron = 26) is' not (c) due to variable oxidation states D
equal to that of: (d) due to unpaired electrons D
(a) p electrons in neon (at. no. = 10) 0 21. Zr and Hf have almost equal atomic and ionic radii because:
(b) s electrons in Mg (at. ,no. = 12) 0 (a) of diagonal relationship D
(c) d electrons in Fe 0 (b) of lanthanide contraction D
(d) p electrons in CI- (at. no. of CI =17) 0 (c) of actinide contraction 0
10. ~The maximum number of unpaired electrons are in: (d) both belong to same transition series 0
[D,C.E. 2006] 22. Which of the following ions has smallest radius?
(a) Fe2+ 0 (b) Fe3+ 0 (a) Mn 2+ 0 (b) Ni2+ 0
(c) Fe4+ 0 (d) Fe 0 2
(c) Ti + 0 (d) V +2
0
Transition Elements or d-hlock Elements and i-block Elements 135---
23. The yellow colour of chromates changes to orange on 36. The effect of mineral acids on the coinage metals:
acidification due to formation of: (a) decreases from Cu to Au 0
(a) Cr3+ 0 (b) Cr20:3 0 (b) increases from Cu to Au 0
(c) Cr2o?- [j (d) 0:04 0 (c) remains 'the same 0 (d) cannot be predicted 0
24. Manganese shows oxidation states from +2 to +7. The most 37. Malachite is a mineral of:
oxidising state known in aqueous solution is: (a) magnesium 0 (b) copper 0
(a) +7 0 (b) -+4 0 (c) aluminiwn 0 (d) iron 0
(c) +3 0 (d) +2 0 38. Copper is extracted from sulphide ore using the ·method:
25. What is the magnetic moment of K 3[FeF6]? (a) carbon reduction 0
[J.E.E. (Orissa) 2005] (b) carbon monoxide reduction 0
(a) 5.91 B.M. 0 (b) 4.89 B.M. 0 (c) auto reduction 0 (d) none of these 0
(c) 3.87B.M. 0 (d) 6.92B.M. 0 39. In the extraction of copper from copper pyrites, iron is
[Hint: Fe3+ E.C. = 2, 8, 8 +5, 11 =.J5 x 7 = 5.91 B.M.] removed as: '
26. Which of the following is an acidic oxide? (a) FeS04 0 (b) FeSi03 0
(a) Mn20? 0 (b) Mn304 0 (c) Fe304 0 (d) Fe203 0
(c) MnO 0 (d) Mn203 0 40. Blister copper is :
(a)a~tuI"e ofirnp_ure_copperand silver 0___ __
27. Which-one of the following ions is-diamagnetic?
(a) Cr2+ 0 (b) V2+ - 0 (b) pl"e~I1Lin the anoQic mud in anelectrQlytic process 0_'__ _
(c) Sc + 3 o (d) Ti 3+ 0 (c)electr01ytically refined copper 0--
28. Transition metals: (d) copper containing about 2% impurity 0
(a) exhibit inert pair effect 0 41. The flux used in the smelting of copper ores is:
(b) have low melting point 0 (a) limestone 0 (b) magnesia 0
(c) do not show catalytic activity 0 (c) silica 0 (d) coke 0
(d) exhibit variable oxidation states 0 42. In the extraction of copper, metal is formed in the Bessemer
29. A metal ion from the first transition has a magnetic moment converter due to reaction:
(calculated) of 3.87 B.M. How many unpaired electrons are (a) CU2S + 2CU20 ~ 6Cu + S02 0
expected to be present in the ion? (b) CU2S ~2Cu+S 0
(a) 1 0 (b) 2 0 (c) Fe + CU20 ~ 2Cu + FeO 0
(c) 3 D (d) 4 0 (d) 2CU20 ~ 4Cu + O 2 0
30: Coinage metals are: 43. High purity copper metal is obtained by:
(a) normal elements 0 (a) carbon reduction 0 (b) hydrogen reduction 0
(b) transition elements 0 (c) electrolytic reduction 0 (d) thermite reduction 0
(c) active elements 0 44. The melting points of Cu, Ag and Au follow the order:
(d) highly electropositive elements 0 (a) Au> Ag > Cu 0 (b) Cu > Au> Ag 0
31. The position of Cu, Ag and Au in the periodic table is in (c) Cu > Ag > Au 0 (d) Ag > Au > Cu • 0
between: 45. Roasting of copper pyrites is done:
(a) alkali and alkaline earth metals 0 (a) to remove moisture and volatile impurities 0
(b) alkali metals and halogens 0 (b) to oxidise free sulphur 0
(c) vm group and zinc metals 0 (c) to decompose pyrites into CU2S and FeS 0
(d) alkaline earth metals and halogens. 0 (d) for all of the above 0
32. Coinage metals show: 46. ]n the electrolytic refining of copper, Ag and Au are found:
(a) only monovalency 0 (b) only divalency 0 (a) on cathode 0 (b) on anode 0
(c) only trivalency 0 (d) variable valency 0 (c) in the anodic mud 0 (d) in the cathodic mud 0
33. . . . . . .is the best conductor of electricity. 47. The alloy of copper and tin is called:
(a) Silver 0 (b) Copper 0 (a) brass 0 (b) bronze 0
(c) Gold 0 (d) Brass 0 (c) german silver 0 (d) type metal 0
34. ,The electrons present in the penultimate orbit of coinage 48. Brass is an alloy containing:
metal atoms are: ,(a) Cu and Zn 0 (b) Cu and Sn 0
(a) 8 0 (b) 2 0 (c) Zn and Sn 0 (d) Cu, Zn and Sn 0
'(c) 18 0 (d) 32 10 49. Gun metiJ is an alloy of:
35. 'When copper is placed in the atmosphere for sufficient time, (a) Cu and AI 0 (b) Cu, Zn and Ni 0
a green crust is formed on its surface. The composition of (c) Cu, Sn and Zn 0 (d) Cu and Sn 0
the green crust is: 50. An oxide of copper which is red in colour has the formula:
(a) Cu(OHh 0 (b) CuO 0 (a) CuO 0 (b) Cu20 0
(c) CuC03 0 (d) CuC03·Cu(OHh 0 (c) CU02 0 (d) CU2~ 0
736 ·GR.B. Inorganic Chemistry for Competitions
51. When a cupric salt is heated with metallic copper and conc. 66. Silver can be separated from lead by:
HCI, a colourless solution is obtained because of the for- (a) fractional crystallisation 0
mationof: (b) amalgamation 0
(a) Cu02 o (b) Cu2Cl2 o (c) filtration 0 (d) addition of zinc 0
(c) H[CuOil o (d) H[CuCI3] o 67. Silver sulphide dissolves in sodium cyanide solution to form
52. ·CuS04·5H20 is called: the complex:
(a) green vitriol o (b) blue vitriol o (a) Na2[Ag(CN)4] o (b) Na[Ag(CN)2] o
(c) white vitriol o (d) gypsum o (c) Na3[Ag(CN)4] o (d) all of these o
53. In the reaction, 68. Red precipitate is obtained when silver nitrate is added to:
2CuCl2 + 2H20 + S02 ~ A + H2S04 + 2HCI; A is: (a) K2Cr04 0 (b) Kl 0
Ja) Cu20 2 0 (b) Cu 0 (c) KBr 0 (d) Na2S2~ 0
(c) 0004 0 (d) CuS 0 fE. Photographic films or plates have. . . . .as an- essential
54. In the reaction between CUS04 and KI, a white precipitate is ingredient.
obtained. The precipitate has the composition: (a) silver oxide 0 (b) silverbrornide 0
(a) Cul2 0 (b) Cu21 0 (c) silver thiosulphate 0 (d) silver nitrate 0
(c) KCuI2 0 (d) CU212 0 70. Percentage of gold in 14 carat gold is:
55. The matte obtained by smelting copperpyrites with coke and Ca) 58 D (b)80--Q---
sand c()ntalns mainly : [B.V.(Pune) . 2006} (c) 40 0 (d) l 4 D - - -
(a) FeS + ZnS 0 (b) CU2S + FeS 0 71. Silver nitrate is usually supplied in coloured bottles because
(c) CuS + FeS2 0 (d) ZnS + CuS 0 it is:
56. The common metal in brass, bronze and german silver is: (a) oxidised in air 0
(a) Cu 0 (b) Mg 0 (b) decomposes in sunlight 0
(c) AI 0 (d) Zn 0 (c) explodes in sunlight 0
57. Copper sulphate dissolves in excess of KCN to give: (d) reacts with air in sunlight 0
[C.B.S.E. 2006] 72. Verdigris is:
(a) [Cu(CN)4]3- 0 (b) [Cu(CN)4]2- 0 (a) basic copper acetate 0 (b) basic h~ad acetate . 0
(c) Cu(CN)2 0 (d) CuCN 0 (c) basic lead 0 (d) none 0
58. From asolution of copper sulphate, the metal used to recover 73. In solid copper sulphate, copper is coordinated to:
copper, is: (a) five water molecules 0 (b) four water molecules [J
(a) Na o (b) Ag o (c) one sulphate ion 0 (d) one water molecule 0
(c) Hg o (d) Fe [1 74. While extracting an element from its ore, the ore is ground
59. Argentite is an ore of: and reacted with dilute KCN solution to form a soluble
(a) Ag 0 (b) Au o complex. The element is:
(c) Pt 0 (d) Cu o (a) lead 0 (b) chromium 0
60. Cyanide process is used to obtain: (c) manganese 0 (d) silver 0
(a) Cr 0 (b) Ag 0 75. Percentage of silver in the alloy german silver, is:
(c) Cu 0 (d) Zn 0 (a) 2.5% 0 (b) 1.5% 0
61. On heating Cu(N0 3h strongly, the material finally obtained (c) 10% 0 (d) 0% 0
is: 76. Preparation of looking mirrors involves the use of:
(a) Cu 0 (b) Cu 20 0 (a) red lead 0
(c) Cu(N002 . 0 (d) Cu(N03h 0 (b) arnmonical silver nitrate 0
62. When NH40H is added to copper sulphate solution, blue (c) arnmonical AgN0 3 + red lead 0
colour is obtained due to formation of: (d) arnmonical AgN0 3 + red lead + HCHO 0
77. The formula of the product formed, when sodium
(a)Cu 2+ [] (b) Cu(NH4S04h 0
thiosulphate solution (hypo solution) is added to silver
(c) [Cu(NH3)4]2+ 0 (d) Cu(OHh 0 bromide is: [E.A.M.C.E.T. 2007]
63. An alloy which does not contain copper, is:
(a) Ag2S20 3 0 (b) Ag2S 0
(a) solder 0 (b) bellmetal 0
(c) bronze 0 (d) brass' 0 (c) Ag3[Na(S203)i1 0 (d) Na3[Ag(S203h] 0
64. Which of the following is the lunar caustic? 78. German silver has: [D.C.E. 2006]
(a) AgN03 0 (1:» Cu202 0 (a) Zn 0 (b) Cu o
(c) Cu02 0 (d) Hg20 2 0 (c) Ni 0 (d) all o
65. Hair dyes contain: [V.LT.E.E.E. 2008) 79. An extremely hot copper wire reacts with steam to give:
(a) copper nitrate 0 (b) gold chloride 0 (a) CuO 0 (b) Cu20 0
(c) silver nitrate 0 (d) copper sulphate 0 (c) CU2~ 0 (d) Cu~ 0
80. Silver is refined by cupellation process. The process removes 95. The liquid metal at room temperature is:
the impurity of: (a) Ca 0 (b) Zn 0
(a) Cu 0 (b) Au 0 (c) Hg 0 (d) Pb 0
. (c) Pb 0 (d) Pt 0 96. Cinnabar is the ore of:
81. Which is least soluble in water? (a) Zn 0 (b) Cd 0
(a) AgCl 0 (b) AgBr 0 (c) Hg 0 (d) Ag 0
(c) AgI 0 (d) Ag2S 0 97. Chemically philosopher's wool is:
82. The compound soluble in annnonia is: (a) Zno 0 (b) BaO 0
(a) Cu(OH}z 0 (b) Al(OHh o (c) HgCl 0 (d) Hg2Cl2 0
(c) Cr(OHh 0 -(d) Fe(OHh o 98. Philosopher's wool when heated with BaO at llOO°C gives
83. AgCI on fusion with sodium carbonate, give,,: the compound:
(a) Ag2C03 0 (b) Ag20 o (a) BaCdD.2 0 (b) Ba + Zn02 0
(c) Ag 0 (d) Ag2C2 o (c) Ba02 + Zn 0 (d) BaZn02 0
84. Which metallurgy involves leaching? [D.C.E. 2006] 99. The purest zinc is made by :
(a) Au 0 (b) Ag o (a) Zone refining 0 (b) Mond's process 0
(c)bQthJaLand(b) 0 (d) none of these - o (c) Poling process 0 (d) Van-Arkel process 0
100. A compound -is yellow whellhot and white when cold..----- .......... .
85. Gold is solJlble in:
compound i s : - -- - -
(a) cone. HCI 0 (b) conc. H2S04 0
(c) conc. HN03 0 (d) aqua-regia 0 (a) Al20:3 0 (b) PbO 0
86. Amongst the following, the lowest degree of paramagnetism (c) Cao 0 Cd; ZnO 0
per mole of the compound will be shown by: 101. The hydroxide which is soluble in excess of NaOH solution
is:
(a) MnS044H20 0 (b) CuS04·5H20 0
(a) Cu(OH}z 0 (b) Fe(OHk: [1
(c) FeS04·7H20 0 (d) NiS04·6H2G 0
(c) Cr(OH)3 0 (d) Zn(0H)2 0
87. Identify the statement which is not correct regarding CUS04'
102. The colour of zinc sulphide is:
(a) It reacts with KI to give iodine 0
(a) yellow 0 (b) white 0
(b) It reacts with NaOH and glucose to give-Cu20 0
(c) brown 0 (d) black 0
(c) It reacts with KCI to give CU2Cl2 0 103. The compound which is widely used as a white pigment,
(d) It gives CuO on strong heating 0 is:
88. What is the effect of shaking dilute H2S04 with a small (a) PbC03 o
quantity of anhydrous CUS04?
(a) The white solid dissolves to form a colourless solution 0
(c) ZnO o
104. Corrosive sublimate is:
(b) The white solid dissolves to form a green solution 0
(c) The white solid dissolves to form a blue solution 0 (a) HgCl2 o (b) Hg2Cl2 o
(d) The white solid turns blue but does not dissolve 0 (c) Hg2Cl o (d) Hg2Cl3 o
89. When copper reacts with hot and cone. H 2S04, gives: 105. Calomelis the name of:
[A~F.M.C. 2006] (a) HgClz o (b) Hg2Cl2 o
(a) H2 o (b) S02 o (c) HgCl 2 + Hg o (d) Hg2Cl2 + Hg o
(c) D.2 o (d) N;z o 1(x). Which of the following compound is used as a purgative?
90. Which silver halide is least soluble in ammonia? (a) CuzCl2 0 (b) CuCl2 0
(a) AgF 0 (b) AgCl 0 (c) Hg2Cl2 0 (d) HgClz 0
(c) AgBr 0 (d) AgI 0 B17. In the reaction, SnCl2 + HgCl 2 ~ A + SnCI4; A is:
91. AgCI precipitate dissolves in NH3 due to the formation of: (a) Hg2Cl2 0 (b) Hg 0
(a) Ag(NH3hCl 0 (b) Ag<NH4)zCl . 0 (c) HgCl 0 (d) HgCl3 0
(c) Ag<NH4)20H 0 (d) Ag(NH3)zOH 0 108. In the reaction, HgCl2 + KI ~ A + KCI; A is:
92. Impurities of lead in silver are removed by: (a) Hgl2 0 (b) K2HgI3 0
(a) Parkes process 0 (b) Solvay process 0 (c) K2Hg4 0 (d) KHgI3 0
(c) cyanide process 0 (d) amalgamation process 0
100. Zinc carbonate is precipitated from zinc sulphate solution
93. Zinc is a member ofIIB or 12th group of the periodic table.
by the addition of:
The other members of this group are:
(a) Na2C~ 0 (b) CaC03 D
(a) boron and aluminium 0 (b) cadmium and mercury 0
(c) silver and gold 0 (d) tin and lead 0 (c) MgC03 0 (d) NaHC03 0
94. Calamine is the ore of: 110. The compound amongst following sublimes on heating, is:
(a) Zn o (b) Pb o (a) HgCl2 0 (b) AgN03 0
(c) Ca o (d) Hg o (c) Zn(N03h 0 (d) Hg2Cl2 0
111. Which of the following is insoluble in cold water? (iii) Acquires yellow colour on heating
[A.I.I.M.S. 2004] (a) ZnO D (b) AI20 3 D
(a) Hg2(N03h D (b) Hg2Cl2 D (c) PbO D (d) HgO D
(c) Hg(N03h D (d) Hg 2(CI0 4h D 125. When excess of SnCl2 is added to a solution of HgCI 2, a
112. In Nessler's reagent the active ion is: white precipitate turning to grey, is obtained. The grey
(a) Ag+ D (b) Hg2+ D colour is due to the formation of:
(c) HgI~- D (d) [Hg4]2- D (a) Hg 20 2 D (b) SnC4 D
113. Sulphide ore of zinc is concentrated by: (c) Sn D (d) Hg D
(a) froth floatation D 126. Essential constituent of an amalgam is:
(b) electromagnetic process D (a) iron D (b) an alkali metal D
(c) gravity process D (c) silver D (d) mercury D
(d) .distillation D 127. Nessler's reagent is:
114. White vitriol is: (a) K2HgI4 D (b) K2HgI4 + KOH D
(a) ZnS D (b) Znso 4 D (c) K2HgI2 + KOH D (d) K2Hg4 + Hg D
(c) ZnS04·7H20 D (d) Znco 3 D 128. If NaOH is added to an aqueous solution of zinc ions, a
lIS. Granulated zinc is made by : white precipitate appears and on adding excess NaOH, the
(a) pourirrgmolterrmetalinwater [J predpitatedissolves.In this solution zirrc exists in the: - - -
(b) pouring molten metal in molten nickel D (a) cationic part l"3:-==--
(c) displacing zinc from a ZnS04 solution D (b) anionic part D
(d) zone refining D (c) both in cationic and anionic parts D
116. On heating ZnCI 2·2H 20, the compound obtained is: (d) there is no zinc in solution D
(a) ZnCl2 D (b) Zn(OH)CI D 129. The formula of haematite is:
(c) Zn(OH)2 D (d) ZnO D (a) Fe304 D (b) Fe203 D.
117. The compound which is used in the preservation of wood (c) FeC03 D (d) FeS2 0
is: 130: The atomic number of iron is 26. The electronic confi-
(a) NaO D (b) HgCl2 D guration is:,
(c) ZnCl2 D (d) Ca02 D (a) 2,8,8,8 D (b) 2,8,15,1 D
118. Mercury is transported in the containers made of: (c) 2,8,13,3 D (d) 2,8, 14,2 D
(a) Ag D (b) Pb D 131. Iron is alan:
(c) AI [] (d) Fe D (a) normal element D
119. Lucas reagent is: (b) representative element D
(a) ZnCl2 + HCI(conc.) [] (b) Mn02 + H 20 D (c) transition element D
(c) H2S04 + HCI D (d) NO + H20 D (d) inner-transition element D
120. Mercury on heating with aqua-regia gives: 132. Which one of the following statements is not correct?
(a) Hg(N03h D (b) HgCl2 D (a) Iron belongs to VIII group D
(c) Hg(N02h 0 (d) Hg2Cl2 [J (b) Iron belongs to third period D
121. Which one of the following statements is wrong? (c) Iron is the member of 3d-series 0
(a) HgCl2 dissolves in hot water D (d) Iron is a transition metal D
(b) HgCl 2 gives HCI when treated with sulphuric acid D 133. Iron is extracted from:
(c) HgCl 2 gives yellow ppt. with NaOH D (a) haematite [] (b) magnesite D
(d) HgCl2 gives white ppt. with ammonium hydroxide D (c) iron pyrites D (d) cha1copyrites D
122. Which one of the following statements is correct? 134. The iron ores are concentrated by:
(a) Hg 2Cl 2 is called corrosive sublimate D (a) gravity ,;eparation D
(b) Hg202 gives white ppt. with ammonium hydroxide D (b) froth floatation process D
(c) Hg 2Cl 2 is used as a purgative D (c) amalgamation D (d) hand picking D
(d) Hg 2Cl 2 is soluble in water [] 135. The materials mixed before the calcined ore is subjected for
123. Mark the correct statement: smelting in the extraction of iron are:
(a) Hg forms an amalgam with iron [J (a) coke and silica D
(b) Hg vapour is non-poisonous D (b) coke and limestone D
(c) Hg is monovalent in mercurous compounds [J (c) limestone and silica D
(d) Oxysalts of mercury are thermally unstable D (d) coke, limestone and silica D
124. Which of the following oxides has the following 136. The smelting of iron in a blast furnace involves all the
characteristics? following processes, except:
(i) Amphoteric nature (a) combustion D (b) reduction 0
(ii) Can be reduced by carbon (c) slag formation D (d) sublimation 0
137.. The maximum temperature 1500"C is obtained in the ..... 153. FeS04·7H20 is known as:
region of the blast furnace used in the extraction of iron. (a) green vitriol 0 (b) white vitriol 0
(a) reduction· 0 (b) fusion 0 (c) blue vitriol 0 (d) vitriol []
(c) combustion 0 (d) slag formation 0 154.. Acidified potassium permanganate is decolourised by:
138. In the extraction of iron in the blast furnace, the reducing (a) white vitriol 0 (b) bleaching powder 0
agent for the ore is: (c) laughing gas 0 (d) Mohr's salt 0
(a) carbon ~D (b) carbon monoxide 0 155. Number of unpaired electrons in Fe2+ ion is:
(c) carbon dioxide 0 (d) silica 0 (a) zero 0 (b) 2 0
139. The iron obtained from the blast furnace is called: (c) 4 0 (d) 5 []
(a) pig iron 0 (b) cast iron 0 156. Iodine is liberated on adding potassium iodide solution to
(c) wrought iron 0 (d) steel 0 a solution of:
140. Purest form of iron is: (a) ZnCh 0 (b) FeCl3 0
(a) pig iron 0 (b) cast iron 0 (c) HgCl2 0 (d) AICl3 0
(c) wrought iron 0 (d) steel 0 157. Mohr's salt is a:
141. The carbon content in steel is: (a) normal salt 0 (b) acid salt 0
(a) 0.21 to 0.25% 0 (b) 2 to 2.5% 0 (c)J)~* slMt 0 (d)duublesalt -~~-
(C)O.2Sto2% 0 (d) 5 to 8% 0 158. Blood red coloured solution is produced when ferric cWolide....
142. Stainress' steel conui:insiron and: solution is treated with:
(a) Zn 0 (b) Cu 0 (a) KSCN 0 (b) KCN 0
(c) AI 0 (d) Cr 0 (c) ~Fe(CN)6 0 (en K3Fe(CN)6 0
143. If red hot steel is suddenly immers,ed in water, the steel 159. The brown ring complex compound is formulated as
becomes: [Fe(H20)s(NO)]S04. The oxidation state of iron is:
(a) soft and malleable 0 (b) hard and brittle 0 (a) 1 0 (b) 0 0
(c) tough and ductile 0 (d) fibrous 0 (c) 2 0 (d) 3 0
144. Axles are made by heating rods of iron embedded in charcoal 160. Ferrous sulphate on heating gives:
powder. The process is known as: (a) S02 and S03 0 (b) S02 only 0
(a) tempering 0 (b) annealing 0 (c) S03 only 0 (d) S02 and O2 0
(c) hardening 0 (d) case hardening [] 2
161. Which one of the following combines with Fe + ion to form
145. Iron is rendered passive by treatment with: a brown complex?
(a) H2S04 (dil.) 0 (b) H3P04 [] (a) N20 0 (b) NO []
(c) RN0 3 (conc.) 0 (d) HCl 0 (c) N 20 3 0 (d) N 20 S 0
146. Nitriding is a process of heating steel in atmosphere of: 162. Finely divided iron combines with CO to give:
(a) ammonia 0 (b) oxygen 0 (a) Fe(CO)s 0 (b) Fez(CO)9 0
(c) carbon dioxide 0 (d) air [] (c) Fe3(COh2 0 (d) Fe(CO)6 []
147. In the metallurgy of iron, when limestone is added to the 163. Bessemer converter is used in the manufacture of:
blast furnace, the calcium ion ends up in: (a) pig iron 0 (b) steel []
(a) slag 0 (b) gangue 0 (c) wrought iron 0 (d) cast iron 0
(c) metallic calcium 0 (d) calcium carbonate 0 164. The colour of FeS04·(NH4hS04·6H20 is:
148. Annealing process is: (a) red 0 (b) blue 0
(a) heating the steel bright red and then cooling suddenly[] (c) white 0 (d) green []
(b) heating the steel bright red and then cooling slowly 0 165. In our country, iron is obtained from the ore:
(c) heating the rods of iron embedded in charcoal [] (a) cassiterite 0 (b) azurite []
(d) heating the rods of iron in ammonia 0 (c) haematite 0 (d) cryolite 0
149. Which one of the metals does not form amalgam? 166. Which one of the following elements constitutes a major'
(a) Zn D. (b) Ag 0 impurity in pig iron?
(c) Cu 0 (d) Fe 0 (a) Graphite 0 (b) Oxygen []
ISO. Rust is: (c) Sulphur 0 (d) Silicon 0
(a) Fe203 0 (b) FeO-xH20 0 167. Which of the following is the correct IUPAC name for
(c) Fe203·xH20 0 Cd) Fe304·xH20 0 ~e(CN)6?
151. When steam is passed over red hot iron, the substances (a) Potassium ferricyanide []
formed are: (b) Potassium ferrocyanide 0
(a) Fe203 + H2 0 (b) Fe304 + H2 0 (c) Potassium hexacyanoferrate (II) 0
(c) FeO+H2 0 (d) FeO+H2 +02 0 (d) Potassium hexacyanoferrate (III) 0
152. Iron is obtained on a large scale from Fez03 by: 168. In the manufacture of iron from haematite, limestone is
(a) reduction with AI 0 (b) calcium 0 added to act as:
(c) reduction with H2 0 (d) reduction with CO 0
(a) slag D (b) an oxidising agent D 182. Which of the following metals exhibit more than one
(c) a reducing agent D (d) flux D oxidation state?
169. Which of the following statements is not true for Mohr's (a) Na D (b) Mg D
salt? (c) Fe D (d) All D
(a) It decolourises KMn04 solution D 183: Platinum, palladium, iridium, etc., are called nobel metals
(b) It is a double salt D because:
(c) Oxidation state of iron is +3 D (a) Alfred Nobel discovered them D
(d) It is a primary standard D . (b) they are inert towards many common reagents D
170. When K4Fe(CN)6 is added to FeC13, the complex compound (c) they are shining, lustrous and pleasing to look at D
formed is: (d) they are found in native state D
(a) Fe3[Fe(CN)6]4 D (b) Fe4[Fe(CN)6h D 184. Which of the following pairs has the same size?
(c) K2Fe[Fe(CN)6] D (d) K2Fe3[Fe(CN)6h D [C.B.S.E. (P.M.T.) 2010]
171. One of the important uses of ferrous sulphate is in the: (a) Zr4+, Hf4+ D (b) Fe2+, Ni2+ D
(a) manufacture of blue-black ink D (c) Zr4+, Ti4+ D (d) Zn2 +, Hf 4 + D
(b) manufacture of writing chalks D 185. Permanent magnet is made from:
(c) manufacture of sulphur dioxide D (a) cast iron D (b) steel D
(d) manufacture .of hydrogen· sulphide [J. (c)wrougnt iron D (d) allofthese 0----·
172. Ferric sulphate on heating gives: 186. ill comparison of ferrous salts, ferric salts are: - - _.._ -
(a) S02 and S03 D (b) S02 only D (a) more stable D (b) less stable D
(c) S03 only D (d) S only D (c) equally stable D (d) none of these D
173. Which of the following metals corrodes readily in moist air? 187. The metal which does not react with cold water but evolves
(a) Au D (b) Ag D hydrogen with steam is:
(6) Ni D (d) Fe D (a) Na . D (b)K D
174. Which of the following has lowest percentage of carbon? (c) Pt D (d) Fe D
(a) Cast iron D (b) Wrought iron D 188. The iron salt used in blue prints is:
(c) Steel D (a) FeC20 4 D (b) F~(C204)3 D
(d) All have same percentage D (c) ~e(CN)6· D (d) FeS04 D
175. In the reaction, 4Fe + 302 ~ 4Fe3++60 2-; which of the 189. The compound that gets oxidised even on exposure to air
following statements is incorrect? is:
(a) It is a redox reaction D D (b) NiS04 D
3 (a) CO2(S04h
(b) Metallic iron is reduced to Fe + D
(c) FeS04 D (d) KMn0 4 D
(c) Fe3+ is an oxidising agent D
190. Anhydrous ferric chloride is prepared by:
(d) Metallic iron is a reducing agent D
176. When AgCl is treated with KCN : [.J.E.E. (W.B.) 2010]
(a) dissolving ferric hydroxide in dilute HCl D
(a) Ag is precipitated D (b) dissolving ferric hydroxide in cone. HCl D
(b) double decomposition reaction occurs D (c) by passing dry C12 gas over heated scrap iron D
(c) a complex is formed D
(d) by passing dry HCl gas over heated scrap iron D
191. In the dichromate dianion:
(d) no reaction occurs D
177. Which of the following will dissolve in excess of ammonia?
(a) 4Cr-O bonds are equivalent D
[A.M.U. (Engg.) 2010]
(b) 6Cr-O bonds are equivalent D
(c) all Cr-O bonds are equivalent D
(a) AgI D (b) AgBr D
(d) all Cr-O bonds are non equivalent D
(c) AgCl D (d) None of these !:J
192. Which one of the following pairs of substances on reaction
178. Mark the variety of iron which has highest melting point:
will not evolve H2 gas?
(a) pig iron D (b) cast iron D
(a) Iron and dil. H 2S0 4 D (b) Iron and steam D
(c) steel D (d) wrought iron D
(c) Copper and HCl(g) D
179. The most stable oxidation state of iron is:
(d) Sodium and ethyl alcohol D
(a) +2 [] (b) +3 D
193. cr0 3 dissolves in aqueous NaOH to give:
(c) -2 D (d) -3 D
(a) crOJ- D (b) Cr(OHh D
ISO. Iron is protected by coating it with a thin layer of:
(c) Cr20~- D (d) Cr(OHh D
(a) Cu D (b) Zn D
194. A student accidently added cone. H 2S04 to potassium
(c) Pb D (d) Mg D permanganate and it exploded due to the fOlmation of an
181. Which is not amphoteric? explosive. Which of the following is formed?
(a) Al 3+ D (b) Cr3+ D [A.M.ll. (Engg.) 2010]
2 2
. (c) Fe + D (d) Zn + D (a) Mn207 D (b) Mn02 D
(c) Mn20S D (d) Mn203 D
TransitiQn Elements Qr d-blQck Elements and l-blQck Elements 741
195. Which Qne €If the iQnicspecies will impart cQIQur tQ an 206. The catalytic activity of transitiQn elements and their
aqueQus solutiQn? cQmpounds is described tQ: [C.E.E. (Kerala) 2002]
(a) Ti4+ 0 (b) Cu+ 0 (a) their chemical reactivity 0
(c) Znz+ 0 (d) Cr3+ 0 (b) their magnetic behaviQur 0
196. AdditiQn €If high proPQrtiQns €If manganese makes steel (c) their unfilled d-orbitals 0
useful in making rails €If rail roads, because ma'lganese: (d) their ability tQ adQPt multiple QxidatiQn states and their
(a) gives hardness tQ steel 0 complexing ability . i. 0
(b) helps the fQrmatiQn €If Qxides €If irQn 0 2fJJ. Which €If the fQllQwing sets isl €If coinage metals?
(c) can shQW highest QxidatiQn state €If +7 0 [D.P.M.T.2003]
(d) imparts special cQIQur tQ steel 0 (a) Cu, Ag, Au 0 (b) Zn, Cd, Hg 0
197. Which €If the fQllQwing statements is nQt CQrrect with (c) Au,Ag,Zn Q (d)Li,Na,K 0
reference tQ ferrQus and ferric iQns? 208. A reduction in the atQmic size with fucrease in atQmic number
(a) Fe3+ gives brown CQIQur with PQtassium ferricyanide 0 is a characteristic €If the elements €If:
z
(b) Fe + gives blue precipitate with PQtassium ferricyanide 0 (a) d-blQck 0 (b) j-block 0
(c) Fe3+ gives red CQIQur with PQtassium thiQcyanate 0 (c) radiQactive series 0 (d) high atQmic masses 0
(d) Fez+.gives browncQleur withammoniurnthiQcyanateD What wQuldhappen when aSQlutiQnof potassium chromate--~
19&. AmQngstthe following, identify the species with an atQm is treated with an excess €If dilute nitric. acid?
in +6 exidatiQn state: [I.I.T. (S) 2000] {A.I.E.E.E.2003]
(a) Cr3+ and Cr20i- are formed 0
(a) MnO"4 0 (b) Cr(CN)[ 0
(b) Cr20i- and H 20 are fQrmed 0
(c) NiFi- 0 (d) CrO:P2 0
199.. What is the shape €If Fe(CO)s mQlecule? [C.B.s.E. 2000] (c) Cr2oi- is reduced to +3 state €If Cr 0
(a) Tetrahedral o (b) Octahedral 0 (d) Cr20i:- is Qxidised to +7 state €If C r E l -
(c) Trigonal bipyramidal 0 (d) Square pyramidal 0 210. The atQmic numbers €If vanadium (V), chrQmium (Cr),
200. hI the standardizatiQn €If Na2S203 using K2Cr207 by manganese (Mn) and iron (Fe) are 23, 24, 25 and 26
iQdQmetry, the equivalent weight €If KZCr207 is: respectively. Which Qne of these may be expected tQ have
rUT. (8) 2001] the highest second iQnisation enthalpy? {A.I.E.E.E.2003]
(a) V 0 (b) Cr 0
(a) MOlecul; weight o (c) Mn 0 (d) Fe 0
211. The radius €If La 3+ is 1.06 A. which €If the follQwing given
(b) MQlecular
o values will be closest tQ the radius €If Lu 3+ (At. nQ. €If
Lu 71, La::::: 57)? [A.I.E.E.E.2003]
o OOI~A 0 ~IA~ 0
(d) Same as mQlecular weight 0 (e) 1.06 A 0
(d) 0.85 A 0
201. Which Qne €If the fQllQwing is the CQrrect configuratiQn €If 212. Which of the fQllowing transition metaJ.s shQWS Qnly +3
Fe3+ (Z = 26)? . [S.C.R.A. 2001] QxidatiQn state? [C.B.S.E. (Medical) 2003]
(a) [Ar] 4i, 3; 0 (b) [Ar14i,3d3 0 (a) Ce 0 (b) Pt 0
(~) [AI:] 3cf 0 (d)[Ar] 4l, 3tf 0
(c) Nd 0 (d) Gd 0
213. The basic character €If the transitiQn metal mQnoxides
202. Which grQUP cQntains colQured iQns out Qf:[C.P.M.T. 2001]
fQllQWS the Qrder (Atomic nQ. €If Ti 22, V 23, Cr = 24,
1. Cu+ 2. Ti4+ 3. CQ2+ 4. Fe2+
Fe::::: 26) : [C.B.S.E. (Medical) 2003; A.I.I.M.S. 2007J
(a) 1,2,3,4 0 (b) 3,4 0 (a) crO> VO>FeO>TiO 0
(c) 2,3 0 (d) 1,2 0 (b) TiO > FeO > VO > crO 0
203. The number of iQns fQrmed on dissQlving Qne molecule €If (c) TiO> VO>CrO >FeO 0
FeS04·(NH4hS04·6H20 is/are: [A.I.LM.s. 2001] ~W>~>~>~ 0
(a) 6 0 (b) 3 0 214. Vitamin -B12 cQntains: [C.B.S.E. (Medical) 2003]
(c) 5 0 (d) 4 0 (a) C0 3+ 0 (b) Zn 2+ 0
Number of electrQns transferred in each case when KMn04
(c) Ca2+ 0 (d) Fe2+ 0
acts as an Qxidising agent tQ give MnOz, Mn2+, Mn(OHh,
215. Which €If the fQllQwing pairs €If iQns have same para-
MnOl- are respectively: [A.I.E.E.E.2002]
magnetic mQment ? [E.A.M.C.E.T. (Engg.) 2004]
(a) 3,5,4 and 1 0 (b) 4,3, 1 and 5 0 2 2
(a) Mn +, Cu + 0 (b) Cu 2+, Ti 3+ 0
(c) 1. 3, 4 and 5 0 (d) 5,4, 3 and 1 0
205. Which Qne €If the fQllowing is an example of nQn typical
4 2
(e) Ti +, Cu + 0 (d) TP+,Ni 2+ 0
transition elements? [P.M.T. (M.P.) 2002] [Hint: Cu 2+ E.C. = 3d 9 -one unpaired electron, Ti 3+ E.C. 3d J_
(a) Li, Na, K • 0 (b) Be, AI, Pb 0 one unpaired electron.]
(c) Zn, Cd, Hg 0 (d) Ba, Ga, Sr 0
216. The colourless species is: [A.I.I.M.S. 2003] (c) H 2S04 is a dibasic acid 0
(a) VCl3 0 (b) VOS04 0 (d) rate is faster in the presence of H 2S04 0
(c) Na3V04 0 (d) [V(H20)6]S04H20 0 (e) only H2S04 is completely ionised 0
217. Lanthanide for which +II and +ill oxidation states are 226. The correct order of ionic radii of y3+, La3+, Eu 3+ and Lu3+
common is: [A.I.I.M.s. 2003] is: [P.M.T. (Kerala) 2007]
(a) La 0 (b) Nd 0 (a) y3+ < La3+ < Eu3+ < Lu 3+ 0
(c) Ce (d) Eu o 0 (b) Lu 3+ < Eu3+ < La3+ < y3+ 0
218. How many electrons are involved in reduction of KMn04 (c) La3+ < Eu 3+ < Lu3+ < y3+ 0
in basic medium? [J.E.E. (Orissa) 2003] (d) y3+ < Lu3+ < Eu3+ < La3+ 0
(a) 1 0 (b) 2 0 (e) Eu3+ < La3+ < Lu3+ < y3+ 0
(c) 5 0 (d) 3 0 227. Excited state of configuration of Mn2+ is:
219. Lanthanides and actinides resemble in: [A.F.M.C. 2004] . [A.M.U. (Ellgg.) 2007]
4
(a) t2g 0 (b) t23 e 2 0
(a) electronic configuration 0 g g
(b) oxidation s,tate 0 (c) ionisation state 0 1
(c) t ge; 0 (d) t~ge~ 0
(d) formation of complexes 0 228. Extraction of zinc from zinc blende is achieved by:
220.- - ------- -- ---- --
Among the following series of transition ions, the one where
.... .... -.. -2
[I.l.T. 2007]
all metal ions have 3d electronic coIlfigllflltion. is (Atomic (it) electrolytic roouciion 0,--------
.....
no. ofTi = 22; V = 23; Cr 24; Mn 25): = ----- (OJ roasfulg Iollowed6yTeauctionwifficarbOri-----O-==----
[C.B.S.E. (p.M.T.) 2004] (c) roasting followed by reduction with another metal 0
(a) Ti3+,V2+,Cr3+,Mn4+ 0 (b) Ti+,y4+,Cr6+,Mn7+ 0 (d) roasting followed by self reduction 0
3 3 2 3 4 5 229. A solution of a metal ion when treated with KI gives a red
(c) Ti4+,V +,Cr2+,Mn + 0 (d) Ti +,V +,Cr +,Mn + 0
precipitate which dissolves in excess of KI to give a
221. Lanthanides are: [CoB.S.E. (p.M.T.) 2004] colourless solution; Moreover, the solution ef metal ion on
(a) 14 elements in the sixth period (Atomic number 90 to treatment with a solution of cobalt (II) thiocyanate gives
103) that are filling 4f-sublevel 0 rise to a deep blue crystalline precipitate. The metal ion is:
(b) 14 elements in the sixth period (Atomic number 58 to [I.I.T.2007]
71) that are filling 4f-sublevel 0 (a) Pb2+ 0 (b) Hg2+ o
(c) 14 elements in the seventh period (Atomic number 90 to (c) Cu 2+ 0 (d) C02+ o
103) that are filling Sf-sublevel 0 230. Identify the incorrect statement among the following:
(d) 14 elements in the seventh period (Atomic number 58 to [A.I.E.E.E.2007]
71) that are filling 4f-sublevel 0 (a) 4f and Sf-orbitals are equally shielded 0
222. The product of oxidation of r
with MnO:; in alkaline (b) d-block elements show irregular and erratic chemical
medium is: [U.T. (S) 2004] properties among themselves 0
(a) 103 0 (b) 12 0 (c) La and Lu have partially filled d-orbitals and no other
(c) 10- 0 (d) 104 0 I partially filled orbitals 0
223. Consider the ground state of Cr-atom (Z 24). The number = (d) The chemistry of various lanthanoids is very similar 0
of electrons with the azimuthal quantum numbers I = 1 and 231. Which one of the following ions is the most stable in
2 are respectively: [A.I.E.E.E.2004] aqueous solution? [C.B.S.E. 2007]
(a) 12 and 4 0 (b) 12 and 5 0 (a) V3+ 0 (b) Ti 3+ 0
(c)·16and4 0 (d) 16 and 5 0 (c) Mn 3+ 0 (d) Cr3+ 0
=
224. Cerium (Z 58) is an important member of lanthanides. 232 Identify the incorrect statement among the following:
_Which of the following statements about cerium is [C.B.S.E. 2007]
incorrect? [A.I.E.E.E. 2004] (a) Lanthanoid contraction IS the accumulation of
(a) The common oxidation states of cerium are +3 and +4 successive shrinkages 0
o (b) As a result of lanthanoid contraction, the properties of
(b) The +3 oxidation state of cerium is more stable than +4 4d-series of the transition elements have no similarities
oxidation state 0 with the 5d-series of elements 0
(c) The +4 oxidation state of cerium is not known in (c) Shielding power of 4f-electrons is quite weak 0
solutions 0 (d) There is a decrease in the radii of the atoms or ions as
(d) Cerium (IV) acts as an oxidising agent 0 one proceeds from La to Lu 0
225. KMn0 4 is a strong oxidising agent in acid medium. To 233. Which of the following ions has a magnetic moment of 5.93
provide acid medium H 2S04 is used instead of HCI. This is B.M.? [p.E.T. (Kerala) 2007]
because: [P.M.T. (Kerala) 2007] (a) Mn2+ 0 (b) 0
(a) H 2S04 is stronger acid than HCI 0 (c) Cr2+ 0 (d) V 3+ 0
(b) HCI is oxidised by KMn04 to Ch 0 (e) Cr3+ 0
Transition Elements or d-block Elements andf-block Elements
234. When hydrogen peroxide is added to acidified potassium of air, its compound B is formed. B reacts with compound
dichromate, a blue colour is produced due to formation of: C to give compound D with liberation of iodine. Then the
[P.E.T. (Kerala) 20071 metal A, and compounds B, C and D are respectively:
(a) ClO:3 o (b) Cr203 0 [P.M.T. (Kerala) lOftSl
(c) GOs 0 (d) crO~- 0 (a) Ti, TiS04, Kl and Til2 0
(e) Cr20?- 0 (b) Zn. ZnS04, Kl and Znl2 o
235. Native silver metal forms a water soluble complex with a (c) Cu, CUS04, Kl and CU2I2 0
dilute aqueous solution of NaCN in the presence of: (d) Cu, CUS04, Kl and CUl2 0
[1.I.T.2008] [Hint: Cu : ls2,2i2p6,3s23p63dlO,4s1 Magnetic moment
(a) nitrogen 0 (b) oxygen o corresponds to one· electron
(c) carbon dioxide 0 (d) argon o 1
Cu + H2S04 + 2:02 ----+ CUS04 + H20
[Hint: 4Ag + 8NaCN + 2H 20 + 02 ----+ 4[NaAg(CNh] +
(E)
4NaOH]
2CUS04 + 4KI CU212 + 12 + 2K2S04]
236. Among the following, the coloured compound is: (C) (D)
[I.I.T. 20081
(a) CuCl 0 (b) K 3[Cu(CN)4] 0 243. What is the correct order of spin only magnetic moment of
Mn?+, €r2+and- y2+? . -·---lA~F;M.C;24J08t--
(c)CuF2 r::J(dHtu(CH;CN)4]B1<'4 0
237. Thecbrrect ordeiof decreasing second ioiiisationenthalpy (a) Mn2+;::;y2+>Cr2+ EJ (b)y2+;::;Cr2+->:Mn4± n
of Ti(22), Y(23), Cr(24) and Mn(25) is: [C.B.s.E. 2008] (c) Mn2+ > Cr2+ > y2+ 0 (d) er2+ > y2+ > Mn2+ D·
(a) Mn>Cr >Ti>Y 0 (b)Ti>Y >Cr>Mn.D [Hint: Ion E.C. Unpaired electrons Magnetic moment
(c) er > Mn > Y > Ti 0 (d) Y > Mn > Cr > Ti 0 V2+ [Ar]3d 3 3 3.86
[Hint : The electronic configurations of M+ ions are : Cr2+ [Ar]3d 4 4 5.0
Cr+ : Ii, 2i2p6,
Mn +: Ii, 2i2l,
y+ : Ii, 2i2p6,
3i3l3d5
5
3i3l3d ,
3i3l3d3 ,
4s1 r
-Stable configuration
Nuclear charge
4s 1 increases
Mn 2 + [Ar]3d 5 5
244. Which has maximum paramagnetic character?[D.C.E. 2008]
(a) [Fe(CN)614- 0 (b) [Cu(H20)4]2+
5.96
0
...]
Ti+ : Ii, 2i2l, 3i3p63d 2, 4s 1 ]

(c) [Cu(NH3)4]2+ 0 (d) [Mn(H20)6]2+ 0
238. Dipping iron article into a strongly alkaline solution of 245. Hybrldisation, shape and milgnetic moment of K3[Co(C0 3hJ
sodium phosphate: [Vl.T.E.E.E.2008] is: [J.E.E. (Orissa) 2fHl8]
(a) does not affect the article 0 0
(a) d2sp 3,
octahedral, 4~9 RM.
(b) forms Fe203·xH20 on the surface 0 0
(c) forms iron phosphate film 0 sp32
(b) d , octahedral, 4.9 B.M.
(d) forms ferric hydroxide 0 (c)
dsp2, square planar, 4.9 B.M. 0 '1
239. When SCN- is added to an aqueous solution containing (d) sp3, tetrahedral, 4.9 B.M. 0
Fe(N03h, the complex ion produced is: [V.J.T.E.E.E.2(08) 246. The spin only magnetic moment value of Cr(CO)6 is:
(a) [Fe(OH2h(SCN)]2+ 0 . (b) [Fe(OH2)sSCN]2+ 0 (a) 0 0 (b) 2.84 0
(c) [Fe(OH2)g(SCN)]2+ 0 (d) [Fe(OH2h(SCN)]6+ 0 (c) 4.90 0 (d) 5.92 0
[Hint: In Cr(CO)6, no orbital is present which is singly
[Hint: Fe 3+ + SCW + 5H20 ----+ [Fe(OH2hSCN]2+1
occupicd, hence magnetic moment value is zero.
240. Which one of the following reactions will occur on heating
AgN0 3 above its melting point? [P.E.T. (Kerala) 2008]
Cr(CO)6 IHIItIHI I I 0 I I I I
(a) 2Ag~03 ~ 2Ag + 2N0 2 + O2 0
(b) 2AgN03 ~ 2Ag + N2 + 302 o 247. Knowing that the chemi$try of lanthanoids (Ln) is
dominated by its +3 oxidation state, which of the following
(c) 2~gN03 ~ 2AgN02 + O2 o statements is incorrect? (A.I.E.E£.. 2f)(9 J
(d) 2AgN03 ~ 2Ag + 2NO + 202 o (a) Because of large size of the Ln(I1I) ions the bonding in
(e) 2AgN03 ~ Ag20 + N 20 3 + O2 o . its compounds is predominantly ionic in character 0
241. Which of the following pairs of transition metal ions are the (b) The ionic sizes of Ln(III) decrease in general with
stronger oxidising ·agents in aqueous solution~? increasing atomic number 0
[P.M.T. (Kerala) 2008] (c) Ln(III) compounds are generally colourless 0
(a) y2+ and Cr2+ 0 (b) Ti 2+ and Cr2+ 0 (d) Ln(I1I) hydroxides are mainly basic 0
3
(c) Mn + and C0 + 3 0 (d) y2+ and Fe + 2 0 248. In context with the transition elements, which of the
2 2 following statements is incorrect? [A.I.E.E.E.2m)'>l
(e) Ni + and Fe + 0
(a) In addition to the normal oxidation states, the zero
242. A transition metal A has spin only magnetic moment value
oxidation state is also shown by these elements in
of 1.8 B.M. When it is reacted with dilute H 2S04 in presence
complexes 0
i
744 GR.B: Inorganic Chemistry for Competitions!
(b) In the highest oxidation states, the transition metals 258. Which of the following oxidation states is the most common
show basic character and form cationic complexes 0 among the lanthanoids? [C.B.S.E. (P.M.T.) 2010]
(c) In the highest oxidation states of the first five transition (a) 4 0 (b) 2 0
elements (Sc to Mn), all the 4s and 3d electrons are used (c) 5 0 (d) 3 0
for bondin§ . 0 259. Which of the following ions will exhibit colour in aqueous
(d} Once the d configuration is exceeded, the tendency to solution? [C.B.S.E. (p.M.T.) Prel. 2010]
involve all the 3d electrons in bonding decreases 0 3
(a) La + (Z == 57) 0 (b) Ti3+ (Z =22) 0
IlIiat ~ In higher oxidation states, Iransition metals show acidic (c) Lu + (Z =71)
3
0 (d) Sc3+ (Z =21) 0
properties and form anionic complexes.] zro. Which6 of the following ions has electronic configuration
249. The oxidant which is used as an antiseptic is : [Ar]d ? [C.B.S.E. (P.M.T.) Prel. 2010]
(a) KBr03 0
(b) KMn04
(J.E.E. (W.B.) 2009]
0
(a)Ni 3
+ 0 (b) Mn 3+ . 0
3
(c) Fe + 0 (d) C03+ 0
(c) C~ _ 0
(d) KN03 IJ
250. 'Electron' is an alloy of : [J.E.E. (W.B.) 2009] 261. How many hydrogen bonded water molecule(s) are
(a) Mg and Zn 0 (b) Fe and Mg 0 associated with CuS04·5H20? [A.M.U. (Engg.) 20101
(c) Ni and Zn 0 (d) A1 and Zn 0 (a) 1 0 (b) 2 0
(c) 3 0 (d) 4 0
251. The temperature of the slag zone in the metallurgy of iron
rising6lasf furnace is : . [c.E.T:-(Karnatab) 2009] 262.. WtiaIistnemagnetic motiicriiorFt?+ ion in rFe(CN)6]:Ff---·--
(a)T500:16~ . o (Of400=7WC . ·tf . (A.M.tJ.<EnggJwl0r~--
(c) 800-1000"C 0 (d) 1200-15O<rC 0 (a) 1. 73 B.M. 0 (b)5.9B.M. 0
252. The magnetic moment of a transition metal is Jf5 BM. (c) Diamagnetic 0 (d) None of these 0
Therefore, the number of unpaired electrons present in it [Hint: [Fe(CN)61>- ---7 It-tin 11' I :I :I [] I: I :I :I
is: [C.E.T. (Kamataka) 2009]
(a) 4 0 (b) 1 0 No. of unpaired eleclron =1
(c) 2 0 (d) 3 0
253. Number of unpaired electrons in Mn 3+ is : p,=~n(n+2) =/3 =1.73 B.M. ]
(J.E,.E. (Orissa) 2009] 263. Which of the following is Vaska's compound?
(a) 2 0 (b) 3 0 [A.M.U. (Engg.) 2010]
(c) 4 0 (d) 5 0 (a) [Ni(pPh3)Clii 0 (b) [Rh(COhOh 0
254. Magnetic moment of (NH4hMnBr4 is ........ BM. (c) Trans IrCI(CO)(PPh 3h 0 (d) IrCl(COh(PPh 3)2 0
[J.E..E. (Orissa) 2809] 264. Mark the correct statement(s) : [P.E.T. (Kerala) 2010]
(a) 5.91 0 (b) 4.91 0 1. Manganese exhibits +7 oxidation state
(c) 3.91 0 (d) 2.46 0 2. Zinc forms coloured ions
255. Electronic configuration of Cu 2+ is: (J..E.E. (Orissa) 2tJOI)] 3. [CoF6]:F is diamagnetic
1 8
(a) [Ar]4s 3d (b) [Ar]4i3d 9
0 0 4. Sc form +4 oxidation state
(c) [Ar]4i3d 7 0 (d) [Ar]4so3d 8 0 5. Zinc exhibits only +2 oxidation state
256. Mn04' reacts with Br- in alkaline pH to give: (a) 1 and 2 0 (b) 1 and 5 0
(J.E.K (Orissa) 2009j (c) 2 and 4 0 (d) 3 and 4 0
(a) Br03',Mn02 0 (b) Br2, MnO~- 0 (e) 2 and 5 0
(c) Br2, Mn0 2 0 (d) BrO-, MnO~- , 0 265. The maximum oxidation state exhibited by actinide ions is :
IlIiat ~ 2Mn04' + Br- + H 20 ---7 20W + 2Mn02 + Br03 ] . [P.E.T. (Kerala) 2010]
257. The correct order of E:2+ IM values with negative sign for (a) +5 0 (b)+4 0
the four successive elements Cr, Mn, Fe and Co is : (c) +7 0 (d)+8 0
[dUE E..K 10111 (e) +6 0
(a) Cr>Mn>Fe>Co 0 (b) Mn>Cr>Fe>Co 0 266. Which of the following is a correct statement?
(c) Cr>Fe>Mn>Co 0 (d) Fe>Mn>Cr>Co 0 (E..A.,M.C.E.T. (Engg.) 2010]
2
(a) Aqueous solutions of Cu+ and Zn + are colourless 0
IlIiIIIl ~ The values are E Mn 2+/Mn =-1.18 V; E~r2+ ICr = 0.91 V; (b) Aqueous solutions of Cu 2+ and Zn2+ are colourless 0
E;e2+ IFe = - 0.44 V ; E~o2+ ICo = - 0.28 V ] (c) Aqueous solution of Fe3+ is green in colour 0
(d) Aqueous solution of Mn04' is colourless 0
. .
SetH : This set contains questions with two or more correct answers.
'2fJ7. Which of the following statements are correct when a mixture 273. Select the compounds 'having metal. in zero oxidation state:
ofNaO and K2Cr207 is gently warmed withconc. H2S04? '(a) Ni(CO)4 0 (b) Cr(CO~ 0
[I.I.T. 1998] (c) F~(CO)9 0 (d) Co(CO)6 0
(a) A deep red vapour is evolved 0 274. Mercurous ion can be represented as:
(b) The vapour when passed into NaOH solution gives a (a) H g + O (b) Hg+-Hg+ o
yellow solution of Na2Cr04 0 (c) Hg!+ 0 . (d) Hl+ 0
(c) Chlorine gas is evolved 0 275. Which of the following are the members of 3d-series?
(d) Chromyl chloride is formed 0 (a) Ti 0 (b) Ag 0
268. Which of the following compounds are coloured due to (c) V 0 (d) Pd 0
charge transfer spectrum? 276. Amongst the following, identify the species with an atom
(Ii) K2Cr2~ 0 (b) KMn04 0 in +6 oxidation stite:
(c) [Fe(H:p)5NO]S04 '0 (d) Mn02 0 (a) KMn04 0 (b) K2Mn04 o
2£f). Which among the following are diamagnetic? (c) ~02[](d)1(39(GN)6
(a)CU2+ O-(b}ZI?F' 0 ttl. Which metals arePresentin geQ1l~_silyel'L
.(crAg+ -O-c(d)tCf+- 0 (a)Cu - - - - . . - 0 -(b) Ni o
270.. Transition metal ions form coloured compounds due to: (c) Zn 0 (d) Ag o
1
(a) d-d transition 0 278.. Transition elements with 4s configuration are:
(b) charge transfer spectrum 0 (a) Cr 0 (b) Mn 0
(c) variable oxidation state 0 (c) Ni 0 (d) Cu 0
. ' (d) partially filledd-orbitals 0 279. The complex fotming tendency of a-transition metal depends
271. Catalysts used in contact 'process of manufacture' of upon:
sulphuric acid are: (a) availability of a number of vacant d-orbitals ' o
(a) NO(g) 0 (b) V20s 0 (b) high ionisation energy o
(c) Mo 0 (d) platinised asbestos 0 (c) small size of its cation or high charge density o
(d) variable oxidation states [I
272. Oxides of which of the following metals show oxidation state
280. Identify the correct statements:
of +8 ?
(a) Iron is the most abundant transition metal o
(a) Ru 0 (b) Os 0 (b) Cast iron is the purest form of iron o
(c) Mn 0 (d) Zn 0 (c) The most stable oxidationstate of iron is +3 o
(d) Iron does not form amalgam. with mercury o
1. (a) 2. (b) 3. (c) 4. (a) 5. (c) 6. (d) 7. (a) 8. (b) 9. (d) 10. (b)
n. (c) 12. (a) . 13. (d) 14. (c) 15. (b) 16. (d) 17. (a) 18. (b) 19. (c) 20. (d)
21. (b) 22. (b) 23. (c) 24. (a) 25. (a) 26. (a) 27. (c) 28. (d) 29. (c) 30. (b)
31. (c) 32. (d) 33, (a) 34. (c) 35. (d) 36. (a) 37. (b) 38. (c) 39. (b) 40. (d)
41. (c) . 42. (a) 43. (c) 44. (b) 45~ (d) 46. (c) 47. (b) 48. (a) 49. (c) 50. (b)
. 51. (c) 52. (b) 53. (a) 54. (d) 55. (b) 56. (a) 57. (a) 58. (d) 59. (a) 60. (b)
61. (b) 62. (c) 63. (a) 64. (a) 65. (c) 66. (d) 67. (b) 68. (a) 69. (b) 70. (a)
71. (b) 72. (a) 73. (b) 74. (d) 75. (d) 76. (d) 77. (d) 78. (d) 79. (a) 80. (c)
81. (d) 82. (a) 83. (c) 84. (c) 85. (d) 86. (b) 87. (c) 88. (c) 89. (b) 90. (d)
91. (a) 92. (a) 93. (b) 94. (a) 95. (c) 96. (c) 97. (a) 98. (d) 99. (a) 100. (d)
101. (d) ·102. (b) 103. (c) l04•.. (a) .105. .(b) 106. (c) 107. (b) lOS... «J_ 1.9', .. (9) no.
lll:(b} ··U2;-(d)··--n3;···(a)· ·······114;·(c)··· ·-115. (a) ·H6.(b)· ... ·-11'1.· (c} ···118.c@)-· U9.-(a). . -:c12O•. (bf...:==-
121. (b) 122. (c) . 123. (d) 124. (a) 125. (d) 126. (d) 127. (b) 128. (b) 129. (b) 130. (d)
131. (c) 132. (b) 133. (a) 134. (a) 135. (b) 136. (d) 137. (c) 138. (b) 139. (a) 140. (c)
141. (c) 142. (d) 143. (b) 144. (d) 145. (c) 146. (a) 147. (a) 148. (b) 149. (d) 150. (c)
151. (b) 152. (d) 153. (a) 154. (d) 155. (c) 156. (b) 157. (d) 158. (a) . 159. (a) . 160... (al
161. (b) 162. (a) 163. (b) 164. (c) 165. (c) 166. (a) 167. (c) 168. (d) 169. (c) 170. (b)
171. (a) 172. (c) 173. (d) 174. (b) 175. (b) 176. (c) 177. (c) 178. (d) 179. (b) 180. (b)
181. (c) 182. (c) 183. (b) 184. (a) . 185. (d) 186. (a) 187. (d) . 188. (b) 189. (c) 190. (c)
191. (b) 192. (c) 193. (a) 194. (a) 195. (d) 196. (a) {197. (d) 198. (d) 199. (c) 200. (b)
201. (c) 202. (b) 203. (c) 204. (a) 205. (c) 206. (d) 207. (a) 208. (b) 209. (b) 210. (b)
2n. (d) 212. (d) 213. (c) 214. (a) 215. (b) 216. (c) 217. (d) 218. (a) 219. (b) 220. (d)
221. (b) 222. (a) 223. (b) 224. (c) 225. (b) 226. (d) 227. (b) 228. (b) 229. (b) 230. (a)
231. (d) 232. (b) 233. (a) 234. (c) 235. (b) 236. (c) 237. (c) 238. (c) 239. (b) 240. (c)
241. (c) 242. (c) 243. (c) 244. (d) 245. (b) 246. (a) 247. (c) 248. (b) 249. (b) 250. (a)
251. (c) 252. (d) 253. (c) 254. (a) 255. (b) 256. (a) 257. (b) 258. (d) 259. (b) 260. (d)
261. (a) 262. (a) 263. (c) 264. (b) 265. (c) 266. (a) 267. (a,b,d) 268. (a,b,c) 269. (b,c,d) 270. (a,b,d)
271. (b,d) 272. (a,b) 273. (a,b;c,d) 274; (b,c) 275. (a,c) 276. (b,c) 277. (a,b,c) 278. (a, d) 279. (a,c) 280. (a,c,d)
Transition Elements or d-block Elements~nd f-block Elements
~ Objective Questions for liT ASPIRANTS ~

1. Mn04 __+:...:X~e=--.:.:Alk=ali=·n:::.e....::ffi:::ed=i=um:::....~) MnOi- 7. An ornament of gold having 87.5% of gold, is of ...... carat.
(a) 21 (b) 18 (c) 15 (d) 24
+Ye - Acidic medium Mn 2 +
[Hint : Pure gold = 24 carat
_ _--?Mn 4+
+_Ze'----_N_e_ulr_al_ffi_ed_iUffi
~~ x 24 =21.0 carat ]
L -_ _
: 87.5% gold =
x, Yand Z are respectively: 8. The highest magnetic moment is shown by the transition
(a) 1,2,3 (b) 1,5,3 metal ion with outer electronic configuration:
2 7
(c) 1,3,5 (d) 5,3, 1 (a) 3d (b) 3d
9 5
[Hint: MnO; + e - All,- med.) MnO~- (c) 3d (d) 3d
5
MnO; +8H+ +5e- Acid med")MnZ+ +4H
[Hint: In 3d configuration, all the d-orbitals are singly occupied.
zO i.e., it has maximum number of unpaired electrons.]
MnO; +4H zO+3e- Mn4+ +80H-]
9. Number of moles of K2Cr207 reduced by one mole of Sn2+
Neu. med")
2. A metal M which is not affected by strong acids like conc. ions is:
HN03;-COnC~" HiS0;fand"concentratedsolutions of alkalies " {a) "1/3 (b) 3
like-KOHand Na0H but"dissolvesincaqua=regia-and-forms (c) I/o (d)o
MCl 3 which is used for toning in photography. The metal M [Hint: CrzO?- + 3Snz+ + 14H+ ~ 2Cr3+ + 3Sn4+ + 7H20
is:
.3 moles of Sn2+ ions reduce:::: 1 mole of Cr2o?-
(a) Ag (b) Hg
:::: I mole of K2Cr20 7
(c) Au (d) Cu
1 mole of Sn2+ ions will reduce = 113 mole of KZCr2~]
[Hint : Au is not affected by concentrated acids and strong
alkalies. However. it dissolves in aqua-regia fonning AuCl3 10. The reason for the stability of Gd3+ ion is: .
which is used for toning in photography. (a) 4f-subshell- completely filled
[HN0 3 + 3HCI ~ NOCI + 2CI + 2H zO] x 3 (b) 4f-subshell - empty
[Au + 3CI ~ AuCI3] x 2 (c) 4fsubshell- half filled
(d) possesses the configuration of a noble gas
2Au + 3HN03 + 9HCI ~ 2AuCl3 + 3NOCI + 6H20] 11. Which is the first man-made element?
3. The metals Rresent in insulin, haemoglobin and vitamin BIZ (a) Sc (b) Tc
are respectively: (c) Os (d) Zr
(a) Zn, Hg, Cr (b) Co, Fe, Zn 12. Select correct statement:
(c) Mg, Fe, Co (d) Zn, Fe, Co (a) PH3 reduces AgN0 3 to metallic Ag
[Hint : Insulin contains zinc, haemoglobin contains iron and (b) Organic tissues turn AgN03 black by reducing it to Ag
vitamin B12 contains cobalt.] (c) AgCN is soluble in KCN
4. Zinc gives Hz gas with H 2S04 and conc. HCl but not with (d) All are correct statements
conc. HN0 3 because: 13. When K ZCr04 is added to CUS04 solution, there is formation
(a) N03" ion is reduced in preference to hydronium ion ofCuCr04 as well as CuCrZ07' Fonnation ofCuCrZ07 is due
(b) conc. HN0 3 is a weaker acid than conc. H ZS04 and conc. to:
HCl (a) basic nature of CuS04 solution
(c) conc. HN0 3 acts as a reducing agent (b) acidic nature of CuS04 solution
(d) zinc is more reactive than Hz (c) this is the typical property of CuS04
[Hint : Zn + H2S04 ~ ZnS04 + H2i (d) there is no formation of CuCrz~
Conc.
14. In K2Cr207, every Cr is linked to:
Zn + 2HCI ~ ZnCl2 + H2i (a) two O-atoms (b) three O-atoms
Conc.
Zn + 4HN03 ~ Zn(N03h + 2N02i + 2H20 (c) four O-atoms (d) five O-atoms
Conc.
[Hint ; The structure of Cr20~- ion is,
NO) ion is reduced to N02 in preference to H30+ ion.]
5. 'Bordeaux mixture' is used as a fungicide. Its composition
is:
0.,
O=Cr~ /Cr=O
/0
(a) caS04 + Cu(OHh
(c) CuS04 + CaO
(b) CuS04 + Ca(OHh
(d) CuO + CaO
-0/ ° ""0-
15. A blue solution of copper sulphate becomes darker when
6. A compound of mercury used in cosmetics, in Ayurvedic and treated with excess of ammonia. This is because:
Yunani medicines and known as Vermilion is: (a) ammonia molecules replace water molecules in the
(a) HgCl2 (b) Hg20 2 solution
(c) HgS (d) HgIz (b) ammonia is stronger ligand than water
(c) ammonia forms a stable complex ion [Cu(NH3)4]2+ with (ii) The aqueous solution of (A) gave a white precipitate
eu2+ ions with sodium chloride solution. The precipitate dissolves
(d) All are correct inN'E40H.
[Hint: The compound (A) is:
[CU(H20)4]S04' H20+4NH40H-----t [CU(NH 3)4]S04+ 9H 20] (a) Pb(N03)2 (b) Ba(N0 3h
Blue 801n. Dark blue soln.
(c) AgN0 3 (d) none of these
16. Sugar in urine-sample can be detected by: [Hint: 2AgN0 3 -----t 2Ag + 2NOz + Oz
(a) Fehling's solution '(b) Benedict's solution AgN03 + NaCI -----t AgCI + NaN03
(c) Tollen's reagent (d) all the three (a), (b) and (c) AgCI + 2NH40H -----t Ag(NH3)zCI + 2H20]
[Hint: Fehling's soln.-Cu(II) ion (complexed with tartrate ion)
is heated in basic, solution with a reducing sugar, brick red
20. An inorganic compound on strong heating gave a blackish
precipitate of CuzO is formed. Mixture of alk. CUS04 and brown powder and two oxides of sulphur. The powder was
sodium potassium tartrate is called Fehling's solution. dissolved in HCI when a yellow solution was obtained which
Benedict's soln.-It contains Cu(Il) ion complexed to gave a blood red coloured solution with thiocyanide ions.
citrate ion. When it is heated with reducing sugar, Cu(Il) The inorganic compound may be:
is reduced to CuzO. (a) eus04 (b) ZnS04
Tonen's reagent-Ammonical AgN03 solution is called
- -(G-}-NiSQ4- ( d ) - F e S Q4-
-Thnen'sreagent.Reducmg sugars give silver riiii:ror res(wiili -
Tollen'g reagent.]- -- -- -[Hint:, ,2FeS04-----t-Fe203+cS0z+S03c-
17. In the process of extraction of gold, Fe203 + 6HCI-----t 2FeC13+ 3H20
Roasted gold ore+CN- +H20 ~ [X]+OH-
Yellow
soln.
[X] + Zn~ [Y] +Au FeCl3 + CNS- ---7 Fe(CNSh + 3CI- ]
Identify the complexes [X] and [Y]: Blood red
coloured 801n.
(a) X =[Au(CNhr. Y =[Zn(CN)4P-
(b) X = [Au(CN)4]3-, Y = [Zn(CN)4]2-
21. When K ZCr04 is added to CUS04 solution, there is formation
(c) X =[Au(CN)zr. Y= [Zn(CN)6]4- of CuCr04 and CuCrZ07' Formation of euCr207 is due to :
(d) X =[Au(CN)4]3-, Y =[Zn(CN)4f- (a) basic nature of CUS04 solution which converts crO~- to
CrzO~-
[Hint: 2Au +4CN- + H zO+!02-----t 2[Au(CNhr +20H- (b) acidic nature of CUS04 solution which converts crO~
[Xl
2[Au(CNhf + Zn-----t [Zn(CN)d- + 2Au 1 to Cr20.r
[YJ (c) CuS04 has a typical property of converting CrO~- to
18. A metal gives two chlorides 'A' and 'B'. 'A' gives black Cr20~-
precipitate with NH40H and 'B' gives white. With KI 'B' (d) none of the above is correct
gives a red precipitate soluble in excess of KI. 'A' and 'B' 22. More number of oxidation states are exhibited by the acti-
are respectively: noids than by the lanthanoids. The main reason for this is:
(a) HgCl2 and HgzClz (b) HgzClz, HgCI2 [A.I.E.E.E.2008]
(c) HgClz and HgCI (d) none of these (a) greater metallic character of the lanthanides than that of
[Hint: 'A' is HgzOz and 'B' is HgClz. the corresponding actinides
/NH z (b) lesser energy difference between Sf and 6d-orbitals than
HgzCl z + 2NH40H-----t Hg"--CI + Hg + NH4C1 +,2H zO
that between 4f and Sd-orbitals
~
Black (c) more active nature of actinoids
(d) more energy difference between Sf and 6d-orbitals than
that between 4f and Sd-orbitals
White 23. Among the following transition elements, pick out the
HgCl z +2KI-----t HgI z +2KCl element(s) with highest second ionisation energy:
Red
HgIz + 2KI-----t KzHgI 4 ] (i)V(Z=23) (ii)Cr(Z=24) (iii)Mn(Z=2S) (iv)Cu(Z=29)
Soluble (v) Zn(Z = 30)
19. An inorganic compound (A) gave the following reactions: (a) (i) and (iii) (b) (ii) and (iv)
(i) The compound on heating gave a residue and a (c) (ii) and (v) (d) (iv) only
gaseous mixture of NO z and Oz. [Hint: Cu+ has stable configuration, [Ar]3d lO .]
::: : :: :: :::; ~::;:~::: :: :: :;::;:::;:::::;; : :::::: ::::::: :;:~: :: ;~ :::: ::: :: :::: ::: :::: ~::: :::
1. (b) 2. (c) 3. (d) 4. (a) 5. (b) 6. (c)· 7. (a) 8. (d) 9. (a) 10. (c) 11. (b) 12. (d)
13. (b) 14. (c) 15. (d) 16. (d) 17. (a) 18. (b) 19. (c) 20. (d) 21. (b) 22. (b) 23. (d).
_.<~~ Matrix Matching Questions for liT A§pirant§

1. Match the Column-I with Column-II: 7. Match the ions of List-I with their characteristics in List-II:
Column-I Column-II List-I List-II
(a) Tc (p) Transition element (a) Fe 3+ o (p) White precipitate with NaCI
(b) Hg (q) Not found in nature (b) Fe2+ (q) Blood red colour with KCNS
(c) Zn (r) Last element of third transition series (c) Cu 2+ (r) Prussian blue
(d) Es (s) Used in galvanization of iron (d) Ag+ (s) Turnbull's blue
2. Match the compounds 1ll List-I with their properties in (t) Chocolate brown precipitate
List-II: with ~Fe(CN)6
List-I List-n S. Match the element in List-I with their properties in List-II:·
(a) K2Mn04 (p) Transition element in +6 state List·I List-n
(b) KMn04 (q) Oxidising agent in acid medium (a) Fe (p) Do not fonn amalgam
(c) K2Cr201(r)¥-anl!fac.turt'!Mr()IIlPYr.olllsj~ <m: .( b ) P t ( q ) E l e m e n t -Qfvm~group
.(d)K;cro~ (s) Manufactured from chr()n:riteore (el Mo.. (r) UsedinbiologicaloxidationoL-=c::-c-- 0
3. MatcnI.ist~rwiiliList-II:
0 0
H20 to O2
List-I List·II (d) Mn (8) Used in X-ray tube
(Property) (Transition elements) 9. Match List-I with List-II:
(a) Highest oxidation state (p) Cr List-I List·II
(b) Highest density (q)Os (a) Ni 2+ (p) Alloy 0
(c) Element with maximum (r) Tc (b) Ti (q) Diamagnetic character

unpaired electrons (c) Misch metal (r) 3d 2
(d) Radioactive transition element (s) Ru (d) Hg (s) .J8 B.M. (Magrietic moment)
4. Match the alloys in List-I with their metal composition in 10. Match List-I with List-II:
List-II: List-I List·II
List-I List-II (a) Cu 2+ (p) Fonn amphoteric oxide
(a) Gennan silver (p) Cu (b) Zn 2+ (q) Diamagnetic and colourless
(b) Gun metal (q) Zn compounds
(c) Brass (r) Ni (c) Cr 3+ (r) Fonn complex with NH3
(d) Solder (s) Sn (d) Sc3+ (s) Fonn complex with KCN
(t) Pb 11. Match Column-I with Column-II:
5. Match List-I with List-II and List-ill: Colunm-I Column-II
List-I List·II List·m (a) Baeyer's reagent (p) CuS04 + Ca(OH)z
(a) Reduction (p) Adam's catalyst (u) TiCl 4 (b) Equivalent mass :::: 158 (q) 1% alkaline KMn04
(b) Polythene production (g) Wacker process (v) Pt (c) Bordeaux mixture (r) Detection of unsaturation
(c) Aldehyde manufacture (r) Natta catalyst (w) PdClz in organic compounds
6. Match List-I with List-II: (d) Nessler's reagent (s) Complex of mercury
List·I List-II
(a) Ag+ (Isoelectronic) with (p) Diamagnetic
(b) Zn2 + (q) Cd2+
(c) Element with lowest density . (r) Sc
(d) Cr (s) Paramagnetic
1. (a-p, q) (b-p, r)
o (c-p, s) (d--q) 7. (a--q, r) (b-s) (c-t) (d-p)
2. (a-p, r) (b-q, r) (c-p, q, s) (d-p, s) S. (a-p, q) (b-p, q) (c-s) (d-r)
3. (a--q, s) (Irq) (c-p) (d-r) 9. (a-s) (b-r, s) (c-p) (d--q)
.4. (a-p, q, r) (b-p, q, s) (c-p, q) (d-s, t) 10. (a-r, s) (b-p, q, r) (c-p, r, s) (d--q)
5. (a-p-v) (b-r-u) (c--q-w) 11. (a--q, r) (b-q) (c-p) (d-s)
6. (a-p, q) (b-p) (c-r) (d-s)
750 . GR.B. Inorganic Chemistry for Competitions

Following questions consist of an Assertion (A) and 6. (A) K2Cr04 is yellow coloured compound.
Reason (R). Use the following key to choose the correct answer: (R) Chromate ion has tetrahedral geometry.
(a) If both (A) and (R) are correct and (R) is the correct 7. (A) Solution of Na2Cr04 in water is intensely coloured.
explanation of (A). (R) Oxidation state ofCr in Na2Cr04 is (+VI).
(b) If both (A) and (R) are correct but (R) is not the correct (A.I.I.M.S. 2003]
explanation of (A). 8. (A) All the members of actinide series are radioactive in
(c) If (A) is correct but (R) is incorrect. nature.
(d) If (A) is incorrect but (R) is correct. (R) The electrons are gradually accommodated in 5f-energy
1. (A) Tungsten has a very high melting point. subshell.
(R) Tungsten is a covalent compound. (A.I.I.M.S. 1997] 9. (A) The spin only magnetic moment of Sc3+ is 1.73 B.M.
2. (A) Mn-atom loses ns electrons fIrst during ionisation as (R) The spin only magnetic moment of an ion is equal to
.compared..to.(n ..:-::l)d_ele.ctrolls.. In(f! +2) ;where n is thenumber of unpaired electrons
in the ion. _ . ._ _. _.
_.(Rl _The_~ff~ctiye JmcJear charge experienced by (n -1)d
electrons is greater than that by ns electrons. 10. (A) Potassium ferrocyanide' isd:fainagneticwIiereas----
(A.I.I.M.S. 2001J potassium ferricyanide is paramagnetic.
3. (A) KMn04 is a coloured compound. (R) Crystal field splitting in ferrocyanide ion is greater than
(R) Colour of KMn04 is due to charge transfer. that of ferricyanide ion.
4. (A) TiC4 is a colourless compound. 11. (A) The free gaseous Cr-atom has six unpaired electrons.
4
(R) Ti + ion has no unpaired electron. (R) Half filled s-orbital has greater stability.
5. (A) KMn04 is oxidising agent in neutral, acidic and in basic 12. (A) Ionisation of transition metals involve loss of ns electrons
medium. before (n -l)d electrons.
(R) Equivalent mass of KMn04 in acidic medium is 31.6. (R) Filling of ns-orbitals take place before the filling of
(n l)d-orbitals.·
1. (c) 2. (a) 3. (a) 4. (a) 5. (b) 6. (b) . 7. (b) 8. (b) 9. (d) 10. (c)
11. (c) 12. (b)

THOUGHT 1 1. In 3d series, the maximum magnetic moment is shown by:
(a) Sc (At. no. 21) (b) V (23)
Two types of magnetic behaviour are found in substances :
(c) Cr(24) (d) Fe (26)
(a) Diamagnetism and (b) Paramagnetism (Hint: Cr-atom has maximum number of unpaired electrons, i.e.,
Diamagnetic substances are those which are repelled by an 6. Hence, the magnetic moment .)6x8=.J4s B.M.]
applied magnetic field. Such substances have no unpaired 2. Which among the following ions has maximum value of
electron. Paramagnetic substances are those which are attracted magnetic moment? .
by an applied magnetic field. Transition metals and many of their (a) eu
2
+ (b) Mn 2+
compounds show paramagnetic behaviour where there are (c) Cr2+ (d) Ti 2+
unpaired electron or electrons. The magnetic moment arise from (Hint: Cu2+ E.C. =2, 8, 8 + 9, j.L =.,f3 B.M. ;
the spin and orbital motions in ions or molecules. Magnetic
moment of n unpaired electrons is given as,
Mn2+ E.C. = 2,8,8 + 5, j.L = J35 B.M.;
C~+ RC. 2, 8, 8 + 4, j.L .fi4 B. M. ;
I! = .In(n+ 2) Bohr Magneton
Ti2+ R.C. = 2,8, 8 + 2,
j.L =.j8 B.M. ]
Magnetic moment increases as the number of unpaired electrons 3. Increasing value of magnetic moments of
increases. (1) [Fe(CN)6]4-, (m [Fe(CN)6]3--, (Ill) [Cr(NH3)6]3+,
(IV) [Ni(H20)4f+ is :
(a) I<II<ill<IV (b) IV <ill<II<l 1. Select the correct statement:

(c) II<ill<I<IV (d) I<II<IV<ill (a) Colour of the transition metal ion arises due to d-d
[Hint: [Fe(CN)6]4- unpaired electron = 0; transition
[Fe(CN)6]3- unpaired electron 1; = (b) Colour of certain oxysalts of transition metals is due to
[Cr(NH3)6]3+ unpaired electron =: 3; charge transfer
[Ni(H20)4f+ unpaired electron 2] (c) Both are correct
(d) None is correct
4. Magnetic moment of [Ni(CN)4]2- is zero but that of
2. Which of the following is paramagnetic as well as coloured
[Ni(H20)4]2+ is 2.83 B.M. It is because of:
ion?
(a) CN- is a strong ligand making two unpaired electrons in
(a) Cu+
Ni2+ to pair up, while in [Ni(H20)4f+ two electrons remain
unpaired as H20 is a weak: ligand (c) Sc 3+
(b) different oxidation state of Ni in two complexes 3. Which is a coloured ion?
(c) both (a) and (b) (a) [Cr(H20)6]3+ (b) [Cu(CN)4]3-
(d) none of the above (c) [Ti(H20)6]4+ (d) [Sc(H20)d+
5. Magnetic moments of Cr (Z == 24), Mn + (Z == 25) and Fe2+ 4. J<2C:r201.gives colQllfecisQlutionm wat~r. ThecoluurisduL_
.(Z=-26) are x, .y andzrespectively. Which of the .following to:
order· iscorrec1:? (a) d-d transition in Cr-atoms
(a) x < y < z (b) x == y < z (b) presence of unpaired electron in d-orbital in oxygen
(c) z < x == y (d) x y == Z (c) charge transfer from 0 to Cr
[Hint: x .J4s; y =: J4s; z = .J24 (d) none of the above
Cr = 6 unpaired electrons, Mn+ =: 6 unpaired electrons, 5. Which of the following compounds is (are) coloured due to
Fe2+ =: 4 unpaired e1ectron.s.]
charge transfer spectra llIid- notiliietod'::dtiansitions?
6. -There are three unpaired electrons in [Co(H20)6f+ and
(a) KMn04 (b) KzCr04
calculated value of magnetic moment on the basis of
. (c) C~ (d) all of these
.In(n + 2) formula is 3.87 B.M. which is lower than the
experimental value of 4.40 B .M. The reason for this difference THOUGHT 3
is due to:
(a) increase in number of unpaired electrons during Photography is based on the nature of silver halides. Except
determination . AgF, the silver halides are photosensitive. These undergo decom-
(b) some contribution of the orbital motion of the electrons position in light and turn black due to formation of free silver.
to the magnetic moment
2AgBr Light) 2Ag + Br2
(c) d-d transition
(d) experimental error The photographic plates or films are prepared in a dark and
dustfree room by applying a light sensitive mixture called emulsion
which is prepared by adding 20 per cent aqueous solution of silver
Most of the compounds of the transition metals are coloured nitrate to ammonium bromide solution containing gelatin.
in the solid or in solution states. The colour of the transition metal When such a fihn is exposed, the emulsion gets affected. Since
ions arises from the excitation of electrons 'from the d-orbitals of different parts .of the body reflect light of varied intensity, the film
lower energy to the d-orbitals of higher energy. The energy or plate is affected proportionately. An actual but inverted image
required for d-d electron excitation is available in the visible range. of the object is thus formed on the film or plate which is not visible
Transition metal ions have the tendency to absorb certain to the eye. It is, therefore, called the latent image.
radiations from the visible region and exhibit the complementary When this exposed film or plate is dipped in a developer which
colour. contains a reducing agent, the parts affected most during exposure
.The transition metal ions which have completely filled are reduced to the maximum. The image becomes visible. It is called
d-orbitals are colourless as the excitation of electron or electrons a negative. The remaining sensitive emulsion on the negative is
is not possible within d-orbitals. The transition metal ions which removed by dissolving it in hypo solution (fixer). Finally, a positive
have completely empty d-orbitals are also colourless. In certain of the negative already prepared is made on silver bromide paper.
oxysalts of transition elements like KMn04' K2Cr201, there are no 1. The compound formt:u on the unexposed photographic film
unpaired electrons at the central atom but they are deep in colour. or plate is:
The colour of these compounds is due to charge transfer (a) silver nitrate (b) ammonium bromide
spectrum. For example, in Mn04, an electron is momentarily (c) diamminesilverbromide (d) silver bromide
transferred from 0 to the metal and thus oxygen changes from 2. The exposed part of the film or plate after developing
02- to 0- and manganese from Mn(+VII) to Mn(+VI). contains:
(a) silver inetal (b) silver oxide 3. Galvanisation means:

(c) silver bromide (d) silver nitrate (a) deposition of Zn on Fe
3. The solution of the developer consists: (b) deposition of AI on Fe
(a) alkaline solution of pyrogallol (c) deposition of Sn on Fe
(b) alkaline solution of quinol (d} deposition of Cu on Fe
(c) either (a) or (1,) 4. Corrosion is an electrochemical process. It involves:
(d) neither (a) nor (b) (a) loss of electrons by iron, Fe ~ Fe 2+ + 2e, i.e., iron
4. Silver halides are used in photography because these acts as'an anode.
compounds: (b) impunties act as a cathode. Electrons are used in forming
(a) are insoluble in water (b) are affected by light • hydroxyl ions.
(c) are soluble in ammonia solution H20 + 0 + 2e ~ 20H-
(d) easily stick on the surface of photographic phite or f11m (c) ferrous ions are oxidised to ferric ions in presence of
5. Silver bromide dissolves in hypo solution forming: dissolved oxygen.
(a) Ag2S20 3 (b) Ag2S
2Fe2+ + 0 + H20 ~ 2Fe3+ + 20H"""'
(c) .Na3[Ag(S203h] (d) NaAgS203
(d) all the above reactions
TffOllGHT'4- 5;Forprevention~ofrusting of iron, which is used in paints'l- -"-"
_ _ _ _ _ _ _ _ _ _ _ _ _ _ "~- _ _ _ _ _ _ _ _ _ _ _ H • • • ___ ••
(a) PbO (bYPb01

The process of corrosion of iron is known as rusting. Rust (c) Pb30 4 (d) PbS04
appears to be a hydrated ferric oxide, Fe203,xH20. Both 02 and
H 20 are required for rusting. Iron can be protected from the rusting THOUGHT 5
by use of following methods:
(i) t\pplyjngpaints, lacquers andenamelson the surface ofiron. Copper is the most noble of the first row transition metals and
(ii) By forming ~ ftrm
aitdcohere~t p~otective coating of occurs in small deposits in several countries. Ores of copIYer
include chalcanthlte (CuS04·5H20), atacamite [Cu2CI(OHh],
ferrosoferric oxide. This is done by passing steam over hot iron.
(iii) By coating a thin film of zinc, tin, nickel, chromium, Cuprite (CU20), copper glance (CU2S) and malachite
aluminium, etc., on the surface of iron. [Cu2(OHhC03].However, 80% of the world's copper production
If plated with zinc, the reaction products of zinc with O 2 and comes from the ore chalcopyrite (CuFeS2)' The extraction of copper
H20 form a coating which sticks to the surface and thereby from chalcopyrite involves partial roasting, removal of iron and
protects iron. self reduction, [I.I.T.2010]
1. Rusting is a corrosion process in which: 1. Partial roasting of chalcopyrite produces :
(a) Zn reacts with 02 (a) CU2S and FeO (b) CU20 and FeO
(b) Sn reacts with 02 and H 20 (c) CuS and Fe203 (d) CU20 and Fe203
(c) Fe is converted into hydrated ferric oxide 2. Iron is removed from chalcopyrite as :
(d) minute holes are formed on the surface of a metal (a) FeO (b) FeS
2. Zinc protects iron from corrosion because: (c) Fez03 (d) FeSi03
(a) it is an active metal 3. In self reduction, the reducing species is :
(b) a stic~ coating is fOlVled on its surface on exposure to (a) S (b) 02-
air (c)sZ- (d) SOz
(c) it is not affected by atmosphere
(d) it has lower oxidation potential than iron
Thought 1 1. (c) 2. (b) 3. (d) 4. (a) 5. (c) 6. (b) Thought 4 1. (c) 2. (b) 3. (a) 4. (d) 5. (c)
Thought 2 1. (c) 2. (b) 3. (a) 4. (c) 5. (d) Thought 5 1. (b) 2. (d) 3. (c)
Thought 3 1. (d) 2. (a) 3. (c) 4. (b) 5.. (c)
1. Explain, why Mn 3+ is less stable than Mn2+ and Mn4+ ions? Fe bcc, fcc
or Co fcc, hcp
· w hy M n3+ d'IsproportlOnate
E xpIam, . .
mto Mn 2+a n d M
n4+ Ni frc
ions? Cu fcc
[Ans. Mn25 ----7 3d 5 , 4i ; Mn 3+ ----7 3d 4 , 4i Zn hcp]
2 5
Mn + ----7 3d , 4so ; Mn4+ ----7 3d 3, 4so 6. Write down the name of catalyst for the following:
On the basis of electronic configuration, Mn2+ and Mn4+ (i) In the synthesis of hydrocarbon in Fischer-Tropsch
are expected to be more stable, hence, Mn 3+ undergoes process.
disproportionation. (ii) Aciams catalyst in reduction.
2Mn3+ ----7 Mn 2++Mn4+]
(iii) Deacon's process of making Cl2 from HCI.
2. Standard reduction potential of copper is greater than that (iv) Reppe synthesis of benzene.
of hydrogen yet it liberates hydrogen from a concentrated (v) Fenton's reagent in the synthesis of aldehydes from
solution of hydrochloric acid. Explain this fact with proper alcohols.
reasoning. _. ._.'_ [Ans.Ei) ColFe(ii)· PtlPtO- . (iiiyeue12 (iv) Ni complexes--
. - . - - Cu2++ 2e -----7 Cllis); . EOCu2+ICu= +0.34 volt (v) FeSQ¥H2Q2}
2H++ 2e -----7 H2(g) ; EOWIH2= 0.00 volt 7. (a) Calculate magnetic moment of Fe 3+ in [Fe(CN)6]3- and
[Ans. When copper is treated with conc. HCl then formation of in [Fe(H20)6]3+.
f-
stable complexion [CuCI4 along with liberation of H2 [Hint : In [Fe(CN)6] 3-, Fe3+ ion has only one unpaired
gas takes place. _ electron. Thus, magnetic moment of Fe3+ will be J3 ,
Cu + 4HCl(conc.) ----7 [CuCI4]2- + 2H+ + H2 i]
i.e., 1.732 B.M. (Ilp= .In(n + 2) B.M., where, n.is
3. Account for the following facts : • number of unpaired electrons). In [Fe(H20)6]3+, Fe3+
(a) An aqueous soiution of FeCl 3 is slightly yellowish in ion has 5 unpaired electrons, hence, its magnetic
colour. moment will be.J3s B.M., i.e., 5.92 B.M.]
(b) Cu(I) compounds are not known in aqueous solution.
[Ans. (b) Arrange following complexes in decreasing order of
(a) An aqueous solution of FeCl 3 is colloidal. It is yellowish in magnetic moment:
colour due to Tyndall effect. [Ni(H20)4]2+, [Ni(CN)4]2-, [Fe(CN)d-, [Fe(CN)6]4-
(b) Cu(I) compounds undergo disproportionation in aqueous
[Ans. [Fe(CN)6]4- = [Ni(CN)4]2- < [Fe(CN)6]3-<
medium.
[Ni(H20)4]2+ ]
CU2Cl2 ----.; CUCl2 + Cu]
4. Answer the following questions: [Hint : In [Fe(CN)6]4- and [Ni(CN)4]2-, central atom has no
unpaired electron, hence, their magnetic moment is
(a) Which is more basic?
zero. In [Fe(CN)6] 3-, there is only one electron with
(i) zr0 2 or Ti0 2 (ii) V 20S or Nb 20 S central Fe3+ ion, hence, its magnetic moment will be
(iii) Os04 or Re02 1.732 B.M. In [Ni(H20)4l+, there are two unpaired
(b) Which is more stable [CoCI6]3- or [IrCI6]3-? electrons with Ni2+ and hence, its magnetic moment
(c) Which forms trans isomer [PtCl2(NH;h] or will be.ts B.M.]
[PtCI(NH3ht? 8. Give the formula of three ions which are coloured due to
(d) Which is more oxidising agent Cr(VI) or Mo(VI)? charge transfer spectra.
[Ans. [Ans. VOl, crOl-, MnO::!]
(a) (i) Zr02 (ii) Nb20 5 (iii) Re02
[Hint : Oxidation state of
(b) [JrCI6]3- is more stable than [COCI6]3-- because in +3 state Ion Colour
central atom
Ir is more stable than Co.
+5 pale yellow
(c) [PtCI 2(NH3h] will form trans isomer.
(d) Cr(VI) is stronger oxidising agent than Mo(VI).] +6 dark yellow
5. Write down the names of crystal structures in which the MnO::! +7 dark purple ]
following elements are present. 9. What happens when?
Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn (i) CO 2 gas is passed through aqueous solution of
[Ans. Element Crystal Structure Na2Cr04'
Sc fcc (ii) Ammonium dichromate is heated strongly:
Ti hcp (iii) Two gases 'A' and 'B' turns acidified K2Cri07 green.
V bec
When these gases are passed through ,water simul-
Cr bcc taneously, solution turns turbid yellow. What' are the
Mn bcc, tet gases 'A' and 'B'?
[Ans. (i) Sodium dichromate, Na2Cr207 is formed, K2S04 + Cr2(S04h + H2 0

(ii) Ni and Cr203 are formed, Green
(iii) 'A' and 'B' are S02 and H2S, ] : When both S02 and fi 2S are passed simultaneously through
[Hint : (i) H20 + CO2 -----7 H2C03 \.water then colloidal sulphur is precipitated.
Carbonic acid \ 2H2S + S02 -----7 2H20 + 3S ]
2Na2Cr04 + H2C03 -----7 t'la2C03 + Na2Cr207 + H20. Yellowish turbidity
a
(ii) (NH4hCrZ07.,----7 N2 + Cr203 + 4H20
(iii) K2Cr207 + 4H2S04-? K2S04 + CC2(S04h + 4H20 + 3[0]
Green
The answer to each of the following questions is a single 5. The change. in the oxidation number of chromium in
•. ~!~ ;::;r,::{:g$oU~p~~d9'electrOns
Mn2+?
are present in
potassill.mclidlromate when it acts as 'an oxidismg agent
6. How many water molecules are associated with a-molecule~-~'~
of Mohr's salt?
2. What is the magnetic moment of Fe3+? 7. When ammonium hydroxide is added to copper sulphate, a
3. How many sigma bonds are present in Cr20~- ion? blue coloured complex is formed. What is the coordination
4. How many electrons are involved in the reduction of KMn04 number of copper in the complex?
in acidic medium? 8. The percentage of impurity iii the 23 carat gold is:
1.' (5) The at. no. of Mn is' 25. The numbet of electrons associated 4. (5) Mn04 + 8H+ ... 5e- . Mn2+ + 4H20
with .Mn2+ == 23 5. (3) . Crzof- -----7 2Cr3+
3d
Oxidation number of Cr in Cr20~~ is +6, change (6 3) .3
The electronic configuration of Mn2+ is : 2, 8, V'LU-'..L!...LL.LLJ
6.(6) The formula of Mohr's salt is : FeS04·(NH4hS04·6H20
2. (6) The electronic c~nfiguration of Fe3+ is : 2, 8, 8 +5. 7. (4) The blue complex is, [CU(NH 3)4]S04'
Mag. moment .j5x 7 '" 6 100
3. (8) The structure of dichromate ion is 8. (4) % Gold =-x23 96
24
Impurities percentage (100 - 96) == 4
o ' '0
~ Jh
o ~/Cr~ ycr~ 0
-07 . 0 B 0-
CHAPTER
15
Coordination Compounds
a.nd Organometa1li~
One of the most important properties of transition metals is that they form
coordination or complex compounds. These compounds play a vital role in our
Contents. - lives. The importance of these compounds can be realised from the fact that life
15.1 Molecular or Addition Compounds would not have been possible without the existence of chlorophyU (Mg-complex)
15.2 Terminology of Coordination Compounds in plants and haemoglobin (Fe-complex) in the blood of animals. One of the
15.3 Nomenclature of Coordination Compounds 'earliest known coordination compoiInd is prussian blue which was accidently
15.4 Werner's Coordination Theory , prepared in 1704 by a Berlin colour maker, Diesbach, by strongly heating animal '
15.5 Isomerism in Coordination Compounds wastes and sodium carbonate in an iron container. In 1753, Macquer prepared
15.6 Bonding in Coordination Compounds : . potassium ferrocyanide by treating prussian blue with alkali. In 1799, Tassaert
(1) Valence Bond Theory obtained an orange compound, COCI3·6NH3, by allowing a mixture of cobalt
(2) Crystal Field Theory ch~oride and aqueous ammonia to stand in air. During the next fifty years, numerous
15.7 Stability of Coordination Compounds in compounds of thls type containing cobalt, platinum, chromium and iron were
Solutions discovered. The field of such compounds has expanded very fast in recent ye~s
15.8 Preparation of Coordination Compounds and coordination compounds are playing important roles in analytical Ghemistry,
15;9 Importance of Coordination Compounds polymerization reactions, metallurgy and refining of metals, organic synthesis,
15.10 Organometallic Compounds electroplating, photography, biochemistry, water purification, textile dyeing and
bacteriology. In addition, the study of these compolli:idshas enlarged our
understanding cif chemical bonding; certain physical properties such as spectral
and magnetic properties and metabolic processes. In this chapter 'some basic
aspects regarding coordination compounds are discussed.
15:1i:!~ MOLECULAR OR "ADDITION COMPOUNDS

When solutions containing two or more simple stable compounds in molecular
proportions are allowed to evaporate, crystals of new substances areo.btained.
These substances aretermed molecular or addition compounds. Some common
examples are: .
K2S04 +A12(S04)3 + 24H20 ------7 K2S04·AI2(S04h·24H20

Alum
Mohr's salt
4KCN + Fe(CNh ------7 Fe(CNh·4KCN'.

CUS04 + 4NH3 ~ CUS04· 4NH 3 surrounded by a group of ions or neutral molecules or

AgCN + KCN ~ KCN·AgCN
both. A coordination compound, thus, consists of either,
Simple stable Addition or molecular (i) a simple cation and a complex anion such as
compounds compounds ~[Fe(CN)6], or
The molecular or addition compounds are of two types: (li) a complex cation and a simple amon such as
(i) Double salts or Lattict: compounds: The addition [Cu(NH3)4]S04, or
compounds which are stable in solid state only but are broken (iii) a complex cation and a complex anion such as
down into individual constituents when dissolved in water are [CO(NH3)6] [Cr(C 20 4h], or
called double salts or lattice compounds. Their solutions
(iv) a neutral molecule such as Cu(Gly)z, Ni(CO)4,
have the same properties as the mixture of individual compounds.
Ni(DMG)z, etc.
For example, when Mohr's salt, [FeS04·(NH4hS04·6H20],
is dissolved in water, it exhibits the properties of FeS04 and 15~ TERMINOLOGY OF COORDINATION
(NH4hS04, i.e., they produce Fe2+, NH/ and SO~- ions in . "" COMPOUNDS
solution. Thus, each ion has its identity in double salt.
2+ + Before further discussion, it is necessary to explain some
FeS04·(NH4hS04·6H20 ~ Fe (aq.) + 2NH4(aq.)
important terms used in the study of coordination compounds.
Mohr's. sal!. + 2S0~--:(aq.) +6H20 These are discussed here. .. ~ .. ~-~~-.~~~ ...
Ca.rnallite;~KCI;MgC12·6H20~·potashalufi:f,
K2S04·AI2(S04h·24H20,etc., are the examples of double salts. 1. Ligands

(ii) Coordination or complex compounds: The addition The neutral molecules; anions or cations which are directly
compounds in which some of the constituent ions or molecules linked with the central metal atom or ion in a complex ion are
lose their identity and when dissolved in water they do not . called ligands. The ligands are attached to the central __ c _;--,:...::=.
break up completely into individual ions, are called coordination or atom through coordinate bonds or dative linkage. With few
compounds. The properties of their solutions are different exceptions, free ligands have at least one electron pair that is
than those of their constituents. When crystals of CuS04-4NH3 not engaged in bonding. Some examples are:
are dissolved in water there is hardly any evidence for the
presence of Cu2+ions or ammonia molecules. A new ion, H-N-H
.. H-O: :C-N: :CI:
[CU(NH3)4]2+, is furnished in which ammonia molecules are I I
H H
directly linked with the metal ion. Similarly, the. aqueous
solution of Fe(CNh·4KCN does not give tests of Fe2+ and The ligand acts as a donor as it donates one or more electron
~ ions but gives the test for a new ion, [Fe(CN)6t-. The pairs to the central metal atom or ion which acts as an acceptor.
ions [CU(NH3)4]2+ and [Fe(CN)6]4- are called complex ions. The ligands are thus Lewis bases and central metal ions or
atoms are Lewis acids. The formation of a complex ion involves
CuS04·4NH3 ~ [Cu(NH3h]2+ + sot following two things:
Fe(CN)z·4KCN ~ 4K+ + [Fe(CN)6]4- (i) Ligands should have lone pair or pairs of electrons which
Thus, a coordination or complex compound may be can be donated to the central metal ion or atom.
defined. as a. molecular compound that results from the (ii) The central atom or ion should have vacant orbitals of
combination of two or more simple stable molecular nearly equivalent energy as to accommodate the electrons
compounds and retains its identity in the solid as well as donated by ligands. This condition is easily fulfilled by atoms
in dissolved state. The properties of such compounds are or ions of transition metals.
totally different than individual constituents. A coordination
compound contains very often but not always a complex Types of· ligands
ion. Ligands can be of following types depending on the number
Some of the common examples of these compounds are: of donor atoms present in them.
[Cu(NH3)4]S04; ~[Fe(CN)6] K2[PtCI6] (i) Mono- or unidentate ligands: They have one donor
[Co(NH 3)6]CI 3 K3[Fe(CN)6] K3[Cr(C 20 4h] atom, i.e., they supply only one electron pair to central metal
[Ni(NH3)6]Cl 2 K[Ag(CN)Zl K2[HgI4] atom or ion. F-, Cc, Br-, H20, NH3, CN-, NO OH-, CO, z,
etc., are examples of mono dentate ligands.
[Ni(DMG)z] [Cu(Glyh] Ni(CO)4 (ii) Bidentate ligands: Ligands which have two donor
DMG= Dimethyl glyoxime ; Gly = Glycine atoms and have the ability to link with central metal ion at
A complex ion may be defined as an electrically charged two positions are called bidentate ligands. Some examples
radical which consists of a central metal atom or ion are:
Coordination Compounds and Organometallics 757
(vi) Hexadentate ligands: They have six donor atoms.
-0
/~0- The most important example is ethylenediaminetetraacetate
ion.
\ c-cI
o
I '\0
Ethylenediamine (en) Oxalate (ox) 1, 10-Phenanthroline (Phen)
H
I
/'"
CH2-N~H
b-o-/ -O-C-O- (vii) Chelating ligands: A bidentate or a poly dentate

.ligaIl(L is. J<Il.Q\\in _1:!Sa,chehltiJlgJigand~if _On. co.ardination_iL. __ _
·11
Q~
II·
._.. _.~.__O_.~~ .__ r~'!ltsj._Iltl1.~j'Qffila,tionQ.f ...~LClo~dQL~C)'klic_.ring.....sJIJl~cJJJLe.-=---~ .
The complexes, thus fonned are called chelates. The word
Glycinate (Gly) 2,2'-Dipyridyl (Dipy) Carbonate
chelate has been derived from the Greek word chele meaning
claw. The complex fonned by Cu 2+ ion with ethylenediamine
(iii) Tridentate ligands: The ligands having three donor
is an example of a chelate.
atoms are called tridentate ligands. Examples are:
H" /H ·[CH2-H2N'\. I(" NH2-CH2]2+
H-N N-H I Cu I
H(\/\H CH 2-H 2N / ~ NH 2-CH 2
2 2
[Cu(enhf+
I 1 I
H C-N-CH
2 . I 2
The followirig are the characteristics of chelates:
(a) Chelating ligands fonn more stable complexes than
H monQdentate ligands. This is called chelating effect. All types
Diethylenetriamine (dien) 2,2',2"-Terpyridine (terpy) .Of polydentate ligands can act as chelating ligands.
(iv) Tetradentate ligands: .These ligands possess four (b) The chelates containing 5 or 6-membered rings including
dQnor atoms. Examples are: metal atom are comparatively more stable. Chelating ligands
which do nQt contain unsaturated groups (dQuble bonds), in
H H
general, fonn five membered stable cQmplexes while chelating
.
I
/N", (CH 2 )2 / N "
I ligands' having unsaturated grQUPS (dQuble bonds) fonn six-
membered stable cQmplexes.
0\'1- . "" / ' (C'.-Y.
~~ N/'" N/~
(c) Ligands with larger groups fonn more unstable rings
.than with smaller groups due to steric hindrance.
H/IH .' HI~H Importance of chelates

Chelates find wide applications in laboratory and industry :
Nitriloacetate Triethylenetetramine (trien)
(i) A number of ions such as Cu2+, Ni 2+, Mg2+, Al 3+, etc.,
(v) Pentadentate ligands: They have five donor atoms. are detected and estimated by the fonnatiQn of stable and
For example, ethylenediaminetriacetate ion. cQloured chelates.
(ii) In water softening.
(iii) In separation .Of lanthanides and actinides.
(iv) In the elimination of hannful radioactive metals from
body. FQr this purpose usually EDTA is used.
(v) In solvent extraction.
(vi) In food preservation.
SOME COMMON POLVDENTATE LIGANDS

Name Formula Abbreviation Dentate character
Carbonate CO~- bidentate
Oxalate C2<?~ ox bidentate
. Ethan-l,2-diamine NH:z-CHr- CH2-NH 2 en· bidentate
" \
1,2-propanediamine NH2-CH-CH2-NH 2 pn bidentate
I
CH 3 .
0- 0
I II
Acetylacetonato CH3- C=CH-C-CH3 acac bidentate
2;2 '-qipyridine ',0-<:> bipy bidentate
Glydnate. ....................~ ....~._ '~'r-~"~--;"- -r'~ ., .NH.2=:CH2=COO-c'\··
-OOC-CH2) ' . <CH2-COO~

Ethylenediaminetetraacetate N-CH 2 -CH2 - N ' , edta hexadentate
-OOC-CH 2 CH2 -COO-
Note : (i) The ligands having two or more donor atoms are also called ligand. The most common coordination numbers exhibited by
polyqentate or multi dentate ligands. metal ions are 2, 4 and 6. The.light transition metals exhibit 4
(li) A multidentate ligand is known as a chehlting ligand if on and 6 coordination numbers while heavy transition metals may
coordination it results in formation of a closed or cyclic ring. exhibit coordination number more than 6. It has been observed
The complexes thus formed are called ehelates. The chelates that in a particular oxidation state, a metal prefers to exhibit the
are comparatively more stable than ordinary complexes.
same coordination number.
(iii) Polydentate ligands have Rexidentate character. It is not
necessary that all the donor atoms present in the polydentate C.N. = :E Number of ligands x. Dentate character of ligands
ligands should form coordinate bonds with central metal atom
or ion. For example, ethylenediamine tetraacetic acid (EDTA)
Some other examples :
which is hexadentateligand can function as pentadentate or Complex Coordination nmnbe"r
.tetradentate ligand with certain metal ions. Similarly sulphate of central metal
ion can also act as monodentate ligand. ~[Fe(CN)6] 6
(iv) There are certain ligands which have two or more donor atoms [Ag(CNhr 2
but in forming complexes only one donor atom is attached to [Pt(NH 3hCI 21 4
metal ion. Such ligands are called ambidentate ligandS'. Some [Ca( edta) ]2- 6
examples of such ligands are: '
(edta is a hexadentate ligand)
M N02 M ONO
Nitro Nitrito
,111·3. Coordination sphere or Coordination
M CN M+-- NC
Cyano Isocyano' entity and counter ions
M SCN M +-- NCS The central metal atom or ion and the ligands that are directly
Thiocyanide Isothiocyanide
attached to it are enclosed in a square bracket. This has been
called coordination sphere or first sphere of attraction or
~ 2. Coordination number coordination entity. It behaves as a single unit because the
The number of atoms of the ligands that are directly bound ligands present in the coordination sphere are held tightly by
to the central metal atom or ion by c::oordinate bonds is known the metal ion. Any ion present outside this sphere is separated
as the coordination number of the metal atom or ion. It is from the complex when the compound is dissolved in the
actually, the number of chemical bonds which the ligands form water, or any other polar medium. The ionizable groups written
with the central metal atom or ion. For example, in [CU(NH3)4]2+ outside the bracket are called counter ions.
the coordination number of copper is 4, in [Co(enh]3+ the ~[Fe(CN)6] ~ 4K+ + [Fe(CN)6]4-
,coordination number of cobalt is 6 as (en) is the bidentate
[Co(NH3)6]Ch ~ [Co(NH3)61 3+ + 3Cr
The charge on the complex ion is the algebraic sum of the L
charges carried by central. metal ion and the ligands attached . L
L:~+;/t
to it.
Charge on th.e complex ion = Oxidation number of metal ion *
+ charge on the ligands : M i
For illustration, see following examples:
Example 1. Assign the charge on the following ions:
L~r~~~JL
(a) [Hg(CN)4f, '(b) [Co (NH3h C14t, (c) [Fe(CN) 6 t. L
Solution.
Square planar Octahedral
(a) The oxidation state of Hg in the complex is +2; So
x = + 2 + 4 x (-1) = -2, i.e., [Hg(CN)4]2- L
(b) The oxidation state of Co in the complex is +3; So

x = + 3 + 2x 0 + 4 x (-1)
== -:cl,i.e., [Co(NH3hC4r
(c) The oxidation state of Fe in the complex is + 2; So
x = + 2 + 6 x (-1)
= -4, i.e., [Fe(CN)6]4--
If the oxidation state of Fe in the complex is + 3;
x = + 3 + 6 x (-1)
= -3, i.e., [Fe(CN)6]3--
Square planar Trigonal bipyramidal
Example 2. Determine the oxidation state of metal in the
. complex ion, [PtCI6]2-. iJ 5. Effective atomic number {EAN}
Solution. Charge on the complex ion =Oxidation state of Ligands are attached with· the central metal ion through
metal + charge on ligands donor atoms. Each donor atom donates one electron. pair to the
central metal ion, i.e., the central metal atom or ion gains
-2 =x + 6 x (-1)
electrons from the donor atoms. In order to explain the stability
or x=+4 of the complex, Sidgwick proposed effective atomic number
The oxidation state of Pt in the complex ion is + 4. abbreviated as EAN,which is defined as the resultant number
of electrons with the metal atom or ion after gaining
iii 4. Coordination polyhedron electrons from the donor atoms of the ligands. The effective
In the coordination sphere, the ligands attached to the central atomic number (EAN) generally coincides with the atomic
metal atom or ion occupy definite positions around the metal number of next inert gas in some cases. EAN is calculated by·
atom ot ion in space giving a definite geometry to the complex the following relation:
ion or coordination entity. The spatial arrangement of the EAN = Atomic number of the metal- number of electrons
ligand atoms which are directly attached· to the central lost in ion formation + number of electrons gained
l\tom or ion is called coordination polyhedron. from the donor atoms of the ligands
The generally observed coordination polyhedra are tetra- The EAN values of various metals in their respective
hedral, square planar, octahedral, square pyramidal, and trigonal complexes are tabulated below:
bipyramidal. .
Complex l\{etal (Oxid. state) At. No. of metal Coordination nwnber Effective atomic number
K 4[Fe(CN)6] +2 26 6 (26 - 2) + (6 x 2) = 36 [Kr]
[Cu(NH3)4]S04 +2 29 4 (29 - 2) + (4 x 2) = 35
[CO(NH 3)6]CI3 +3 27 6 (27 - 3) + (6 x 2) 36 [Kr]
Ni(CO)4 0 . 28 4 (28 ,.- 0) + (4 x 2) = 36 [Kr]
K 2[Ni(CN)4] . +2 28 4 (28 2) + (4 x 2) = 34
K2[PtC16] +4 78 6 (78 - 4) + (6 x 2) = 86 [Rn]
K3[Cr(C 20 4h] +3 24 6 (24 3) + (6 x 2) = 33

K3[Fe(CN)6] +3 26 6 (26 3) + (6 x 2) = 35
K2 [HgI4] +2 80 4 (80 2) + (4 x 2) = 86 [Rn]
[Ag(NH3h]CI +1 47 2 (47 - 1) + (2 x 2) '" 50
K2 [PdCI 4] +2 46 4 (46 - 2) + (4 x 2) 52
Just as the octet is useful in formulating the bonding in .' Names of the ligands
compounds of the light elements, the notion of an EAN provides·
(i) Anionic ligands rnding with -ide are named by replacing
a rough guide for bonding in coordination compounds. Quite
-ide with suffix -0 or ,replacing ~e by -0.
a few, but not all, metals: achieve the EAN of a noble gas
through coordination (see above table) .. The,EAN concept has AniO~ \ SY~bOI Name as ligand
been particularly successful for complexes of low valent metals Chloride CC Chlorido
Bromide Br-:. Bromido
(oxidation state ~ +2);
Cyanide CW Cyano
Oxide 0 2- Oxo
6.~J:lomoleptic_and_heterolepnc_C~QlJ]pJexes - PeroXiaec--~---- ---~'Peroxo--
Complexes in which a metal is bound to only one kind of Hydroxide OW Hydroxo

Sulphide S2- Sulphido
donor groups, e.g., [Cr(NH3)6]3+ are known as homoleptic.
Other examples are :[Fe(CN)6] 3-, [PtC4]Z-, [Hg4f- etc. Amide NHi" Amido
Nitride N 3- Nitrido
Complexes in which a metal is bound to more than one p 3-
Phosphide Phosphido
kind of donor groups are known as heteroleptic. Examples
Ligands whose names end in -ite or -ate become -ito or
are : [Co(en)zClz]+, [Cr(NH3)4CI2]+, [Fe(H20MC20 4)]+,
-ato, i.e., by replacing the ending -e with -0.
etc.
Anion Symbol Name as ligand
7. Homonuclear and polynuclear complexes Carbonate CO~ Carbonato
Oxalate C2 0t- Oxalato
Complexes in which only one metal atom is present are
Sulphate SO~- Sulphato
known as homonuclear complexes. Complexes in which more
Nitrate NO] Nitrato
than one metal atom. is present are known as polynuclear
Sulphite S05- Sulphito
complexes.
Acetate CH3COO- Acetato
Nitrite ONO- (bonded through oxygen) Nitrito-o
15.3 NOMENCLATURE OF COORDINATION
COMPOUNDS
{ NO
z (bonded through nitrogen) Nitrito-n
or Nitro
Since several thousands of complexes (coordination com- (ii) Neutral ligands are called with the same names as their
pounds) are known and the number is constantly increasing, neutral molecules or with their special names, e.g.,
it is necessary to adopt a uniform system of naming these
compounds. The International Union of Pure and Applied
C6HSN or aN
---? Pyridine .
Chemistry (IUPAC) published rules for the systematic naming PH3 ---? Phosphine
of coordination compounds in 1957. Some modifications in (C 6 HshP ---? Triphenylphosphine
these rules were made in 1962 and 1971.
However, trivial names for certain coordination compounds
are still in use, e.g., Kt[Fe(CN)6] and K3[Fe(CN)6] are called ~s
HzN-CS-NH2
Thiourea
0-0
Dipyridyl
potassium ferrocyanide and potassium femcyanide even today.
H20 Aquo (Aqua) NH3Ammine
The following rules are adopted these days for naming all
CO Carbonyl; NO Nitrosyl;
types of coordination compounds:
CS Thiocarbonyl; NS Thionitrosyl
.(1) If a coordination compound is ionic, the name of cation
Note: In the case of poly-dentate amino ligands we use single 'm' in
is given first whether or not it is the complex ion followed by
the spelling, i,e., amine is written, e.g.,
the name of the anion just like naming a simple salt. The names
of cation and anion are separated by a space. / CH 2-CH 2",
(2) Within a complex ion, the ligands are named first followed en; NH2 NH2 ethylenediamine
by the metal ion. (ethane-l ,2-diamine)
_*i (iii) Positively charged ligands have suffix -ium. Coordination compounds containing complex cationic ion:
NHt Ammonium; NO+ Nitrosylium; [Pt(NH 3)6]CI 4 Hexaalnmineplatinum(IV) chloride
NH 2- NH) Hydrazinium; Noi Nitronium [CO(NH 3)4H20C1]Cl Tetraanunineaquochloridocobait(llI) chloride
(iv) If the number of a particular ligand is more than one in [Cu(en)2] S04 Bis (eptane-l ,2-diamine) copper(II) sulphate
the complex ion, the number is indicated by using Greek numbers [Cr(H 20)4CI2t Tetraaquodichloridochromium(ill) ion
such as di, tri, tetra, penta, hexa, etc. [Fe(H20MC204)]zS04 Tetraaquooxalatoiron(llI) ·sulphate
However, when the name of the ligand includes a number, [Cr(NH3)4(ONO)Cl]N03 Tetraamminechloridonitrito-o-chromium(llI)
e.g., dipyridyl, ethylenediamine, then bis, tris, tetrakis are used nitrate
in place of di, tn, tetra, etc. [Ag(NH 3h]CI Diammine silver(I) chloride
(v) Order of naming ligands: When more than one type [Co(NH3)s(NCS)]C12 Pentaammineisothiocyanatocobalt(llI)
of ligands are present, they are named in alphabetical order chloride
[{ (C6HshPhRh]CI Tris (triphenylphosphine) rhodium(I)
without separation by hyphen. This rule has come in force chloride
after 1971 convention.
Coordination compounds containing complex anionic ion: __ _
Note.: In the. old system, (i)JheJigandsarenamed..in.theQrder of
. _1l.e.8..a:tive,:neu!t:!lL!lIl.<!.PQsitive without~~M.!ltimL.by_hyphens.... K.4[~~i<::'N'2§L PO!lIs.si lllI! hex.!.cYaI!()ferrat~UllL:~~~~ _ _ _ ... ~ ...
. (ll) when there are severaI ligands ofsanlt:- kind, ihese-~lisied . K3[Fe~CN)6] . Potassium hexacyanofeirate (ill)
.alphabetically. K3[Cr(C20 4h] Potassium trioxalatochromate (1lI)
For example, in the complex [Cr(NH3)4Cl(N02)t, the K3[CO(C204hCI2] Potassium dichloridodioxalatocobaltate (III)
ligands are named in the order of ammine, chlorido and K 2 [HgI 4 ] Potassium tetraiodidomercurate (II)
nitrito-N in accordance to new convention. However, according K2[PtCI 6] Potassi.um hexachloridoplatinate (IV) .
to old convention, the ligands are named in the order of chlorido, Na[Ag(CNh] Sodium dicyanoargentate (I)
nitrito-N and ammine (fITSt negative ligands in alphabetical [Ni(CN)4]2- Tetracyanonickelate(lI) ion
order and then neutral ligand). Na3 [Co(N0 2)61 Sodium hexanitrocobalta!e (III)
(3) The oxidation state of the central metal is shown by K 3[Fe(CN)sNO] Potassium pentacyanonitrosyl ferrate (II)
Roman numeral in bracket immediately following its name. Coordination compounds containing complex cationic and
(4) Complex positive ions and neutral coordination com- anionic ions :
pounds have no special ending but complex negative ions always [Cr(NH3)6][CO(CN)6] Hexaamminechrornium (III)
end in the suffix -ate. In most of the cases, the suffix -ate is hexacyanocobaltate (III)
fixed to English names of the metals but in some cases -ate is [Pt(NH3)4HCuCI4] Tetraammineplatinum (II)
fixed with Latin names of metals. tetrachloridocuprate (II)
Name of components present in coordination sphere ~e [Cr(NH3)6][CQ(Cz04hl Hexaamrninechromium (III)
written in continuum, e.g., trioxalatocobaltate (ill)
[Pt(PY)4][PtCI 4] Tetrapyridine platinum (II)
K3[Fe(CN)5NO] Potassium pentacyanonit:osylferrate(II~ tetrachloridoplatinate (II)
Continuum Non-ionic coordination compounds :
Fe(CO)s Pentacarbbnyliron(O)
Element Metal as named· in anionic complex
Triamminetrinitro cobalt (III)
Cobalt Cobaltate Cu(GlYh Diglycinatocopper (II)
Nickel Nickelate
Chromium Chromate Ni(DMGh Bis (dimetbylglyoximato) nickel (II)
Iron Ferrate (6) Bridging groups in bidentate ligands: In a
Copper Cuprate polyatomic complex which contains tWo or more central metal
Silver Argentate ions, the ligands which act as bridge between two metal atoms,
Lead Plumbate the Greek letter fl (mu) separated by a hyphen is written before
Note: In the case of mercury we may use both mercurate and their names. For example, the complex
bydrazinate.
(5) The name of the neutral coordination compound is given in
one word only as the name ofNi(CO)4 is tetracarbonylnickel (0).
[(en 2 )co<:,)co(enh}S04h is named as:
The following examples will make the rules more clear.
Bis (ethane-l ,2-diamine) cobalt(III)-Il-amido-fl-hydroxo bis
(ethane-l ,2-diamine) cobalt(III) sulphate
762 ORB. Inorganic Chemistry for Competitions
Or Thus, the charge on the complex anion is -1.

Tetrakis (ethane-I ,2-diamine) -Il-amido-Il-hydroxodicobalt (ID) Therefore, the fonnula of the coordination compound is
sulphate. r OH 1 K[PtCI3(NH3)]
2. Tetraammineaquachloridocobalt(m) chloride
The complex (H20),Fe< )Fe(H 20)' (SO,), is Cation : [CoCI(H20)(NH3)4t
x = oxid. number of Co + algebraic sum of
named as: 0
the charges on the ligands
Tetraaquoiron(ID) -1l-dihydroxotetraaquoiron(ID) sulphate. = +3 + (- 1) + 0 +4 x 0 = +2
Writing the formula of a coordination Anion =Cl-
(Two anions neutralise the charge on the cation)
compound from its IUPAC name
Therefore, the fonnula of the given coordination compound
Following rules are followed in writing the fonnula of a is
coordination compound :
[CoCI(H20)(NH3)4]CI2
1. Fonnula of the cation whether simple or complex is
. 3. Tetraamminediaqllacobalt(llI) chloride
written fIrst, followed by that of an anion.
~2~The ~coordinafiofFsphereis~writtell~ in: ~sqlia:re~bnfckets. Cation:.[Co(NH3h(FI20)i1~
3. The following sequence of symbols within the coordination +3 + 0 + 0 = x
sphere is followed: x=3
(i) Metal atom .. (ii) Anionic ligands :. Molecular fonnula of the complex is :
(iii) Neutral ligands . (iv) Cationic ligands [CO(NH3)4(H20)2]CI 3
(a) If there are\ a number of ligands of same type (anionic, 4. Sodium ethane·l,2·diaminetetraacetatochromate~m
neutral or cationic), they are listed alphabetically, according to Cation: Na+
fIrst alphabet of their fonnula. For example, if NO), SO~-, Anion: [Cr(edta)t
OH-, Br-, etc., are present, they are written as Br-, NO), OIr x = oxid. state of chromium + algebraic sum
~s~ ... of charges on the ligands
(b) When two ligands have same defIning atom; the ligand = +2 + (- 4) x 1 =-2
\Vith fewer such atoms is cited fIrst followed by the ligand Thus, two Na+ ions should be present in the complex to
having more atoms. For example, SO~- precedes S2~-' neutralize the charge.
(c) When the number of defIning atoms are same, Therefore. molecular fonnula of the complex will be
subsequent, symbol decides the sequence. For. example, NH2 Na2[Cr(edta)]
precedes N02 because H comes before O.
4. Poly atomic ligands are enClosed in parentheses but all 1~Jj WERNER'S COORDINATION THEORY·
ligands are fonnulated without any space in between.
S. The number of cations or anions to be written in the Werner, in 1893, proposed coordination theory to explain the
fonnula is calculated on the basis that. total positive charge on properties and structures of various metal ammines of cobalt,
the cation must be equal to the total negative charge on the chromium, platinum, etc. It was ftrst successful attempt which
anion, as the complex as a whole is electrically neutraL satisfactorily described the fonnation of coordination com;;;
6. Sometimes abbreviations for certain ligands are used in pounds from stable molecules. The important postulates of
parentheses instead of their structural fonnulae. For example, coordillation theory are:
1. Every element exhibits two types of valencies:
(en) ethylenediamine (dmg) dimethylglyoximato
(ethane-I, 2-diamine) (a) Primary valency and (b) Secondary valency.
(dien) diethyleneniarnine (py) pyridine (pyridyl) . In modem terminology, primary valency corresponds to
(nien) niethylenetetraarnine (phen) 1,1O-phenanthroline the oxidation state of the central metal and secondary valency
(acac) acetylacetonato (gly) glycinato represents the coordination number of the metal. Primary
(dipy) dipyridyl (tripy) nipyridyl valency is satisfIed by negative ions. This is also called principal,
(edta) I ethane-l,2-diamine (ox) oxalato ionisable or ionic valency. Its attachment to the metal is
tetr,aacetato
J shown by dotted "lines.
Few examples are given here to explain the above rules. The secondary valency is satisfIed by neutral molecules or
1. Potassium amminetrichloridoplatinate(II) negative ions. This valency is non-ionic or non-ionisable. The
Cation: K+; Anion: [PtCI3(NH3)t donor atoms of .the ligands which satisfy the coordination
x = oxid. number of Pt + algebraic sum of number are directly attached to the metal atom and shown by
charges carried by ligands thick lines. Thus, the coordination compound, CoCI3·6NH3,
= + 2 + 3 x (-1) + 0 = -I . may be represented as: .
CI has coordination number 6, the complex is octahedral, i.e.,

i six positions around the metal are occupied by six donor
H3N~1/NHa atoms of the ligands octahedrally. On the other hand, if the
coordination number is 4, the geometry of the complex may
H3N ---'.Co.-,-- NH3
be tetrahedral or square planar. This postulate predicted the
CV7 ~-'CI existence of different types of isomerism in coordination
. HaN . NHa compounds.
Every metal has a fixed coordination number. For example, Examples:
Co(ID) and Pt(IV) were recognised as having coordination Octahedral . Squareplanar Tetrahedral
number 6 while CU(ll) has 4. In order to designate materials [Cr(NH 3)6]3\ [Ni(CN)4]2-; [Ni(CO)4];
held by secondary valencies, it has become customary to
[Co(NH3)d+ ;[Cr(H20)~]3+; [Ni(NH3)4]2+; [CuX4]2-; [ZnCI4]2-;
enclose the metal and all such materials in square bracket when
writing formulae. For example, coordination compounds such [Fe(CN)61 2-; [Fe(F6)] 3-; [CU(NH 3)4]2+; [NiX4]2-
as CoC13·6NH3 and PtC14·6NH3 are written as [Co(NH3)6]CI3 [Pt(NH 3)6]4+ ;[PtC1612~ X:= Cl-, Br- r
and [Pt(NH3)6]C4 respectively.
llc[CofNH3)4C12]Gl, Wernerwasableto isolatetwDcisomers;=-::c:c-
2~Everyelem.efittenilsto .satisfybolliitsC- ~Piiillii.i:Y' and He predicted an octahedral structure for coordination number
secondary valencies. A negative ion when present in the
6, because only octahedral structure can form two isomers
coordination sphere shows a dual behaviour. It may satisfy
(1, 2- and 1, 6-). The planar hexagonal and trigonal prism
both primary and secondary valencies. The presence of negative
arrangements will give three isomers each,
ion in the coordination sphere reduces the charge on the complex
ion by the amount of charge possessed by it and the negative CI
ions present in the coordination sphere are not ionised. Thus,
the following coordination compounds will have varying number
of ionisable chlorine atoms but coordination number remains
the same.
CI CI
1,2- or cis-isomer 1,6~ or trans-isomer
Similarly, the existence of two geometrical isomers of the

complex, Pt(NH3hCI2, was proved by accepting square planar
configuration ..
PtC14·6NH3 [Pt(NH3)61C14 +4 6 4 5
The postulates of Wemer's coordination theory were actually
PtC14,5NH3 fJiIl(NH3)5CI1C13 +3 i 6 4
based on experimental evidences rather than theoretical. A large
PtC1 4,4NH 3 [Pt(NH3)4CI21CI2 +2 I 6 3 number of metal ammines were studied by Werner using molar
PtC1 4·3NIJ3 [Pt(NH3hCI3]Cl i +1'. 6 2 conductance values as to ascertain the number of ions per
PtC14· 2NH 3 [Pt(NH 3)zC141 I 0 i 6 Non-electro- molecule and chemical methods such as precipitation of CI- by-
lyte AgN03 as to determine the number of ionisable ions percr
molecule. The following experimental data regarding cobalt
3. The ligID:lds which satisfy the secondary valencies are . ammines well supported the postulates that. the secondary
directed towards fixed positions in space. The geometry of the valency of 6 is maintained in all the cobalt amrnines and when
complex ion depends on the coordination number. If the metal the cr ion enters the coordination sphere, it decreases the
L positive charge on the complex ion by one unit.
L
L
L~L
H'N~sr'
CI~N~
I I
!
Pt Pt
L L L L
L
CI CI HaN CI
L L Cis-isomer Trans-isomer
Octahedral Square planar Tetrahedral .
764 GR.B.. Inorganic Chemistry for Competitions
No. of ions in Ionisable cr ions

Molecular formula Molar conductance Secondary valency louie formulation
molecules (precipitation with AgN03)
CoCl 36NH 3 4::30 4 3 6 [Co(NH 3)6]C1 3

CoC1 35NH3·H20 430 4 3 6 [Co(NH 3)5H20 ]C13
CoC1 35NH 3 250 3 2 6 [Co(NH 3)5C11C12
CoC1 34NH 3 100 2 6 [Co(NH 3)4CI2]CI
CoC1 33NH 3 0 Non-electrolyte 6 [Co(NH 3hCl3.1
Werner theory is also supported by the conductance [Pt(NH3)4CI2]Br2 and [Pt(NH 3)4Br2]CI2
measurements. Tetraamminedichlorido- Tetraarnminedibromido-
platinum(IV) bromide platinum(IV) chloride
[Co(H 20)6]CI3 [Co(H20)sCI]CI2 [Co(H20)4Cl2]CI
(A) (B) (C) [Co(NH3)4CI2]N0 2 and [Co(NH3)4ClN02]Cl
Tetraamminedichlorido- Tetraamminechloridonitrito-n-
[Co(H20)6Cl 2] cobalt(lII) nitrite cobalf(ITI) ch16riae -~-------
- - -mfUydrateisomerlsm:This type
In above complexes A, B, C and D, the primary valency is when different number of water molecules are present'inside
satisfied by 3, 2, 1 and 0, Cl- ions respectively. Thus, conduc- and outside the coordination sphere. This isomerism is best
tance of equimolar aqueous solution of these complex lie in illustrated by the three isomers that have the formula
following order:
CrCI3·6H20.
A>B>C>D (a) [Cr(H20)6]CI3~Violet. All-the six water molecules are'
coordinated to Cr. It has three ionisable chloride ions.
15.5. 1 ISOMERISM IN· COORDINATION
(b) [Cr(H20)sCI]C12·H20-Green. Five water molecules
COMPOUNDS
are coordinated to Cr. It has two ionisable chloride ions. One -
The compounds having same molecular formula but different water molecule outside the coordination sphere can be easily
physical and chemical properties on account of different lost.
structures are .called isomers and the phenomenon as (c) [Cr(H20)4C12]CI·2H20-Green. Four water mole-
isomerism; Isomerism in coordination compounds may be cules are coordinated to Cr. It has one ionisable Cl- ion. Other
divided into two main types: examples of hydrate isomerism are:
(1) Structural isomerism 7 (2) Stereo-isomerism
[CO(NH3)4H20Cl]Br2 and [Co(NH 3MBrh]CI·H 20
1. Structural Isomerism Tetraammineaquochlorido- Tetraammineaibromidocobalt(III)
cobalt(III) bromiae chloriae monohydrate
It is displayed by compounds that have different ligands [Cr(enh(H20)Cl]Clz and [Cr(en)zCl2]CI·H 20
within their coordination spheres. The different types of Aquochloriao bis (ethyleneaiamine) Dichlorido bis (ethylenediamine)
structural isomerism shown by coordination compounds are chromium(III) chloriae chromium(III) chloride
discussed below: monohyarate
(i) Ionisation isomerism : This type of isomerism arises (iii) Coordination isomerism: This type of isomerism
when the coordination compounds give different ions in solution. is observed in the coordination compounds having both cationic
For example, there are two iso~ers of the formula and anionic complex ions. The ligands are interchanged in both
Co(NH 3)sBrS04' the cationic and anionic ions to form isomers. Some examples
are:
[Co(NH 3)sBr]S04 ~ [Co(NH 3)sBr]2+ + SO~-
(Violet) Pentaamminebromido- [Pt(NH 3)4] [CuC1 4] and [Cu(NH3)4] [PtCI 4]
cobalt(UI) ion Tetraammineplatinum(II) Tetraamminecopper(II)
tetrachloridocuprate(II) tetrachloridoplatinate(II)
This isomer gives a white precipitate of BaS04 with BaCl2
solution. [Cr(NH 3)6](CO(C 20 4h] and [Co(NH 3)6] [Cr(C 20 4h]
[fO(NH3)sS04]Br· ~ [Co(NH3)sS04t + Br-
Hexaamminechromium(III) Hexaamminecobalt(III)
trioxalatocobaltate(III) trioxalatochromate(III)
(Red) Pentaamminesulphato-
cobalt(III) ion [Cr(NH3)6][Cr(SCN)6]
Hexaamminec hrom i um(III)
Above isomer gives light yellow precipitate with AgN03
hexathiocyanatochromate(III)
solution. Other examples of ionisation isomerism are:
Coordination Compounds and Organometallics
and [Cr(NH3MSCNhl[Cr(NH3h(SCN)4] (1) Geometrical isomerism: This isomerism is due to

Tetraamminedithiocyanatochromium(III) ligands occupying different positions around the central metal
diamminetetrathiocyanatochromate(III)
atom or ion. The ligands occupy positions either adjacent or
(iv) Linkage isomerism: This type of isomerism occurs opposite to one another. This type of isomerism is also known
in complex compounds which contain ambidentate ligands as cis- and trans- isomerism.
like NO:?:, SC~, CN-, S20~ and CO. These ligands have two Geometrical isomerism is very much common in coordination
donor atoms but at a time only one atom is directly linked to number 4 and 6 complexes.
the central metal atom of the complex. These types of isomers Square planar complexes (coordination number four)
are distinguished by infra-red (I.R.) spectroscopy. For example, exhibit geometrical isomerism.
[Co(NH3)sN02]Cl2 and [Co(NH3)sONO]CI2 are linkage (i) Complexes with general formula, Ma2b2 '(where both a
isomers as NO:?: is linked through N or through O. and b are monodentate) can have cis- and trans-isomers.
[Co(NH3)sN021CI2 and
Pentaamminenitrito-n-cobalt(ill)
[Co(NH 3)sONOJCI2
Pentaamminenitrito-o-cobalt(ill)
a~b a~a H3N~CI H3N~NH3
M M Pt Pt
chloride (yellow) chloride (red)
b a b b CI NH3 . CI CI
Another example of this type of isomerism is: Trans-isomer Cis-isomer Tmns C~
, ,
[Pd(dipy)(SCNh] and [Pd(dipy)(NCSh] [Ma2bz]
. Dipyridyltlithi9.cyanato- . . Dipyridyldiisothiocyanatoc til) Cbmplexeswithgeneral forinula, MaiDc can have
palladium(ll) . palladium(ll)
and trans-isomers.
(v) Polymerisation isomerism: This type of isomerism
exists in compounds having same stoichiometric composition a~a a~c
but different molecular compositions. The molecular composi-
tions are simple multiples of the simplest· stoichiometric b~C b~a
arrangement. For example in the following three compounds,
the second and third compounds are polymers of the first.
Cis Trans Cis
.
[Pt(NH3hCIN021
Trans
[Pt(NH3hCI2]; [Pt(NH3)4][PtC14]; [Pt(NH3hClh[PtCI4] (iii) Complexes with general formula, Mabcd can have three
(i) (ii) (iii) isomers.
[Note : (ii) and (iii) compounds are actually not the examples of
polymerisation, i.e., (i) compound is not acting as a monomer
afVlb afVld afVlb
in the formation of (ii) and (iii) compounds.]
(vi) Coordination position isomerism: This type of
d lL:~~~:~~L C~b C~d
(i) (ii) (iii)
isomerism is exhibited by polynuclear complexes by changing
the position of ligands with respect to different metal atoms Example: [Pt(NH 3)(NH20H)(N02)(Py)]N0 2.
present in the complex. For example, (iv) Square planar complexes having unsymmetrical bidentate
ligands can also show geometrical isomerism. For example,
Co(02)CO(~'!-!'h Cl2
NH2 ]2+ platinum glycinato complex, [Pt(Glyh], exhibits geometrical
(NII')4 isomerism .
r . Unsymmetrical
(Both the chloro ligands are with same cobalt ion.)
NH ]2+
and (NIl3hC1CO(02)Co(NH ,hCl
r Symmetrical
(Same ligands are linked with both cobalt ions.)
[Ma4t± and [Ma3bt± type square planar complexes do
2. Stereo-isomerism not show geometrical isomerism.
Tetrahedra. and Linear complexes
Compounds are stereo-isomers when they contain the same
ligands in their coordination spheres but differ in the way that These complexes do not show geometrical isomerism
. these ligands are arranged in space. Stereo-isomerism is of because the geometry of these ligands is definite, e.g.,· in
two types, viz., geometrical isomerism and optical isomerism. tetrahedral complexes, any two ligands lie at 109~8'; while in
linear complexes, the two ligands lie at 180°.
,.r
Octahedral complexes of the type Ma4b2 and Ma3b3 exhibit molecules are. optical isomers. The optical isomers are pair of
geometrical isomerism. molecules which are non-superimposable mirror images of
b each other. The essential requirement for a substance to
$b.$a $b $b
b b b
be optically active is that the substance should not have
a plane of symmetry in its structure. The isomer which
a~a a~a a~b a~a

rotates the plane of polarised light to right direction is termed
dextro (d-form) while the isomer which rotates the plane of
,a b a b polarised light to left direction is termed laevo (I-form). The
pis Trans, ,Cis Trans;
., "Y two optically active isomers are collectively called enantiomers.
[M~b:!l ' [Maabsl
Enantiomers are mirror image to each other and their physical
Example: [Co(NH3)4CI2]CI, [Co(NH3hCI3] properties are different.
Octahedral complexes of general formula, Mabcdef, can Optical isomerism is expected in tetrahedral complexes of
have fifteen geometrical isomers. the type Mabcd but no optical isomer has been isolated until
Facial and Meridional Isomers now.
However, compounds containing two unsymmetrical
A set of three, ligands (similar) may be' arranged on an
bidentateligands have been resolved into optical isomers and '
octahedron in all cis~fashion, giving facial or 'fac' isomer. In
are known . for .. Be(II), . . Zn(II) and B(III). -For. example:----
otherWOfas;tnreeslmila:r:-llgandsonthe same face of
octahedron give rise to the facial isomer.
Bis';benzoy Iacetonato:berylliumoI):-eXlllbitS opticailsomensm.
NHa H C·
a , O-C
/CHa i: CHa, c-o '/:
CH . ,
a ;,c-O" / \. : ! \ /O-~
H-C" B e C - H 1H-C Be C-H
..." 'C~O/ -\ /- -:\.. I"'-o=c/ .. _.
/ O=C :. C=O ,
HsC6 . 'H C : H C/ HSC6
s 61 S 6
Mirror plane
b
1,2;3 or facial isomer Optical isomers rarely occur in square planar complexes on
cr
. account of the' presence of axis of symmetry.
A set of three similar' ligands may be arranged on an
Optical isomerism is very common in octahedral com-
octahedron with one pair trans (meridian of octahedron), giving
plexes. Octahedral complexes of general formulae,
rise to meridional or 'mer' isomer.
[Ma2b2C2]n±, [Mabcdef], [M(AAhf±, [M(AAha2t±,
NHs
I
1 (where AA = symmetrical bidentate ligands)
I·
1 a
[M(AAhabt:!; and [M(ABht±
cr~; cr 'I'
Co:>!- .
(where AB unsymnietricalligands)
f show optical isomerism.
H3N .
:I .cr Examples:
I
I (a) [Ma2b2c2t±; [Pt(Pyh(NH~hCI2]2+ .
I
1,2,6 or meridional isomer
NH3 2+ ,,
I
py 2+
r
I
Note: 1. Geometrical isomerism is not observed in complexes of ,
w.~ ~CI
py I
coordination number 2 and 3. I
I
. .
l
2. Geometrical isomerism is not observed in complexes of I
I Pt
I
coordination number.4 of tetrahedral geometry. I
I
3. The complexes of general fommlae, Ma3b or Mab3, or Ma4, of Cl . NH3 I

I H3N ,Cl'
I
I
square planar geometry do not show geometrical isomerism. NHa I
I . NHa
4 .. The complexes of general formulae, Ma6 and Masb, of Mirror
octahedral' geometry do. not' show geometrical isomerism. Ci$-d-isomer Cis-i-iSomer
S. 'Fac' and 'mer' isomers of an [Ma3b3l octahedral complex are (b) [Mabcdef]; [Pt(py)NH~02CIBrI]
optically inactive.
'(2) Optical isomerism: A coordination compound which
can rotate the plane of polarised light is said to be optically
active. When the coordination compounds have same formula
but differ. in their abilities to rotate directions of the plane of
ttzN~.
.
Sr
.
Pt.' -
.. 1
, I
I
I
I
I
1
I
,,
,,
,
pttzpy
'.
Br
Pt
CI' .. ' .. NHa 1 ,, HaN" '. CI

polarised light are said to exhibit optical isomerism and the I
I ,
I I
d-isomer Mirror I-isomer
Ii (1) Valence bond theory
It is the simpiest of the three theories and was developed
[~r I [~l
. mainly by Pauling. It describes the bonding in terms of hybridized
orbitals of the central metal atom or ion. The theory mainly
deals with the geometry (i.e., shape) and magnetic properties
of the complexes. The salient features of the theory are:
(i) The central metal loses a requisite number of electrons
d-form Mirror f:.form
to form the ion. The number of electrons lost is the valency
of the resulting cation. In some cases, the metal atom does not
lose electrons.
(ii) The central metal ion or atom (as the case may be)
makes available a number of empty s-, p- and d-atomic orbitals
equal to its coordination number. These vacant orbitals hybridize
together to form hybrid orbitals which are same in the number
as the atomic orbitals hybridizing together. They are vacan!, ___ _
Cis-/~isomeL __ ..
equivalent in energy and havt!<!efi!'i~~g~~Il!~tly·_ ._..::.=.===C.
S-ome --6'fthi- coi:ti:ffion- hybridizcii orbitals met in the
Trans form of [M(AAha2Jn± does not show optical coordination compounds are listed below:
isomerism. (For details see chapter 2 on valency.)
(e) [M(AA)2abt±; [Co(enhNH3Cl]2+ Coordi- Type of I
I . nation., _h)'bri•.,,_.c.,Geomet~,.-. --,-."'---.~..cExamples-··· .. _-"
[~
n~ber dization
I
I '
,
r
I
I
CI .
I '2+ 2 Linear [Ag(NH 3ht, [Ag(CNhr'
NH,
I
c~
I
,,,
I
3 Trigonal planar [HgI3r
["'Nrw.Cis-d-isomer
I
I
I
Mirror
eo
Cis-I-isomer
4 Tetrahedral
Square planar
Ni(CO)4, [Ni(X4)]2-, [ZnC4]2-,
[CuX4)2-, where X =
[Ni(CN)4f-, [Cu(NH3)4]2-
cr,
Br-, r
[Ni(NH 3)4]2+
5 Trigonal Fe(CO)s, [CuCIs]3-
I
bipyramidal
,
I
g~
~
I IY
I
I
Square [SbFs]2~ "
I
pyramidal i
,~91Y
I
,
I gly " Gr ' 3
I 6 Octahedral i, [Cr(NH3)61 +, [Fe(CN)6)3-
, ,,
I
gly I gly (Inner orbital) '\ ' . ,

I , , 3' U '
Mirror
(Outer orbital) [FeF61 -, [Fe(H20)6] ,
: 2+
! [Ni(NH 3)6]
Cis- or trans-d-isomer , Cis- or trans-J-isomer ,
Some more examples are : (iii) The non-bonding electrons of the metal occupy the
[Cr(oxh]3-; [Fe(dipYh]2+; [Cr(oxh(H20hr; [Pt(enht+' ',inner orbitals. These are grouped in accordance with Hund's
rule, however, under the influence of some strong ligands,
1.' BONDING IN COORDINATION there may be some re-arrangement of electrons in the atomic
COMPOUNDS orbitals (against Hund's rule). The d-orbitals participating in
this process of hybridization may be either (n -1) d2sp3 or
Werner was first t.o describe the structures and the existence . nsid2, The complexes thus formed are referred to as inner or
of various types of isomerism in coordination compounds.' low spin and outer or high spin complexes, respectively.
However,. the nature of bonding between central metal atom , (iv) The ligands have at least one a-orbital containing a lone
and ligands in the coordination sphere has been explained by pair of electrons. Vacant hybrid orbitals of the metal' atom or
the three well. known theories. These theories are : ion overlap with the a-orbitals containing lone pair or electrons
1. Valence bond theory of the ligands to form M ~ ligand ,cr-bond. This bond is called
2. Crystal field theqry coordinate bond (a special type of covalent bond) and possesses
3. Ligand field or 'molecular orbital theory a considerable amount of polarity.
--- y--
(v) It is possible to predict the magnetic properties of the complex if the geometry of the complex ion (or vice-versa) is known.
If the complex contains unpaired electrons, it is paramagnetic in nature whereas if it does not contain unpaired electrons, i.e.,
all are paired, the complex is diamagnetic in nature. Complexes having unpaired electron are coloured.
The number of unpaired electrons and the geometries of the complex ions having central metal ion with configurations d 1
to d 9 are related to each other as shown below:
The shapes and magnetic nature of some of the common complexes of metals of 3d~series have been described on the basis
of valence bond theory in the table given below:
Number of unpaired electrons for different geometries
Octahedral
Tetrahedral (sp~ Square planar (dsi)
dl
d2 2 2 2 2
d3 J 3 3 3
4
d 4 4 2 4
1
6
d 4 2 0 4
d7 3 3
(Shifted to higher orbits)
dS 2 o 0 2
(2 electrons shifted)
d9
Limitations of valence bond theory: The valence bond theory was fairly successful in explaining qualitatively the
geometry and magnetic properties of complexes. However, it has a number of limitations.
(i) The theory does not offer any explanation about the spectra of complex (why most of the complexes are cotoured).
(ii) Sometimes the same metal ion assumes different geometry when formation of complex ion takes place. The theory is
unable to explain why at one time the electrons are rearranged against the Hund's rule while at other times the electronic
configuration is not disturbed.
(iii) The theory does· not offer an explanation for the existence of inner-orbital and outer-orbital complexes.
(iv) The theory does not explain why certain complexes are labile while others are inert.
(v) In the formation of [CU(NH3)4]2+, one electron is shifted from 3d to 4p-orbital. The theory is silent about the energy
availability for shifting such an electron. Such an electron can be easily lost, then why [CU(NH3)4f+ complex does not show
reducing properties.
(vi) The changes in energies of the metal orbitals on formation of complex are difficult to calculate mathematically.
Inner orbital octahedral complexes Outer orbital octahedral complexes

or low spin complexes or bigh spin complexes
i. These complexes are forined by hybridization of d2si hybridisation. l. These complexes are formed by hybridisation of sid 2 hybridisation.
These are fonned by strong ligands. These are formed by weak ligands.
2. These complexes generally possess less number of unpaired electrons 2. These complexes generally possess greater number of unpaired
i.e., they show either low or no magnetic moment. electrons i.e., they show high magnetic moment.
3. These are less reactive i.e., more stable. Substitution reactions are 3. These are reactive i.e., less stable. Substitution reactions are easy to
difficult to occur. occur.
Coordination Compounds and Organometallics Z69·
Note: (i) Mn+ ions which have one, two or three electrons in 3d negatively charged ends of arrgnoniamolecules. These attractive
orbitals prefer to form inner orbital octahedral complexes. forces bind the ligands to· the metal ion. The bonds between
8 9
(ii) M"+ ions which have d and d configurations prefer to metal and the surrounding ligands are purely ionic. This theory
form outer orbital octahedral complexes. does not consider any orbital overlapping.
4 5 6
(iii) M"+ ions which have d , d and d configurations may form (b) The repulsive forces arise between the lonepairs on tbe
either inner .oi outer orbital complexes. It depends on the ligands and electrons in the d-orbitals of the metal or atom. The
nature of the ligand. crystal field theory mainly focuses on these repulsive forces.
(iv) M"+ (Pt2+, Pd2+, N·2+1 , AU 3+ ,etc. . d 8 confiIguratlon
. ) havmg '. . These forces are responsible for causing a considerable effect
mainly form square planar complexes. ., on the relative energies of the d-orbitals of the central metal ion
(v) M"+ having dO, d 5 and dlO configurations prefer to form or atom.
tetrahedral complexes. (iv) In a free transition metal or iO.n, there .are five
d-orbitals which are designated as dxy, dyz,dz;x> d:J. _;- and d;}.
(2) Crystal field·tO:ory The five d-orbitals are divided into two sets depending on the
Crystal field theory was proposed by H. Bethe (1929) and natur~ of their orientation in space.
Van Vleck (1932) and was originally applied to ionic crystals (a) The three d-orbitals (dxy , dyz , dzx) which orient in the
to explain their optical properties and is, therefore, called crystal regions between the coordinate axes are designated as t2g
field theory. However, this theory was applied to the study of orbitals (pronounced as "t-two-g").t2g,?:()rbitals arethree-folclc:c
coordination compounds in 1950. The valence bond theory degenerate. Tbese are non-axial orbitals. .
represents the ligand metal bond as covalent, with an electron (b) The other two orbitals (d:J.- v2), d?- which orientalong
pair, shared between the metal and the ligand donor atom. The the axes are called eg, orbitals (pronounced as "e-g"). ego orbi-
valence bond theory is frequently used but it is not adequate tals are two fold degenerate. These are also called axial-orbitals.
to explain properties of complexes such as colour and tz
[The names g and egare derived from spectros~opic terms.I.
magnetism~ Currently, the bonding in coordination complexes In a free transition metal ion or atom, all the five d-orbitals
is usually described by crystal field theory or ligand field theory. have same energy, i.e., they are degenerate. However, when
This theory accounts for more satisfactory explanation for the the ligands approach the central metal ion or atom, the electrons
properties of complexes especially colour and magnetism. The of the d-orbitals of the central metal ion or atom are repelled
main points of the theory are: . by lone pairs of the ligands. As a result of these interactions,
(i) According to crystal fieldtheory, the bonding in complex the degeneracy of d-orbitals of th~ metal ion is lost depending
ions is purely electrostatic. This theory regards the ligand atoms on the orientation of ligands in space. The d~orbitals split into
of ionic ligands such as F, Cl- or C~ as negative point .two sets of orbitals having different energies.· This is called
charges (also called point charges) and if the ligand molecules crystals field splitting. Itis the basis of crystal field theory. The
are neutral, these are regarded as point dipoles or simply dipoles, extent of splitting depends on the number of ligands and their
the negative end pointing towards central metal ion. position around the metal atom or ion. The spHtting is different
in different structures with different coordination numbers.
of
Splitting d-orbitals in octahedral complexes: Let us
consider an octahedral complex, TM 4]n+; in which the central
metal ion is placed at the centre of the octahedron and is
(Ammonia molecule) (Water molecule) surrounded by six ligands which reside at the six corners of
the octahedron as shown below.
(ii) The complex is regarded as a combin~tion ofac:~al .Z
··~J':_l_-~L.
metal ion surrounded by ligands which act as point Gharges or
point dipoles. The arrangement of ligands around'the central
x
metal ion or atom is such that the repulsion between these I ,//~~/1,
~~l*··
negative points or dipoles is minimum. .'
(iii) Interactions betweeri positively charged nuCleus of the
central metal ion or atom and the negatively charged ligands
are of two types: . . y
(a) The attractive forces arise due to the positive metal ion The electrons in d-Orbitals of the metal cation are repelled
and the negatively charged ligands or the negative end of a by negative point charge or by the negative 'end of the dipole
polar neutral molecules. For example, in the case of complex of the ligands. This repulsion increaSes the energy of all the
ion, [Fe(CN)6]3-, the interactions are between Fe3+ ion and five d-orbitals.·If.all the ligands approaclring the metal cation
negatively charged C~ ions whereas. in the complex; are at an equal distance from each of d-orbitals (i.e., the ligand
[Cr(NH3)6]3+, the interactions are. between Cr3+ion and. field is sphericallJ: symmetrjcal), the energy of each of the nve
770 GR.B. Inorganic Chemistry for Competitions _
Geometry (shape) and magnetic nature of some of the complexes

(Application of valence bond theory)
IAtom lion I Configuration

Oxidation '!ype of
state of hybridi-
Geometry
shape
No. of
unpaired
Magnetic
nature
• complex
metal zation electrons
1~_(_1)__~___________(2_)__________-+__(_3)__+-_(4_)-r___
(5_)__+-_(6_)-+___(7_)~
3d 4s 4p
lulHIHlfltl 0 I I I I +2 2 Paramagnetic
IUIHIHI f I f I UJ I: I: I: ! +2 Tetrahedral 2 Paramagnetic

Sp3
[Ni(CN)4Y+· IHIr+IUIH!:1 ~ I: I:! I +2 dSp2. Square planar o Diamagnetic - _. .

....+ -.·~-c-:--::c--••·.·.-:-c_--..t-:-_Rearr.ang~ment.--dsp~---------- ....- --- -.. ------ - . • ---- ----r--.- ..~.__- --~--I-...· i-.-.-.-..--.-.:-..-:-::-:-··••-.-..-:t==.=
--.------.... ..
Ni IHIHIHI fit I !llI I I I I o 2 Paramagnetic
Ni(CO)4 IHIHlulUIHI UJ I:.I: I: ! o Tetrahedral o Diamagnetic 1---
Rearrangement Sp3
3d 4s 4p 4d
[Ni(NH 3)6F+ IHlulHI f I f I [II I: I: 1: 1 I: I:·1 I I I
. +2 sp 3d 2 Octahedral 2 Paramagnetic
(Outer)
sp 3d 2
3d 4s 4p
Itltltltltl 0 I I I I +2 5 Paramagnetic
[Mn(CN)6J4-- IHIHI t I: I: I [II. I: I: I: I +2 d 2sp3 Octahedral 1 Paramagnetic

Rearrangement d 2sp3 (Inner)
Itltltlfltl [II 1:1:1:1

'-------v------
+2 Tetrahedral 5 Paramagnetic
Sp3
IHIHIUIHltl 0 I I I I +2 Paramagnetic
IHIHlulHI t I [II I: I : I: I
'-------v------
+2 Tetrahedral Paramagnetic
Sp3
[Cu(NH3)4P+ It +It +It +It +1.: I [II I: I : It I +2 dSp2 . Square planar Paramagnetic
One electron is shifted from 3d- to 4p-orbital I
Contd. ...
(1) (2) (3) (4) (5) (6) (7)

3d 4s 4p
Cr3+(d 3) Itit It I I I D I I I I +3 3 Paramagnetic
[Cr(NH3)6P+ Itltltl:I:1 .
II]
d sp3
I: I:
2
1: ! +3 d 2sp3
(Inner)
Octahedral 3 Paramagnetic
4d
[Cr(H2O)6P+ Itit It I I I IIJ I: I: .-
I: I J: I: ! I I I +3 sp 3d 2
(Outer)
Octahedral 3 Paramagnetic
sp3d 2
C o3+(d 6) It tl tit Itit I D I I I I +3 4 Paramagnetic
[COF6P~
- ---
IHI tl t It Itl
.... ..
,II] 1:1:1:1
=
!: I: ! I I I .
+3
......... _-
sp 3d 2 Octahedral 4 Paramagnetic
- - - - - - - - - - - - - _...............
-
--
...
--
sp3d z :::(OmerT ...

~.
~~-----~------
-- ~
~.
~--
~
[CO(NH3)6P+ IHIHIH! : I: I . I: I: I:!II] +3 d 2sp3 Octahedral 0 Diamagnetic

Rearrangement d sp3 2 (Inner)
...::. - .- 1-
Co2+(d'l) IttlHI tit It I D I I I I +2 3 Paramagnetic
[Co(H2O)6]2+ It tit II tit It I II]

, I: I: .I: I I: I: I I I I +2 sp 3d 2 Octahedral 3 Paramagnetic
(Outer)
sp 3d 2
Fe 2+(d 6) Ittl t It Itit I D I I I I +2 4 Paramagnetic
[Fe(CN)6]4- IHIHIHI : I: I
, ..
II] I: I: I: I +2 d 2sp3 Octahedral 0 Diamagnetic
Rearrangement d sp32 (Inner)
[Fe(HzO)6F+ IHI tit Itit I IIJ I: I: .I: I I: I: I I I I +2 sp 3d 2 Octahedral 4 Paramagnetic

(Outer)
sp 3d 2 -- -
[Fe(NH 3)6F+ Same +2 sp 3d 2 Octahedral 4 Paramagnetic

(Outer)
Fe 3+(d 5) Itltltltltl D I I I I +3 5 Paramagnetic
",
[Fe(CN)6P- IHlttl t I: I: I
,
II]
,
I: I: I: I +3 d 2sp3 Octahedral 1 Paramagnetic
d 2sp3 (Inner)
Fe Ittl tit Itit I ~ II I I 0 4 Paramagnetic
Fe(CO)s IHlttIHIH! : I II] , I: I·: I: I 0 dSp3 Trigonal 0 Diamagnetic

dsp 3 (Inner) I bipyraruidal
d-orbitals increases by the same amount, i.e., all the d-orbitals higher than the energies of dxy, dxz and dyz orbitals. Therefore,
remain degenerate, although tQey possess higher energy. it is clear that introduction of the ligands removes the
However, this is not possible as it is only hypothetical situation. degeneracy of the five d-orbitals, splitting them into two sets
\.. of degenerate orbitals; the lower energy set consists of the dxy,
z z
\ dxz and dyz orbitals and higher energy set comprises the
dx2 _ y2 and dz2 orbitals [Fig. 15.2 (i)]. The three lower energy
orbitals are collectively called the t2g orbitals while the two
higher energy orbitals are called eg orbitals.
y x y Thus, an energy difference exists between two sets of
orbitals. This energy difference is called crystal field splitting
energy (CFSE) or crystal field stabiIization energy and is
(a)
z z z
x (t29+e g)
orbitals in
free ion
(a) (b) (c)
(b) Fig. 15.2 (ii) Crystal field splitting of d-orbitals in an octahedral

complex (a) Five degenerate d-orbitals of free metal cation
(b) Hypothetical degenerate d-orbitals at higher energy
Fig. 15.1 The shapes of the five d-orbitals and their
orientations with respect to an octah~dral level under spherically symmetrical ligand field
array of charged ligands (c) Splitting of d-orbitals ,under the influ~nce of 'ligands.
As the lobes of the dx2 y2 and dz20rbitals [Fig. 15.l(a)] represented by Ao {the subscript 0 stands for octahedral). It
point directly towards the ligands, an electron in either of these measures the crystal field strength of the ligands. The crystal
orbitals is nearer to the electron pairs of the ligands than if it field splitting occurs in such a way that average energy of the
was in a dxy, dxz or dyz orbitals, with lobes pointing between d-orbitals does not change. .
the ligands [Fig. 15.1(b)]. Thus, the repulsions between the Thus, three orbitals lie at an energy that is - ~ ~ below the
ligands and the dx2 _ y2 and dz2 orbitals are greater than the average d-orbital energy· and two d-orbitals lie at an energy
repulsions between the ligands and dxy, dxz and dyz orbitals. +~~ above the average energy. The energy gap between t2g
Consequently, the energies of dx2. y2 and dz2 orbitals are
and eg sets is also denoted by 10 Dq. Energy of t2g orbitals is
d-orbitals in a d-orbitals in an 4 Dq less than that of hypothetical degenerate d-orbitals and
free metal ion octahedral complex ion that of eg orbitals is 6 Dq above that of the hypothetical
degenerate d-orbitals. Thus, tZg set loses an energy equal to .
-0.4 Ao or - 4 Dq ,,vhile eg set gains an energy equal to
+0.6 L\() or +6 Dq.
Crystal field splitting in tetnlhedral complexes: The
tetrahedral arrangement of four ligands surrounding the metal
ion M m + may be depicted as shown in Fig. 15.3.
The three d-orbitals, i.e., t2g orbitals are close to the.
Decreasing distance between metal ion and the ligands
approaching ligands. As a result of this, the t2g electrons suffer
Fig. 15.2 (i) The changes in the energies of the d-orbitals more repulsion than eg electrons. The energy of t2g orbitals
of a metal ion as an octahedral complex is formed. As the increases more than eg orbitals. The splitting is shown in Fig.
ligands approach the metal ion, the initially degenerate 15.3.
d-orbitals split into two new sets of degenerate orbitals.
of the complex. ~e lobes of d z2 orbital lie out of the plane but'
, the belt around the centre of the orbital lies in the plane of the
complex is somewhat affected by electrostatic field of the
ligands. The splitting of d-orbitals in square planar complex
can be depicted as shown in Fig. 15.4.
Spectrochemical series: For any given metal cation, the
magnitude of crystal field splitting energy depends on the nature
, of the ligands. The greater the ease with which the ligand can '
approach the metal ion, the greater will be the crystal field
splitting caused by it. The ligands' which affect only a small
degree of crystal field splitting are termed weak field ligands
while those which affect a large splitting are called strong
.- field ligands•
.-
Average energy,/ When the ligands are arranged in order ofthemagnitude-~f,,-,
,~Jy~ial",jjel,<l"slllittillg,lhe,a.rrflIlgement,Jhus,ccQbtaitled-is.fallOO---c-.:c=
, spectrochemical, series.
/ " " , ':",:",c"',,, ' ' ' , , : " 2-
'1- <Bf<cr < NO) < F < Olr < OX < H20 < py
spherical crystal
W~ak,f1eld ligands IncreaSing crystal field
(t2g + eg) field
orbitals ;:=NtI3< el1< qipy< (}::P~_el1,:::N"p2,<S._~rr< ,<;Q_,_'
in free ion ---,----,-'-;---'---,,--:--" Strong field ligands
Fig. 15.3 Crystal field splitting of d-orbitals in a From the above arrangement it is clear that ligands before
tetrahedral complex H20 such as C NO'3, OH-, etc., are weak field ligands while
the ligands after H20 such as NOl, CN-, CO, etc., are strong
The energy gap between two sets of orbitals is designated field ligands. Stronger field ligands cause greater crystal splitting ,
as lJ.t (The subscript t indicates, tetrahedral complex). It is i.e., lJ. o value for octahedral complex is high.
observed that lJ. t is considerably less than lJ.o . It has been found Besides the nature of ligands, there are some other factors
that, which affect the crystal field splitting energy. These factors
4
lJ.t =§lJ.o are:
(i) The position of transition metal in .the periodic
Crystal field splitting in square planar complexes: The
table: The magnitude of lJ.o incre,ases in gQing down a group.
square planar arrangement of four ligands surrounding the
i.e., an ion of an element in the first transition series has a
metal ion may be considered as derived from octahedral by
smaller value of lJ.o than the ion of a heavier member of the
removing two ligands from z-axis. On account of removing . compIexe$ 0 f N·12+ and Pt2+
same group. Thus, companng
negative charges from z-axis, dZ2, dxz and dyz orbitals having with the same ligand, it is, observed that platinum complexes
z-component become more stable; As the lobes of diJ.'_y2 point
have larger crystal field splitting. The crystal field splitting,lJ.o•
towards the ligands, the orbital has highest energy and the is about 50% higher for second transition series compared to
lobes of dxy orbital, lie between the ligands, it is thus next the first whereas the third series in about 25% higher than
highest in energy. The lobes of dxz and dyz are least affected second. There is sm,all increase' in the crystal field splitting
by electrostatic field of the ligands as they lie out of the plane
along each series.
(ii) The oxidation state of the metal: Generally, the
higher the oxidation state of the metal, the greater the crystal
field splitting. For example, most of the cobalt (II) complexes
have low values of lJ. whereas all cobalt (ill) complexes have
high values, of lJ..
, (iii) The number of ligands : The crystal field splitting
for a tetrahe~al environment is about 4/9 that for an octahedral
environment.
Distribution of d-electrons in tZg and eg orbitals in
d-orbitals in octahedral complexes: The distribution of d-electrons ill
free ion
t2 g and ,e g orbitals takes place on the basis of the nature of
Fig. 15.4 Splitting of d-orbitals in square planar complex ligands. Two cases may arise.
4
(I) -F.heu :-he ligands are weak:
Under the influence of (ii) For each of d , d 5 , d 6 and d7 there is difference in the
weak ligands, the energy difference, ~ , between t2g and eg arrangement of electrons in weak and strong ligands field.
sets is relatively small and hence all the five d-orbitals may be (iii) Weak field complexes of d 4 , d 5 , d 6 and i ions have
supposed to be degenerate, i.e., all the d-orbitals have nearly greater number of unpaired electrons than those of strong field
the same energy and the distribution of electrons in t2g and eg complexes and thus, the resultant spins of weak field complexes
sets occurs according to Hund's rule, i.e., electrons will pair have higher value than strong field complexes.
up only when each of the five d-orbitals is at least singly Hence, the complexes of weak field ligands are called high
occupied. When the ligands are weak, the first three electrons spin complexes and the complexes of strong field ligands are
numbered 1,2,3 go to t2gSet, those numbered 4, 5 go to eg called low spin complexes. .
set, those numbered 6, 7, 8 go to t2g set and the remaining two
electrons numbered 9, 10 will occupy eg set. This can be Calculation of CFSE
shown as: Each electron occupying t2g orbital results in lowering of
l, 2, 3 ---? 4, 5 ---? t6, 7, 8 ---? 89, 10
t 2g 8g 2g g energy by -0.40 ~ (or -4 Dq). Similarly, each electron
In complexes of weak ligands, ~ is less than P (P is called occupying eg orbital results in increase of energy by +0.60 ~
average pairing energy which is the energy reqriiredto pair two (or +6 Dq). Thus,
electrons Tn: thesanie--:::Omita1);:'~~Theoaaliedfi:if'crystaffiaa- --- ~-----~-:::.=CFSE -=-=( OAx- +:.:0:-6)')=86-::'- -
splitting energy, tends to force as many electrons to t2g set where, x = number of electrons occupying t2g orbitals
while P tends to prevent the electrons to pair in the t2g level. and y = number of electrons occupying eg orbitals.
{ii) When the ligands are strong: Under the influence Negative value of CFSE indicates net lowering in energy,
of strong ligands, the energy difference between t2g and eg i.e., gain in stability.
sets is relatively high and thus the distributioh of d electrons
Calculation of CFSE Values for til to d lO
in t2g and eg sets does not obey Hund's rule. The first electrons
Configurations
numbered 1,2,3,4,5,6 will go to t2g set and remaining four
electrons

GRB Inorganic Chemistry IIT JEE PDF

Загружено:

Сведения о документе

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

GRB Inorganic Chemistry IIT JEE PDF

Загружено:

Авторское право:

Доступные форматы

PREFACE

Chemical Bonding 68-156

Acids and Bases 157-177

General Principles of Extraction of Metals 178-208

.. Revision Exercisoe1 (Ch~pt'r 1 to 4) floe - 214.

Hydrogen and its Compounds (nai , 215-265

Alkali Metals and their Compounds (ClrouplAor1,na1, 266-315

Alkaline Earth Metals and their Compounds (Group IIAor2, nai,

• R,vl.lon 1".roill-2 (Chapter 5 to 7) 357 ..... 381

Elements of Group I~IA or 13 [Th. loron Family (nr np1)] 362'-407

Elements of Group IVA or 14 (EI.m.ntlofClrbon "Imlly, nrnpl) 408-460

Elements of Group VA or 15 '46t--529

10.1 Position in Periodic Table (461), 10.2 Abnormal Behaviour of

Elements of GrQup VIA or 16 (The Oxygen Family, ns'lnp4)

11.1 Position in Periodic Table (530), 11.2 Abnormal Behaviour of

Elements of Group VilA or 17 (Halogens, ns'lnp5) 57'6-624

12.1 Position in Periodic Table (576), 12.2 Anomalous Behaviour of

•:. Revision Exercise-3 (Chapter 8 to 13) 645-650

--+--i+--·d-bloCK Elements (Transition hlernen'ts)---.t--i---;--t--+--t-.....,

Coordination Compounds and Organometallics

.. Rlvilion &)(lrOIII-4 (Chapter 14 to 15) 811- 818

Qualitative Inorganic Analysis 884--920

.:. RevisiOn ExerciallilB (Chaptof 18 to 18) 921 =026

Contents: Object and Need of Classification of Elements

Fig. 1~2 Mendeleev's Periodic Table (Published in 1872)

Modern (Modified) Mendeleev's Periodic Table

Fr Ra Act Ku(Rf) Ha Unh(Sg) Uns(Bh) Uno Une Uun

~------ - - - Inner Transition Elements - - - - - - - - - ----7

Fig. 1.3 Modem Mendeleev's Periodic Table

At. No. 18 19 . 27 28 52 53 90 91 2nd p<riod Li OJ 2) Ne (10) 8

element having different atomic masses but same atomic

SCIENTISTIPERSONS. AFTER WHOM ELEMENTS HAVE BEEN NAMED

- AND THE PERIODIC TABLE 5 Boron B [Hel U 2pl

Z Element Symbol Structure Z Structure

36 Krypton Kr [Ar] 3dlD 4s2 4p6 Period - 7

45 Rhodium Rh [Krl ~ Ssl 96 Curium Cm [RnIS{ 6d 1 7i

.. Fig. 1.4 Periodic table, illustrating division of elements

2 Li Be 1s' Valence-shell configuration B C N 0 F Ne

7 Fr Ra ACi.. Rf Db 5g Bh Hs Mt Os Rg Uub Uut Uuq Uup Uuh

Fig. 1.5 A Modern Form of the Periodic Table (Long Form)

(ix) With exception of Be and Mg, they decompose water

• (ii) p-Block Elements

3d-series Configuration 4d-series Configuration 5d-series Configuration 6d-series Configuration

Fig. 1.6 d-block elements

- - - - - - - - - - - - - - d-Block Elements (Transition Metals) - - - - - - - - - - - - - -

Fig. 1.7 A Modern form of the Periodic Table

1.1 o~l THE SCREENING EFFECT OR B 2, 3 :::: 2 x 0.35 +2 x O.~ = 2.40

(5d Sf), (6s 6p), etc, 1.11~1 EFFECTIVE NUCLEAR CHARGE

X A and XB are the electronegativities of elements A and I

A comparison of three types of radius shows that covalent 3 Na Mg Al Si P S CI <l>

differentiating electrons enter into 4f levels. Since these

,g 1.50 ~i \Na 1\ ,., Jl.J\\ I'

Conclusions (v) In 4f-series, there is continuous decrease in size with

1.13~ IONIC RADIUS

Thus,electronegativity of an atom on Pauling scale

1 2 13 14 15 16 17 electronegativity are non-metals. Fluorine with highest

Li Be B C N 0 F The combining capacity of an element is termed the

(IV) NATURE OF HYDRIDES

'i SUMMARY AND IMPORTANT POINTS TO REMEMBER' 1

-: ••• - PRACTICE PROBLEMS -:~" •• ~

'LtllST~T'ONS OF OBJECTIVE QUESTIONS

~:;~II~~~IIV ~ ;~d~,iat~dI~iE>~:"'~. 37; '. The halogens. are:

strength of the acids?