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Mishra

for Class XI & XII, Engineering & Medical


Entrance and other Competitive Exams
Manoj Mishra

Chemistry at a Glance is part of a three book series, designed especially for


students aspiring to be future engineers and doctors. This book will help students
to prepare for engineering (JEE, BITSAT and Boards) and medical entrance
examinations (AIPMT and AIIMS). The book follows a crisp presentation approach
to simplify concepts to enable easier understanding and retention. It would act as
an indispensable tool to crack the examinations.

The other two books in these series are on physics and mathematics.

for Class XI & XII, Engineering & Medical


Entrance and other Competitive Exams

Manoj Mishra
Cover image: Shutterstock.com www.pearson.co.in

Size: 165x229mm Spine: 13mm ISBN : 9789332522077 Title Sub Title Edition Authors / Editors Name With CD Red Band Territory line URL Price mQuest
Chemistry
at a Glance

Manoj Mishra
B. Tech (Chemical Engineering)

'HOKL‡&KHQQDL

Chemistry at a Glance Final.pdf 1 4/1/2014 12:26:01 PM


Copyright © 2014 Dorling Kindersley (India) Pvt. Ltd

No part of this eBook may be used or reproduced in any manner whatsoever without the
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publisher reserves the right to remove any material in this eBook at any time.

ISBN 9789332522077
eISBN 9789332537378

Head Office: 7th Floor, Knowledge Boulevard, A-8(A), Sector 62, Noida 201 309, India
Registered Office: 11 Community Centre, Panchsheel Park, New Delhi 110 017, India

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Contents

Preface v
Acknowledgements vi

1. Chemical Arithmetic ������������������������������������������������������������������������������������������������������������������������������ 1�1-1�8


2. Atomic Structure ����������������������������������������������������������������������������������������������������������������������������������� 2�9-2�23
3. Gaseous State ��������������������������������������������������������������������������������������������������������������������������������������� 3�24-3�31
4. Thermodynamics �������������������������������������������������������������������������������������������������������������������������������� 4�32-4�43
5. Chemical Equilibrium ������������������������������������������������������������������������������������������������������������������������ 5�44-5�49
6. Ionic Equilibrium �������������������������������������������������������������������������������������������������������������������������������� 6�50-6�62
7. Solution and Colligative Properties �������������������������������������������������������������������������������������������������� 7�63-7�73
8. Solid State ��������������������������������������������������������������������������������������������������������������������������������������������� 8�74-8�85
9. Chemical Kinetics ������������������������������������������������������������������������������������������������������������������������������� 9�86-9�95
10. Electrochemistry ���������������������������������������������������������������������������������������������������������������������������� 10�96-10�109
11. Nuclear Chemistry ���������������������������������������������������������������������������������������������������������������������� 11�110-11�118
12. Surface Chemistry ���������������������������������������������������������������������������������������������������������������������� 12�119-12�137
13. Periodic Classification ����������������������������������������������������������������������������������������������������������������� 13�138-13�140
14. Chemical Bonding ���������������������������������������������������������������������������������������������������������������������� 14�141-14�155
15. S-Block Elements ������������������������������������������������������������������������������������������������������������������������� 15�156-15�161
16. P-Block Elements ������������������������������������������������������������������������������������������������������������������������� 16�162-16�182
17. D- and F-Block Elements�������������������������������������������������������������������������������������������������������������� 17�183-17�191
18. Metallurgical Extraction ������������������������������������������������������������������������������������������������������������� 18�192-18�212
19. Coordination Compounds �������������������������������������������������������������������������������������������������������� 19�213-19�231
20. Salt Analysis ���������������������������������������������������������������������������������������������������������������������������������� 20�232-20�244
21. Nomenclature of Organic Compounds ������������������������������������������������������������������������������������ 21�245-21�266
22. Isomerism ������������������������������������������������������������������������������������������������������������������������������������ 22�267-22�277
23. General Organic Chemistry ������������������������������������������������������������������������������������������������������ 23�278-23�289
24. Organic Reactions������������������������������������������������������������������������������������������������������������������������ 24�290-24�341
25. Biomolecules �������������������������������������������������������������������������������������������������������������������������������� 25�342-25�353
26. Polymer ���������������������������������������������������������������������������������������������������������������������������������������� 26�354-26�362
27. Analytical Text of Organic Compounds ���������������������������������������������������������������������������������� 27�363-27�370

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Preface

Although excellent books in chemistry are available for teachers and students, but there is a need for
a book that serves the demand of competitive examinations. In examinations like JEE-Main,
JEE-Advanced, AIIMS and other PMTs, students face fresh problems and complexities that undermine
their confidence. Therefore, I have tried my best to offer solutions to students and inspire confindence
through this book.
The main feature of this book is lucid explaination of concepts, simple language and inclusion
of frequently-asked questions from NCERT syllabus.
All the suggestions for improvement are welcome and shall be gratefully acknowledged�

—Manoj Mishra

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Acknowledgements

I am grateful to Pearson Education, for showing their faith in me, and for providing me an opportunity to
transform my years of teaching experience and knowledge into the present book, Chemistry at a Glance�
I would like to thank all my colleagues and my friends, for their valuable criticism, support and advise,
without which this work could not be completed� It's my pleasure to acknowledge all my students who
gave me inspiration for writing this book� I wish to thank my parents and all my family members, for their
support and cooperation in bringing out this book� I also thank my computer operators and managers, for
their hardwork and dedication in completing this task� I extend my special thanks to my elder brother
Sanjay Mishra, and Janmejai Tiwari who have motivated and inspired me for writing this book�

—Manoj Mishra

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ChemiCal
Chapter 1
arithmetiC

1.1 Mole ConCept

The ‘mole’ in Latin means heap or mass or pile. A mole is a collection of atoms or molecules or ions whose
total weight in grams is equal to the atomic weight of an element or molecular weight of a compound or
formula weight of an ion respectively.
Equal number of mole of different elements contains equal number of atoms. Therefore, it is
convenient to express amounts of the elements in terms of moles. The concept of mole is based upon
Avogadro’s hypothesis.
Avogadro’s hypothesis: Under similar conditions of temperature and pressure, equal volumes of all
gases contain equal number of molecules and hence equal number of moles.
e.g., v µ n if P and T are constant
v
v = kn at STP k= = 22.4 litres/mole
n
Standard molar volume: Volume of 1 mole of gas at STP is called standard molar volume. Numerically,
it is equal to 22.4 litres.

1.1.1 Application of Avogadro vs Hypothesis


1. Determination of Atomicity: Atomicity means number of atoms present in one molecule of an
elementary gas, e.g., H2, N2 and O2 have atomicity of 2 while noble gases have atomicity of 1 etc.
However, atomicity is not defined for a compound.
2. Relationship between molecular mass and vapour density: The vapour density of any
gas is the ratio of densities of the gas and hydrogen under similar conditions of temperature
and pressure.
ρgas Mol. mass
=
VD = .
ρ H2 2
Avogadro number: The number of atoms of carbon present in 12 g of C–12 has been found
experimentally to be 6.02 × 1023. This number is also known as Avogadro’s number.

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1.2 Chemistry at a Glance

1.1.2 Different Ways of Expressing Mole


Weight in gram
(i) Number of g mole or g molecule or mole of molecule =
Molecular weight
Number of molecule
=
Avogadro number (N A )
Weight in gram Number of atoms
(ii) Number of g mole or g atom or mole of atoms = =
Atomic weight Avogadro number (N A )
Volume of gas at NTP Number of molecules
(iii) Number of moles of gases = =
Standard molar volume Avogadro number (N A )

1.2 lAWS oF CHeMICAl CoMBInAtIon

Formation of chemical substances occurs through certain rules. These rules are called law of chemical
combination.
(a) Law of conservation of mass: This law was given by Lavoisier in 1774. It is also known as law of
indestructibility of matter.

A + B → C + D
t=0 wA wB 0 0
y = tcomp 0 0 wC wD

from law of conservation of mass, wA + wB = wC + wD


The more generalized form of law of conservation of mass is the principle of atomic conservation.
Principle of atomic conservation (POAC): According to this principle during a chemical
change atoms remain conserved and if atoms remain conserve, then mole of atom will also be
conserved.
i.e., number of atoms of an element in a reactant = number of atoms of that element in a product.
⇒ Mole of atoms of element in a reactant = mole of atoms of that element in a product.
e.g., if we consider the decomposition of KClO3
KClO3(s) → KCl(s) + O2(g)
If we want to relate amount of KClO3 with amount of O2, then we apply POAC for O atom
Mole of atom of O in KClO3 = Mole of atom of O in O2.
⇒ 3 × mole of KClO3 = 2 × mole of O2
WKClO3 WO2
⇒ 3× =

MKClO3 M O2

Advantages of POAC over other methods:


1. POAC can be applied even in an unbalanced reaction.
2. POAC can be applied in those cases where all reaction steps and their sequence are not given in
the problem.
(b) Law of definite or constant proportion: ‘A chemical compound always contains the same
elements combined together in fixed proportion by mass,’ i.e., chemical compound has a fixed

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Chemical Arithmetic 1.3

composition and it does not depend on the method of its preparation or the source from which
it has been obtained. It is observed that C and O are always combined in the ratio of 3:8. to
form CO2.

Note:
This law is not followed for isomers.

(c) Law of multiple proportions: This law was given by Dalton in 1808. According to this law,
‘if two elements combine to form more than one compound, then the different masses of one element
which combine with a fixed masses of the other element bear a simple ratio to one another.’
N and O combine to form five products as tabutated hereunder.

N O Simple ratio
N2O 28 parts 16 parts 1
N2O2 28 parts 32 parts 2
N2O3 28 parts 48 parts 3
N2O4 28 parts 64 parts 4
N2O5 28 parts 80 parts 5

The masses of oxygen which combine with same mass of nitrogen in the five compounds bear a
ratio of 1:2:3:4:5.
(d) Law of reciprocal proportions: This law was given by Richter in 1794. According to this
law, ‘when definite mass of an element A combines with two other elements B and C to form a
compound, their combining masses are in same proportion or bear a simple ratio to the masses of B
and C which combine with a constant mass of A.’
e.g., Na, H and Cl

+
D+ $
+

1
&
O

1D % &O &
1D&O

when Na and Cl combine with 1 part of hydrogen, then the ratio of their weight will be some whole
number multiple of ratio in which they combine themselves.
(e) Law of gaseous volumes: ‘Gases react with each other in the simple ratio of their volumes and if
the product is also in gaseous state, the volume of the product also bears a simple ratio with the
volume of gaseous reactants, when all volumes are measured under similar conditions of temperature
and pressure.’
N 2(g) + 3H2(g) 
→+ 2NH2(g)
Example: 1 volume 3 volume 2 volume
1 : 3 : 2

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1.4 Chemistry at a Glance

1.3 teRMS USeD In StoICHIoMetRY

(a) Limiting reactant: Reactant that is present in the smallest stoichiometric amount.
or
If two or more reactants are mixed and if the reaction were to proceed according to the chemical
equation to completion whether it does or not, the reactant that would first disappear is termed as
the limiting reactant.
2H2(g) + O2(g) → 2 H2O(v)

Moles before reaction 10 7 0


Moles after reaction 0 2 10

The reaction stops only after consumption of 5 moles of O2 as no further amount of H2 is left to react
with untreated O2. Thus, H2 is a limiting reagent in this reaction.
(b) Per cent Yield: The amount of product obtained by assuming that the reaction goes cleanly and
completely is called theoretical yield. The actual yield of a product is the amount present after sepa-
rating it from other products and reactants and purifying it. It is always less than the theoretical yield.
Actual yield
per cent Yield = × 100
Theoretical yield

1.4 lAW oF CHeMICAl eqUIvAlenCe

During a chemical change, number of gram equivalent of reactants and products involved are
always equal.

A + B C + D
wA wB wC wD
EA EB EC ED

Amount of substance in gram


⇒ Number of gram equivalent of a substance = .
Equivalent mass of the substance

wA wB wC wD
From law of chemical equivalence, = = =
E A E B EC E D

1.5 eqUIvAlent MASS

Equivalent mass or chemical equivalent: The number of parts by mass of the substance which
combine or displace directly or indirectly 1.008 parts by mass of hydrogen or 8 parts by mass of oxygen or
35.5 parts by mass of chlorine or 108 parts by mass of silver.
Relation between atomic mass, equivalent mass and valency:
Atomic mass
Equivalent mass = ; Atomic mass = equivalent mass × valency
n

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Chemical Arithmetic 1.5

Atomic weight Molecular weight


Equivalent weight of element = ; Compound =
Valency Valency factor
Molecular weight Molecular weight
Acid = ; Base = ;
Basicity Acidity
Formula weight Molecular weight
Ion = ; Acid salt =
Charge Replacable H-atoms

1.6 MetHoD oF DeteRMInIng eqUIvAlent WeIgHt


(i) Hydrogen displacement method: This method is used for metals which react with an acid to
evolve hydrogen gas. Equivalent weight of the metal is the weight of the metal which displaces
1.008 g of H2 or 11200 c.c. of H2 at STP.
(ii) Oxide formation or reduction of the oxide method: In this method, a known weight of the metal
is converted into its oxide directly or indirectly. Knowing the weight of the metal oxide formed, the
weight of oxygen combined can be calculated. Alternatively, a known weight of the metal oxide may
be reduced to metal whose weight is determined.
Equivalent of the metal is the weight of the metal which combines with 8 g of oxygen.
(iii) Chloride formation method: A known weight of the element is convered into its chloride
directly or indirectly whose weight is determined.
Equivalent weight of element is the weight of the elements which combines with 35.5 g of
chlorine.
(iv) Metal displacement method: This method is based upon the fact that a more electroposi-
tive metal displaces a less electropositive metal from its salt and one gram equivalent of the
Weight of metal added
metal added displaces one gram equivalent of the metal. Hence,
Weight of metal displaced
Equivalent weight of metal added
=
Equivalent weight of metal displaced
(v) Double decomposition method: For a reaction of the type
AB + CD → AD ↓ + BC
(e.g., AgNO3 + NaCl → AgCl ↓ + NaNO3)
Weight of AB taken Equivalent weight of AB
Weight of AD formed Equivalent weight of AD
Equivalent weight of A + Equivalent weight of B
=
Equivalent weight of A + Equivalent weight of D
Knowing the equivalent weights of any two radicals out of A, B and D, that of the third
can be calculated.

1.7 MetHoDS oF DeteRMInIng AtoMIC WeIgHt

Dulong and petit’s method: According to dulong and petit’s law, for solid elements (except Be,
B, C and Si),

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1.6 Chemistry at a Glance

Atomic weight × Specific heat = 6.4 approx.


6.4
\ Approx. atomic weight =
Sp. heat
Exact atomic weight = Equivalent weight × Valency
Approx. atomic weight
\ Valency =
Equivalent weight

Vapour density method: If we consider a chloride of formula XCln with vapour density D, then
2×D
Valency (n) =
E x t 35.5
⇒ Ax – n × Ex

1.8 eMpIRICAl AnD MoleCUlAR FoRMUlA

Empirical formula: It is the simplest formula of a compound which gives the simplest whole number
ratio of the atoms of the various elements present in one molecule of the compound, e.g., empirical
formula of glucose (C6H12O6) is CH2O.
(i) Molecular formula: It is the actual formula of a compound which gives the actual number of
atoms of various elements present in one molecule of the compound, e.g., molecular formula of
glucose is C6H12O6.
(ii) Relationship between empirical formula and molecular formula
Molecular formula = n × empirical formula where n is any integer such as 1,2,3 ......etc.
Molecular mass
n=
Empirical formula mass
(iii) Calculation of empirical formula mass: It is obtained by adding the atomic masses of the various
atoms present in the empirical formula.
(iv) Calculation of molecular mass
Molecular mass = 2 × Vapour density (VD)
Calculation of empirical formula: First calculate percentage of oxygen = 100 – Sum of percentages of
all other elements, then EF is calculated through the following steps:

Element Percentage Relative number of atoms Simplest Simplest whole


% age atomic ratio number ratio
=
Atomic mass

1.9 volUMetRIC AnAlYSIS


It is a method which involves quantitative determination of the amount of any substance present in a
solution through volume measurements. For the analysis, a standard solution is required. The purpose of
any titration is to make a non-standard solution standard or for identification of an unknown compound.
All volumetric calculations are based upon law of chemical equivalence.
Different types of titrations are possible which are summarized as follows:

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Chemical Arithmetic 1.7

(i) Redox titrations: To determine the strength of oxidizing agents or reducing agents by titration
with the help of standard solution of reducing agents or oxidizing agents.
K 2Cr2O7 + 4H2SO4 → K 2SO4 + Cr2 (SO4 )3 + 4H2O + 3[O]
[2FeSP4 + H2SO4 + O → Fe2 (SO4 )3 + H2O]× 3
Examples:
6FeSO4 + K 2Cr2O7 + 7H2SO4 → 3Fe(SO4 )3 + K 2SO4 + Cr2 (SO4 )3 7H2O
Number of g equation of oxidizing agent used = Number of g equation of reducing agent used
(ii) Acid–base titrations: To determine the strength of acid or base with the help of standard
solution of base or acid.
Example: NaOH + HCl → NaCl + H2O and NaOH + CH3COOH → CH3COONa + H2O, etc.
Solution required to bring about the completion of the reaction with a measured volume of the
unknown solution.
N ×V
Simple titration N1V1 = N2V2, \ N1 = 2 2
V1
Back titration: Back titration is used to find the percentage purity of the impure substance.
The g equation of substance under estimation = (N1V1 – N2V2)
Double titration: Mixture of NaOH and Na2CO3 in a solution:
For Same beaker problem

$FLGZLWK $FLGZLWK
SKHQROSKWKDOHLQ PHWK\ORUDQJH
YROXPH YROXPH
UHTXLUHG 9 1D2+ UHTXLUHG 9
1D&2

NV1 ≡ Meq of NaOH + meq of 1/2


Na2CO3 NV2 ≡ Meq of 1/2 Na2CO3
For separate beaker problem
$FLG
$FLGZLWK
ZLWKS+
PHRUDQJH

0L[WXUH 0L[WXUH

NV1 ≡ Meq of (NaOH + 1/2 Na2CO3)


NV2 ≡ Meq of (NaOH + Na2CO3)

1.10 volUMe StRengtH oF H2o2


Hydrogen peroxide is highly reactive and unstable, and hence, it is packed and sold in the form of its aque-
ous solutions. The concentration of such solutions is expressed as ‘volume strength’.
v
\ Molarity of solution, (M) =
11.2
v
⇒ Normality of solution, (N) =
5.6
17v
⇒ Strength of solution
5.6

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1.8 Chemistry at a Glance

1.11 peR Cent StRengtH oF oleUM

Mixture of H2SO4 and SO3 is called oleum. It is also known as fuming H2SO4. Concentration of oleum
sample is expressed in terms of per cent strength of oleum.
X per cent of oleum means 100 g of oleum sample on dissolving in water that produces x g of H2SO4.
H2SO4 + SO3 H2SO4
+ H2O  →
100 − y y xg
 
100 g

 98  18
⇒ X − 100 =y  − 1  =y ×
 80  80
(X − 100) × 80 (X − 100) × 40
=⇒ y =
18 9
(X − 100) × 40
\ per cent of free SO3 in oleum =
9

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atomiC StruCture
Chapter 2
2.1 Dalton’s atomic theory

This theory was proposed by John Dalton in 1803. The important features are listed
below:
(i) Atom is the basic unit of all the elements and molecules.
(ii) Atom is indivisible.
(iii) It can neither be created nor be destroyed.
(iv) Atoms of different elements differ in terms of their atomic masses due to which their properties
differ from each other.

2.2 Discovery of cathoDe anD anoDe rays

Cathode rays were discovered by William Crookes with the help of a discharge tube, which was invented
by Julius Plucker.

*DVDWORZ3 7RYDFXXPSXPS

&DWKRGH $QRGH
± 

&DWKRGH5D\V

+LJKYROWDJH
'LVFKDUJHWXEH

• Colour of light depends upon the nature of a gas in the discharge tube.
• The value of e/m for cathode rays = 1.76 × 108 coulombs/gm.
• The fluorescence was caused due to the bombardment of the walls of the tube by rays emanating
from cathode. So, they are called as cathode rays.

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2.10 Chemistry at a Glance

Properties of cathode rays:


(i) They travel in a straight line.
(ii) They have heating effect.
(iii) They consist of material particles because they can rotate light paddle wheel.
(iv) They are deflected towards +ve plate when an electric field is applied. It shows that they are –vely
charged.
(v) When a magnetic field is applied perpendicular to the path of cathode rays, they get deflected in the
direction expected for –ve particles.
(vi) They can ionise the gas through which they pass.
(vii) They can produce X-rays.
(viii) They can penetrate through thin metal foils.
(ix) The e/m ratio for the particles in the cathode is independent of the nature of the gas taken in the
discharge or the nature of the cathode.
Anode or cathode rays: Anode rays were discovered by Goldstein in 1886. He used a perforated cath-
ode in the discharge tube.
*DVDWORZ3 7RYDFXXPSXPS

&DWKRGH  $QRGH
± ± 
 ±
$QRGH
UD\V

+LJKYROWDJH
'LVFKDUJH7XEH

For anode rays, e/m = 9.58 × 104 coulombs/g.


Properties of anode rays:
(i) They travel in a straight line.
(ii) They show heating effect.
(iii) They consist of material particles.
(iv) In an electric field, they are deflected towards –ve charged plate. Hence, they are positively charged.
(v) In a magnetic field, they are deflected in the direction expected for +ve particles.
(vi) They can ionize the gas through which they pass.
(vii) They can produce X-rays.
(viii) They can penetrate through thin metal foils.
(ix) e/m ratio of anode rays is independent from the nature of anode but it depends upon the nature of
gas taken in the discharge tube.

2.2.1 Determination of the Ratio of Charge to Mass (e/m) of Electron


When a charge particle of charge (q) and mass (m) moves through an electric field region of intensity (E),
q 2× v2
then specific charge of particle = , where v is velocity of particles, x is vertical deflection between
m E2

Chemistry at a Glance Final.pdf 16 4/1/2014 12:26:02 PM


Atomic Structure 2.11

E
electrical plate and l is length of electrical region with intensity (E) velocity of particle (V) = . Where B
B
 q  2×E
is magnetic field intensity and specific charge   = 2 2 .
m B 


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±TPĺY

2.3 millikan’s oil Drop experiment

This experiment was performed by R. E. Millikan in 1909 for the determination of charge on a particle. If
a spherical oil drop is moving with constant velocity (v) through air with coefficient of viscosity (h), then
9ηv
radius of oil droplet r = . However, when thin oil droplet is passed through an electric field,
2(ρ − ρ0 )

18π η3 v 3
then charge on oil drop q =
E 2(ρ − ρ0 )g

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e= ∵ q = ne
nE 2(ρ − ρ0 )g

S. No. Fundamental Particles Mass Charge Discoverer


1. Electron (e )–
9.1 × 10
–31
kg –1.6 × 10 C–19
J. J. Thomson
2. Proton (P) 1.672 × 10 –27
kg +1.6 × 10 C–19
Goldstein
3. Neutron (n) 1.675 × 10 –27
kg 0 Chadwick

Note:
In this experiment X-rays are used to ionize the molecule of air so that electrons freed from air molecule may stick to oil
droplets to make droplets electrically sensible.

Chemistry at a Glance Final.pdf 17 4/1/2014 12:26:02 PM


2.12 Chemistry at a Glance

2.4 Discovery of atomic number

He observed that the frequency of a particular spectral line gradually increased with the increase of atomic
mass of the element. But it was soon realized that the frequency of the particular spectral line was more pre-
cisely related with serial number of the element in the periodic table which he termed as atomic number (z).
— —
√n = a(z – b); where n is frequency of spectral line, a is slope of line in plot between √n and z and

ab is intercept made by line on √n axis.
The term atomic number was given by H. G. J. Moseley in 1912–1913. To perform this, he
considered gas discharge tube in which he took variety of metal targets (anode) starting from aluminium
metal and ending with gold.
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2.5 rutherforD’s atomic moDel

2.5.1 Rutherford’s Experiment (1908–1909)

Observation:
(i) Most of the a particles passed through the metal foil straight without any deflection.
(ii) Some of them (1 per cent) got deflected at different angles.
(iii) About 1 out of 8000 a particles got deflected at 180°.
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2.5.2 Rutherford’s Nuclear Atomic Model (1911)


(i) Most of the inner part of an atom is empty.
(ii) All protons are accumulated at the centre of the atom in a very small volume called nucleus.
Nucleus is a highly charged body which contains almost entire mass of the atom.
(iii) The electron are present in the extra-nuclear space and are not stationary but move with high
velocity under the influence of the centripetal force (CPF). Due to this motion, the centrifugal
force (CFF) is also developed which according to Rutherford counter balances the CPF. Therefore,
electron follows a circular path called orbit.

Chemistry at a Glance Final.pdf 18 4/1/2014 12:26:02 PM


Atomic Structure 2.13

2.5.3 Significances of Rutherford’s Atomic Model


2.5.3.1 Calculation of distance of closest approach or effective nuclear radius

Effective nuclear radius or distance of closest approach is defined as that radius of the sphere or
spherical region around the nucleus from where the a-particles gets deflected.
4ze2 ze2 1 2ze2
\ Distance of closest approach,
= d0 = 2
= 2
4 πε0mv πε0mv 4 πε0 KE

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=H
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f

2.5.3.2 Calculation of radius of nucleus

In an atom, the radius of nucleus is proportional to the cube root of the number of nucleons within it.
R = R0 A1/3cm; where R0 = 1.33 × 10–13cm,
A = number of nucleons or mass number, and
R = radius of the nucleus.

2.5.3.3 Number of a particles striking at an angle q


z2
N(θ) ∝ 4
; N(q) = Number of a-particles per unit area that reach the screen at a scattering
sin (θ / 2)
angle of q.

2.5.4 Demerits of Rutherford’s Atomic Model


Clark Maxwell’s Theory: According to Clark Maxwell, when a moving charged particle is subjected to
acceleration, it always loses energy in the form of electromagnetic radiations.

Electron

Nucleus

1. In Rutherford’s model, an electron moves in circular orbits. Being a charged particle, it should lose
energy as it is continuously subjected to acceleration. If this happens, e- should start moving in
smaller orbits and should finally hit the nucleus. This will make an atom unstable. However, an atom
is stable suggesting that the Clark Maxwell law is not valid.
2. The spectrum was found to be discontinuous.
3. What is the cause of origin of spectrum?

Chemistry at a Glance Final.pdf 19 4/1/2014 12:26:02 PM


2.14 Chemistry at a Glance

2.6 Quantum theory

Quantum theory was given by Max Planck in 1901. He developed this theory to explain the mode of
absorption and emission of energy by black bodies. Later on, Einstein said that this theory is of general
applicability. The important points are summarized hereunder.

Note:
Einstein gave another name photon for quanta. One photon is equal to hn.
(i) The absorption or emission of energy is a discontinuous process.
(ii) The energy is absorbed or emitted in the form of massless bundles. The energy associated with each bundle is
known as one quanta and is given by E = hn; where h = Planck’s constant; n = frequency of radiation absorbed
or emitted.
(iii) The energy can never be absorbed or emitted in fractions. It is absorbed or emitted either as hn or its +ve integral
multiples, E = nhn; (where n = 1, 2, 3,......).

2.7 bohr’s atomic moDel

2.7.1 Bohr’s Atomic Model


In 1913, Bohr applied quantum theory on atoms and gave the following postulates.
1. Electrons follow a circular path called orbit.
2. An atom may contain many circular orbits. Each orbit is associated with quantized (i.e., fixed)
amount of energy. Some orbits are of special kind and are known as ‘stationary states’. An electron
prefers to be in the stationary state because then its energy does not change.
3. The angular momentum of an electron moving in a circular orbit is quantized and is given by
h
mvr = n ; where h = Planck constant, n = Principal quantum number.

The angular momentum generates orbital energy of an electron. Since mvr is quantized the orbital
energy of an electron will also be quantized (i.e., fixed) and different for different orbits.
4. An electron may change its energy by changing its original circular orbit. This electron may achieve
by absorbing or emitting a quantized amount of energy.

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Chemistry at a Glance Final.pdf 20 4/1/2014 12:26:02 PM


Atomic Structure 2.15

2.7.2 Significances or (Merits) of Bohr’s Atomic Model

2.7.2.1 The radius of the orbits or the size of the atom

 (4 πε0 )h 2  n2 n2
=r = 2 2 
xa 0 ; where n = 1, 2, 3, ....
 4 π me  z z
where a0 is Bohr radius having the value 0.529 Å.

2.7.2.2 Velocity of the electron

 2πe2  z z
=Vn =  V0 ; where V0 is Bohr velocity having the value 2.18 × 106 m/second.
 4 πε h
0  n n

2.7.2.3 Frequency of revolution

 me 4  z 2 z2 z2
f=   = f0= 3= 6.56 × 1015 3 revolution/second
 4ε h  n
2 3 3
n n
 0 

2.7.2.4 Energy of the electron

Let Ek and Ep be the kinetic energy and the potential energy respectively of the electron in the nth orbit.
Then, the total energy is equal to the sum of Ek and Ep,
 2π2me 4  z 2  z2  J  z 2  eV
i.e., En = E k + E p −  2 2 2
= −2.18 × 10−18  2  =
−13.6  2  .
 (4 πε0 ) h  n  n  atom  n  atom
3.827 × 10–20 cal = 1eV = 1.602 × 10–19J
1 cal = 4.184 J = 2.61 × 1019 eV
1 ev/atom = 96.485 kj/mol

2.8 electronic spectrum

(i) Emission spectra: When the light emitted from some source is directly passed on to a prism and then
observed on a photographic film after dispersion, the resultant spectrum is called emission spectrum.
(ii) Types of emission spectra: If the source of light emits white light, e.g., sun or bulb, the spectrum
consists of seven bands of colours (VIBGYOR) lying continuously and the specturm is called con-
tinous spectrum. If some volatile salt is placed in a Bunsen flame or electric discharge is passed
through a gas at low pressure and the light emitted is resolved through a prism, the spectrum con-
sists of a number of bright lines against a dark background and is called line spectra or atomic
spectra.
(iii) Absorption spectra: When white light is passed through the solution or vapours of a chemical
substance and then analysed by the spectroscope, some dark lines are observed in the otherwise
continuous spectrum at the background. The spectrum thus observed is called absorption spec-
trum. These dark lines are observed at the same wavelengths where coloured lines were obtained in
the emission spectrum of the same substance.

Chemistry at a Glance Final.pdf 21 4/1/2014 12:26:02 PM


2.16 Chemistry at a Glance

(iv) Every element gives a characteristic line spectrum differing from line spectra of all other elements.
Hence, it is like a finger print of the element.
(v) In case of atoms, the energies are emitted or absorbed during electronic transition only thereby
giving lines in the spectrum. Hence, their spectrum is called line spectrum or atomic spectrum.
In case of molecules energies are absorbed for rotational, vibrational and electronic transition
thereby producing groups of lines called bands and their spectrum is called band spectrum.

2.8.1 Line Spectrum of Hydrogen


(i) The line spectrum of hydrogen consists of Lyman, Balmar, Parchen, Bracpet, Pfund and Humphrey
series. The first series lies in the ultraviolet region, the second in the visible region, the next two in
the infrared region and the last two in the far-infrared region.
(ii) Rydberg’s formula for calculation of wave number of lines in the hydrogen spectrum is R and is
called Rydberg constant and its value is 109677 cm–1.
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Note:
1. Total number of spectral lines obtained from any energy laval n to ground state = n(n – 1)/2.
( n − n1 + 1)
2. Total number of spectral line between any two energy state n1 and = n2 ( n2 − n1 ) 2 .
2
3. In any series, first line = transition from (n1 + 1) → n1, also called a-line, second line = transition from
(n1 + 2) → n1, also called b-line and so on. e.g., In Lyman series a-line = 2 → 1; b-line = 3 → 1; g-line = 4 → 1.
Determination of wavelength of transition:
When the electron in the initial stationary orbit of PQN (n1) jumps to the another stationary orbit of
PQN(n2), then the difference in energy
2π2me 4 z 2  1 1 
∆E =E n 2 − E n 1 =−  − 
(4 πε0 )2 h 2  n22 n12 
2π2me 4 z 2  1 1  hc
∆E =  − = = hc ν ; where ν , is wave number.
(4 πε0 )2 h 2  n12 n22  λ
1  1 1 
⇒ ν= = R H z 2  2 − 2  is Rydberg’s equation.
λ  n1 n2 
me
where 2 3
= 1.097373 × 107 m–1, is known as Rydberg’s constant.
8 hc

Chemistry at a Glance Final.pdf 22 4/1/2014 12:26:02 PM


Atomic Structure 2.17

Experimental value of R = 1.096768 × 107 m–1, is known as Ritz constant.


Thus, there is very good agreement between the Rydberg and Ritz constants and this also support the
postulates of Bohr.

2.8.2 Determination of Ionization Potential (IP) or


Ionization Energy (IE)
Ionization energy (IE) or ionization potential is defined as the amount of energy required to remove the
most loosely bound electron from an isolated gaseous atom of an element. The lesser the ionization
energy, the greater is the ease of the formation of a cation.
In an atom there are infinite number of orbits. To remove an electron from an atom means to send
electron in infinite number of orbits i.e., n2= ∞.
R H hcz 2 2.18 × 10−18 z 2 J 13.6z 2 eV
⇒ IP or IE = E = 2
= 2
=
n1 n1 atom n12 atom

2.9 Demerits of bohr’s atomic moDel

1. When the energy of electron present in a multielectron system was determined with the help
of Bohr’s postulate, it was found to be not in agreement with experimental values. It means that
Bohr theory is applicable only for the system containing only one electron. e.g., H, He+,
Li++, etc.
2. According to Bohr, an electron follows a fixed path, i.e., a circular orbit. If this is true, then po-
sition and velocity both can be determined simultaneously with high degree of accuracy. This
is against the Heisenberg’s uncertainty principle, according to which an electron never follows
a fixed path.
3. Bohr’s theory failed to explain the directional nature of a covalent bond and hence the shape of the
covalent molecules.
4. Bohr’s theory failed to explain the band (or fine) spectrum of hydrogen.
5. Bohr’s theory could not explain the splitting of lines of (Zeeman effect) and influence of an electric
field (Stark effect).

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2.10 photoelectric effect

Emission of an electron from a metal surface when exposed to light radiations of appropriate wavelength
is called photoelectric effect. The emitted electrons are called photoelectrons.

Chemistry at a Glance Final.pdf 23 4/1/2014 12:26:02 PM


2.18 Chemistry at a Glance

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According to Einstein: Theroy of photoelectric an effect maximum KE of ejected electron = ab-


sorbed energy – work function.
⇒ (KE)max = hn – f
1 1 
KEmax = hν − hν 0 = hc  −  ;
 λ λ0 
where n0 and l0 are threshold frequency and threshold wavelength respectively.

2.10.1 Work Function or Threshold Energy


It may be defined as the minimum amount of energy required to eject electrons from a metal surface. It is
represented by f. The energies of electrons liberated by light depend on the frequency of the light.

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2.10.2 Stopping Potential


The minimum potential at which the plate photoelectric current becomes zero is called stopping poten-
tial. If V0 is the stopping potential, then eV0 = h(n – n0).

2.10.3 Laws of Photoelectric Effect


(i) Rate of emission of photoelectrons from a metal surface is directly proportional to the intensity of
incident light.
(ii) The maximum KE of photoelectrons is directly proportional to the frequency of incident radiation;
moreover, it is independent of the intensity of light used.
(iii) There is no time lag between incident of light and emission of photoelectrons.
(iv) For emission of photoelectrons, the frequency of incident light must be equal to or greater than the
threshold frequency.
(v) The greater the work function of a metal, the more the energy is needed for an electron to leave the
surface and the higher the critical frequency for photoelectric emission to occur.

Chemistry at a Glance Final.pdf 24 4/1/2014 12:26:02 PM


Atomic Structure 2.19

Note:
−6
hc 1.240 ×10 1
λmin
= = m = λmin ∝
eV V V
The X-rays produced at a given accelerating potential V vary in wavelength but none has wavelength shorter than a
certain minimum value lmin. Increasing V decreases l min.

2.11 Duality of matter


Photoelectric effect phenomenon can be explained on the basis of particle nature of electron but it is not
possible to explain the interference and the diffraction phenomenon which are properties of wave.
In 1905, Einstein suggested that light has dual nature. By 1920, it has been suggested that the
matter has dual nature.
In 1924, De Broglie postulated that the electron also has dual nature, i.e., particle as well as wave.
He succeeded in deriving an expression which showed relationship between the wave and particle nature
of a moving electron.
h h h h
De Broglie wavelength: = λ = = =
mv p 2eVm 2mKE

2.12 heisenberg’s uncertainty principle

The position and velocity of a big particle can be determined simultaneously with high degree of
accuracy. However, this is not true for the tiny particles like electron, proton, neutron, etc. This principle
states that:
‘If we try to determine the position of a tiny particle accurately then there will be some uncertainty
associated with the determination of its velocity and if the velocity is known accurately then its position
will have some uncertainty’.
According to principle of optics, the accuracy with which the position of a particle can be measured
depends upon the wavelength of light used. The uncertainity in position is ±l. The shorter the wavelength
means higher the frequency and higher the energy. This high-energy photon on striking the electron
changes its speed as well as direction.
h h
∆x × ∆p ≥ and ∆x × ∆υ ≥
4π 4 πm

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Orbital: The small volume around the nucleus where the probability of finding an electron is maximum,
i.e., 90 to 95 per cent is known as orbital.

Chemistry at a Glance Final.pdf 25 4/1/2014 12:26:02 PM


2.20 Chemistry at a Glance

2.13 Wave mechanical moDel


The wave mechanical model is based on quantum mechanics which is developed independently by
Schrödinger and Heisenberg. In quantum mechanics, duality of matter is taken into consideration.
Important features of wave mechanical model:
(i) The exact position and velocity of e– cannot be determined simultaneously with high degree of
accuracy. However, electron is present in a 3-dimensional space around the nucleus where
probability of finding the e– is maximum. This space is called an orbital.
(ii) Each orbital possess an unique orbital wave function value, these values; are outcome of solution of
Schrödinger wave equation.
(iii) Many orbital wave functions are possible for an e–, therefore there exist many quantized energy
orbitals.
(iv) The wave function y is simply a function of coordinate of e– and has no physical significance as
such. However, y2 gives us the probability of finding e– at a point inside an atom.
(v) By finding y2 at different points around the nucleus in an atom we can predict the region of space
around the nucleus called orbital.
(vi) All the information about an electron is stored in its orbital wave function value and Schrödinger 
wave equation makes it possible to extract this information out of y.
Schrödinger wave equation: For an e– moving in 3-dimensional space around the nucleus.
Hy = Ey ; where H is a mathematical operator called Hamiltonian operator.
H = T + V; where T is kinetic energy operator and V is potential energy operator.
2 2 –
T=
− ∇ where V2 = Laplacian operator
2m
∂ 2 ψ ∂ 2 ψ ∂ 2 ψ 8 π2 m
+ + + 2 (E − V)ψ =
0
∂x 2 ∂y 2 ∂z 2 h

2.14 shape of orbital


The position and energy of an electron may be determined with the help of certain numbers called
quantum numbers. An electron is said to be identified or described or characterized when its position and
energy is known. For the complete description of an electron, we need help of the following four quantum
numbers.
(i) Principal quantum number (PQN) (Bohr).
(ii) Azimuthal quantum number or subsidiary quantum number or secondary quantum number or
angular momentum quantum number or orbital quantum number (Somerfield).
(iii) Magnetic quantum number (MQN) (Lande).
(iv) Spin quantum number (Uhlenbeck and Goudsmith).
Principal quantum number represents the main shell, azimuthal quantum number represents the
number of subshells present in the main shell, magnetic quantum number represents the number of
orbitals present in the subshell and spin quantum number tells the direction of spin of the electron, i.e.,
clockwise or anticlockwise. Further, principal quantum number tells about the size, azimuthal quantum
number about the shape and magnetic quantum about the orientation of the orbital. Also, principal
quantum number tells about the energy of the electron, whereas azimuthal quantum number tells about
the angular momentum of the electron.

Chemistry at a Glance Final.pdf 26 4/1/2014 12:26:02 PM


Atomic Structure 2.21

The values of quantum number are related to each other as follows:


n = 1, 2, 3, 4, ....
For a given value of n, l = 0 to n – 1
For a given value of l, m = –1 to +1 including ‘0’
For a given value of m, s = + 1/2, –1/2
Designation of the subshells:

Value of l Sub-shell
0 s
1 p
2 d
3 f

Thus, number of subshells in the nth shell = n


Number of orbitals in a subshell = 2l + 1
Number of orbitals in nth shell = n2
Radial probability distribution curves: Radial probability is R = 4pr2 dry2. The plots of R versus
distance from nucleus are as follows:

 
  
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SUGU\

 
  
 
  $  c
  
           
 c U c  c U c U c

In the plots of radial probability versus distance from the nucleus, number of peaks i.e., region of
maximum probability = n - l.
For example, 2s has two peaks, 3s will have 3 peaks, 2p has one peak, 3p has two peaks and so on.
Shapes of s, p and d-orbitals
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Chemistry at a Glance Final.pdf 27 4/1/2014 12:26:02 PM


2.22 Chemistry at a Glance

Spherical (radial) nodes and nodal planes


A spherical surface within an orbital on which the probability of finding the electron is zero is called a
spherical or radial node. The number of spherical or radial nodes in an orbital = ( n – l – 1).
For example, 1s orbital (n =1, l = 0) has no spherical node
2s orbital (n =2, l = 0) has one spherical node
2p orbital (n =2, l = 1) has no spherical node
3p orbital (n =3, l = 1) has one spherical node and so on.
A plane passing through the nucleus on which the probability of finding the electron is zero is called a
nodal plane. The number of nodal planes in an orbital = l for example
s orbital (l = 0) no nodal plane
p orbital (l = 1) one nodal plane
d orbital (l = 2) two nodal planes and so on.
Pauli’s exclusion principle: Pauli exclusion principle states that ‘No two electrons in an atom can have
the same set of four quantum number’ or ‘an orbital can have maximum two electrons and they must have
opposite spin.’
Aufbau principle
Aufbau principle states that ‘in the ground state of the atom, the orbitals are filled in order of their
increasing energies, starting with the orbital of lowest energy.’ The word aufbau is a German word which
means building up. The increasing order of energy and hence that of filling of orbitals is as follows:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5p, 6s, 4f, 5d, 6p...
This can be remembered from the adjoining diagram in which starting from the top, the direction of
arrows give the order of filling.

V

V S

S G
V

S G I
V
G
V S I

V S G

V S

Note:
In case of H-atom, the energies of atomic orbitals increase as follows:
1s < 2s = 2p < 3s =3p = 3d < 4s = 4p = 4d = 4f and so on.
i.e., subshells of the same main shell have equal energies.

Chemistry at a Glance Final.pdf 28 4/1/2014 12:26:02 PM


Atomic Structure 2.23

The order of energies and hence that of filling of orbitals can be calculated by (n + l) rule which states as follows:
(i) Orbitals are filled in order of increasing (n + l) values.
(ii) If two orbitals have the same (n + l) values, the orbital with lower value of n is filled first.

2.14.1 Hund’s Rule


Hund’s rule of maximum multiplicity states that ‘pairing of electrons in the orbitals belonging to the same
sub-shell (degenerate orbitals) does not take place till each orbital of that sub-shell has got one electron
each, i.e., is singly occupied Orbitals must have their electron with spin in the same direction (so that
repulsion is minimum and stability is maximum).
Half-filled and fully-filled electronic configurations are more stable because of (i) greater symmetry
and (ii) greater exchange energy.

2.15 electronic configuration of ion

First write the electronic configuration of a neutral atom. For cation, remove the number of electrons
equal to the units of +ve charge on the cation, starting from the outermost shell. For anion, add number of
electrons equal to the units of –ve charge on the anion.

2.16 Diamagnetic anD paramagnetic substances

2.16.1 Diamagnetic Substances ↿⇂ (Paired Spin)


Substances having all electrons paired are known as diamagnetic substances and their magnetism as
diamagnetism.
The magnitude of diamagnetism is very small because of cancellation of magnetic moment due
to spin motion and also due to quenching of orbital motion (nullified due to other atom’s orbitals
molecule).

2.16.2 Paramagnetic Substances ↿ (Parallel Spin)


All substances having one or more unpaired electrons are called paramagnetic substances and their
magnetism paramagnetism. The magnitude of paramagnetism is much higher than diamagnetism
because of full contribution of spin motion of the electron.
The magnitude of paramagnetism increases with increase of number of unpaired electrons.
In general, paramagnetic substances are more reactive than diamagnetic substances.
Magnetic moment of paramagnetic substances
=µ N(N + 2) BM (1 BM = 9.27 × 10–24 J/T); where N is the number of unpaired electrons.
(i) All paramagnetic substances except hydrogen also have some diamagnetism but converse is
not true.
(ii) Ion with unpaired electron in d or f orbitals will be coloured. For example Cu+ with electronic
configuration [Ar] 3d10 is colourless and Cu2+ with electronic configuration [Ar] 3d9 (one unpaired
electron in 3d) is coloured (blue).

Chemistry at a Glance Final.pdf 29 4/1/2014 12:26:03 PM


Chapter 3 Gaseous state

3.1 StateS of Matter


Matter exists in three states, viz. solid , liquid and gas. All the three phases can exist together at a particular
temperature and pressure, e.g., ice (s) water (l) water (g) vapour can exist together at 0.01°C and
4.58 mm pressure.

S. No. Solids Liquids Gases


1. Molecules are closely packed Molecules are less closely Molecules are sufficiently
packed apart from one another
2. Mutual forces of attraction are Mutual forces of attraction Mutual forces of attraction
the strongest are weaker than those in are almost negligible
solids
3. The density of solids is high The density of liquids is Gases generally have low
lower than that of solids but densities
is much higher than gases
4. The positions of molecules Molecules of a liquid Molecules of a gas have
in the cystal lattice are fixed have greater freedom of large rotatory, vibratory and
and hence solids do not have movement. They have some translatory motions
translatory or rotatory motion translatory and rotatory
but only possess vibratory motions in addition to the
motion vibratory motion
5. Molecules of a solid possess Molecules of a liquid have Gas molecules are most
lowest energy higher energies than that energetic
of solids
6. Solids have both a definite Liquids do not have definite Gases neither have definite
shape and a definite volume shape but have definite shape nor definite volumes
volumes
7. Solids possess least compress- Liquids have slightly higher Gases possess high
ibility and thermal expansion compressibility and thermal compressibility and thermal
expansion than those of expansion
solids

Chemistry at a Glance Final.pdf 30 4/1/2014 12:26:03 PM


Gaseous State 3.25

3.2 CharaCteriStiC ProPertieS of gaSeS


There are four parameters that can describe the characteristics of a gas completely.
(i) Amount of gas
(ii) Temperature (T)
(iii) Pressure (P)
(iv) Volume (V)

3.2.1 Unit of Volume


1 litre (1L) = 103 cm3 = 1 dm3 = 103 ml
1m3 = 103 dm3 = 106 cm3 =103 L

3.2.2 Pressure
Atmospheric pressure is measured with a barometer from the height of the mercury column that stands in
a tube filled with mercury and inverted into a trough containing mercury. P = ∫gh
p = density g = gravitational contant h = height of mercury in column

9DFXXP

0HUFXU\+J

K PP
$WPRVSKHULF
SUHVVXUH

Pressure of a gas is measured with a manometer and is equal to the difference in levels of Hg in the
two limbs with a closed limb manometer and is equal to atm pressure minus difference in levels in case of
an open limb manometer.
1atm = 76 cm of Hg = 760 mm of Hg = 760 torr
= 101,325 Pa or Nm–2
= 101.325 k Pa

Note:
Mercury is filled in barometer because it is the heaviest liquid and its thermal expansivity is minimum.

Chemistry at a Glance Final.pdf 31 4/1/2014 12:26:03 PM


3.26 Chemistry at a Glance

3.3 gaS LawS

3.3.1 Boyle’s Law


Robert Boyle in 1662 gave a relationship between volume and the pressure of gas which is known as Boyle’s
law. According to this law, ‘At constant temperature, the pressure of a given mass of a gas is inversely
proportional to the volume of a gas.’ It means that if we increase the pressure, volume will decrease and vice
versa. P ∝ 1/V (at constant temperature);
\ PV = Constant ..........(i)
Equation (i) shows that PV is a constant. It means that if we increase pressure, the volume will de-
crease in the same proportion and ultimately their product will remain constant.
P1V1 = P2V2
7!7 7!7
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7
3 7
7 7
7
7 7
9 9 ORJ9 3

3.3.2 Charle’s Law


At constant pressure and number of mole, the volume of a gas is directly proportional to the absolute tem-
perature, V µ T (n and P are constant)
V1 V2 V3
⇒ V/T = constant i.e. = = = ---; where T is temperature in Kelvin.
T1 T2 T3

3!3 3!3
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9W WDQT P Yv 3!3
SRODWLRQ 3 3
9 97 3 ORJ
3 3 9

 ƒ&  W ƒF
7 7 ORJ7

1
⇒ Vt = V0 (1 + αt) where α =
273.15
Changing origin to –273° C, we get a straight line passing through origin. Then at that scale
temperature T in K will be T = 273.15 + t.

3.4 gay LuSSaC’S Law or aMonton’S Law

Pressure of a given mass of a gas is directly proportional to its absolute temperature if its volume is kept
constant.
P1 P2 P3
\ = = = ... (At constant v and n)
T1 T2 T3

Chemistry at a Glance Final.pdf 32 4/1/2014 12:26:03 PM


Gaseous State 3.27

3.4.1 Avogadro’s Law


It states that under similar conditions of temperature and pressure equal volume of different gases contains
equal number of molecules and hence equal number of moles.
\ V α n (at constant P and T)
Where n is the number of moles of gases
\ V=k×n (k is constant)
V1 V2 V3
V/n = k or = = = ...
n1 n2 n3
Alternative form of Avogadro’s law, P/M = constant if P and T are constants.

3.4.2 Combined Law


It is the combined result of Boyle’s law and charle’s law,
PV P1V1 P2 V2
= cons tan t =
T T1 T2

3.5 ideaL gaS equation

Ideal gas equation is obtained by combining all the gas laws. Consider a gas having pressure P, temperature,
T and volume V.
For a gas having variable pressure, volume, temperature and number of mole;
PV PV
∝n ⇒ = R×n ⇒ PV = nRT
T T
where R = Universal gas constant and is same for all gases
\ PV = nRT
The above equation is called or ideal gas equation

Relationship between density and pressure of an ideal gas


w
If m is the mass of the gas and M is its molecular mass, then n =
M
Substituting this value of PV = n RT, we get
w w RT RT m
PV = RT or P = or P = d ; where d = density of the gases. Thus, density of the gas
M V M M V
is directly proportional to its pressure at constant temperature.

Nature of the gas constant, r


Value of the gas constant R in terms of different units
R = Work done per degree per mol.
R = 0.0821 litre atm K–1 mol–1 = 82.1 cm3 atm K–1 mol–1

Chemistry at a Glance Final.pdf 33 4/1/2014 12:26:03 PM


3.28 Chemistry at a Glance

= 8.314 JK–1 mol–1 = 8.314 k Pa dm3 K–3 mol–1


= 8.314 × 107 ergs degree–1 mol–1
= 1.987 ≈ 2 cal degree–1 mol–1

3.6 daLton’S Law of PartiaL PreSSure


‘If two or more gases which do not react chemically are enclosed in a vessel, then the total
pressure exerted by the gaseous mixture is equal to the sum of the partial pressures that each
gas would exert when present alone in the same vessel at the same temperature’. Mathematically
P = p1 + p2 + p3 +....
(i) Aqueous tension: The pressure exerted by the water vapour at a particular temperature is called
aqueous tension at that temperature. It depends only on temperature. Its value becomes atmospheric
pressure at boiling point of liquid.
(ii) Calculation of pressure of a dry gas from that of the moist gas: When a gas is collected over
water at t°C, it is moist. According to Dalton’s law of partial pressures.
Pmoist gas = Pdry gas + aq. tension (at t°C) or Pdry gas = P moist gas – aqueous tension (at t°C)
Partial prassure of watr vapour in air
Relative humidity: R.H.
= × 100
Saturated vapour pressure i.e., aq tension

3.7 aMagat’S Law of PartiaL VoLuMe


Amagat’s law of partial volumes: This law is similar to Dalton’s law of partial pressures. According to
this law, ‘the total volume of a mixture of non-reacting gases is the sum of their partial volumes where
partial volume of a gas is the volume occupied by that gas at the same temperature and at the pressure of
the mixture’. Mathematically VT = n1 + n2 + n3 +.....
Average molecular weight of a gaseous mixture:
∑ ni Mi
Mmix = ; where ni is the number of moles and Mi is the molecular weight of component i.
∑ ni

3.8 diffuSion and effuSion


‘Under similar conditions of temperature and pressure, the rates of diffusion of different gases are inversely
proportional to the square root of their densities’. Mathematically
r1 d2 M2
= = (∵ Molar Mass = 2 × Vapour Denisty)
r2 d1 M1
Volume of gas diffused Number of moleof gas diffused
Rate of diffusion = =
Time taken Time taken
Pressure of gas diffused Distance travelled by the gas
= =
Time taken Time taken
For the volumes diffused in the same time (t1 = t2)
V1 d2 M2
= =
V2 d1 M1

Chemistry at a Glance Final.pdf 34 4/1/2014 12:26:03 PM


Gaseous State 3.29

PA 0 N A
∎ For a gas effusing through a small hole of area A0 rate of effusion, r = where P is applied
2πMRT
pressure; NA is avogadro number; M is molecular mass of gas and T is applied temperature.
Difference between diffusion and effusion: Diffusion refers to the spreading of a gas throughout the
space or into a second gas or substance, whereas effusion refers to the escape of a gas through an orifice
(a tiny hole).

3.9 KinetiC theory of gaSeS


(i) Every gas is made up of a large number of extremely small particles called molecules. All
the molecules of a particular gas are identical in mass and size and differ in these from
gas to gas.
(ii) The molecules of a gas are separated from each other by large distances so that
the actual volume of the molecules is negligible as compared to the total volume
of the gas.
(iii) The distance of separation between the molecules is so large that the forces of attraction and
repulsion between them are negligible.
(iv) The force of gravitation on the molecules is also supposed to be negligible.
(v) The molecules are supposed to be moving continuously in different directions with different
velocities. Hence, they keep on colliding with one another (called molecular collisions) as well as on
the walls of the containing vessel.
(vi) The pressure exerted on the walls of the containing vessel is due to the bombardment of the
molecules on the walls of the containing vessel.
(vii) The molecules are supposed to be perfectly elastic hard spheres so that no ener-
gy is wasted when the molecules collide with one another or with the walls of the ves-
sel. The energy may however, be transferred from some molecules to the other
by collision.
(viii) Since the molecules are moving with different velocities they possess different kinetic energies.
However, the average kinetic energy of the molecules of a gas is directly proportional to the absolute
temperature of the gas.

3.9.1 Kinetic Gas Equation


PV = 1/3 display m n u2; where P = pressure of the gas, V = volume of the gas, m = mass of each
molecule, n = total number of molecules, Vrms = RMS velocity (RMS = root mean squans velocity)
Relationship between average KE and Absolute temperature
1 2 1 2 2 1 2 2
=PV =
mnVrms =MVrms . =MVrms KE
3 3 3 2 3
3 3
\ KE = PV = RT for 1 mol of an ideal gas
2 2
3R 3
=
KE = T kT = Average kinetic energy per molecule; where N is Avogadro’s number and
2N 2
k = R/N = Boltzmann constant.

Chemistry at a Glance Final.pdf 35 4/1/2014 12:26:03 PM


3.30 Chemistry at a Glance

3.10 VariouS SPeed terMS uSed for gaSeS

It is a plot of fraction of molecules versus the corresponding velocities at a particular temperature. This is
shown below alongwith the effect of temperature.

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77
9PS9PS

7
7

9PS 9PS 6SHHG

Most probable velocity (Vmp): This is the velocity possessed by the maximum fraction of the molecules
2RT
at a particular temperature. Vmp =
M

Root mean square (RMS) velocity (Vrms): It is the square root of the mean of the squares of the velocities

ν + ν + ν + ... + ν 2n
2
1
2
2
2
3 3RT 3PV 3P
of the molecules, i.e.,=
Vrms = = =
n M M P
Average velocity (Vav): It is the average of the different velocities of the molecules i.e.
ν1 + ν 2 + ν 3 + ... + ν n 8RT
=
Average velocity (n) = Vav = Vav =
n πM
Relationship between Vmp, Vav and Vrms:
Vav = 0.921 Vrms
Vmp = 0.816 Vrms
Vny : Vav : Vams = 1 : 1.128 : 1.224
At a given temperature, Vmp < Vav < Vrms

3.11 reaL gaSeS


A gas which obeys Boyle’s law, etc. or ideal gas equation (PV = nRT) under all conditions of temperature
and pressure is called an ideal gas. A gas which obeys these laws only when temperature is high or pressure
is low is called a real gas.

3.12 CoMPreSSibiLity faCtor


The extent of deviation of a real gas from an ideal behaviour is expressed in terms of compressibility
PV
factor, Z, defined as Z =
nRT

Chemistry at a Glance Final.pdf 36 4/1/2014 12:26:03 PM


Gaseous State 3.31

For ideal gas, Z =1 at all temperatures and pressures. For real gases, 1
greater is the departure in the value of Z from 1, greater is the deviation +H
from ideal behaviour. When Z < 1, the gas is said to show negative = +
deviation. This implies that gas is more compressible than expected &2
from ideal behaviour and under such a condition, attractive forces are  ]
,GHDO
dominating over repulsive forces. When Z >1, the gas is said to show
JDV
positive deviation. This implies that gas is less compressible than
3
expected from ideal behaviour. Under such a condition, repulsive force
are dominating over attractive forces.

3.13 Van der waaL gaS equation


 a   an2 
Van der Waal’s equation:  P + 2  (V − b) = RT for 1 mol of the gas and  P +  (V − nb) =
nRT
 V   V 2 
for n moles of the gas, a and b are constant called Van der Waals constants
Significance and units of Van der-Waals constants: ‘a’ gives the idea of the magnitude of attractive
an2 (p × V 2 )
forces among the gas molecules. As correction in pressure is p = , therefore, a = = atm
V n2
L mol . As correction in volume n = nb, therefore, b = n\n = L mol .
2 –2 –1

3.14 CritiCaL terMS uSed for gaSeS


The temperature at which the gas behaves ideally to a certain range of pressure is known as Boyle’s
a
temperature. TB =
Rb
The temperature above which the gases cannot be liquified even by the application of high pressure
8a
is called critical temperature. TC =
27 Rb

Note:
a
(i) Critical pressure, PC = and critical volume, VC = 3b
27b 2
2
(ii) Guldberg’s rule TBP = TC , where TBP is boiling point and TC is critical temperature of the substance.
3
∆Hvap
Trouton’s rule: ≈ 88J / mol . k
Tb
2a
(iii) Inversion temperature, Ti =
Rb
\ We can say that Ti = 2TB
TC = 8/27 TC
For any substance, TBP < TC < TB < Ti

Chemistry at a Glance Final.pdf 37 4/1/2014 12:26:03 PM


Chapter 4 thermodynamiCs
4.1 IntroductIon

It is the study of energy changes associated with various physical and chemical processes. In thermo-
dynamics, speed of change is not considered and it also does not consider the time element involved in
transformation. Laws of thermodynamics are also not applicable at microscopic level.
∎ In a closed system, boundaries are impermeable.
∎ In an open system, boundaries are permeable.

4.1.1 Terms Used in Thermodynamics


System and surrounding: System is the specified portion of the universe in which we are observing
physical or chemical change. It is surrounded by real or imaginary boundary. Rest of the universe outside
the defined system is called surrounding.

4.1.2 Types of System

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4.1.3 Thermodynamic Properties

(a) Intensive properties: Properties which are independent of quantity of matter, e.g., pressure,
specific heat, surface tension, viscosity, boiling point, specific volume, etc.
(b) Extensive properties: Properties which depends upon quantity of matter, e.g., total mass, volume,
number of moles, etc.

Chemistry at a Glance Final.pdf 38 4/1/2014 12:26:03 PM


Thermodynamics 4.33

∎ All thermodynamic quantities whose name include prefix specific or molar are always intensive.
∎ Extensive properties are additives, whereas intensive properties are not additives.
∎ Ratio of two extensive variables are always intensive.
∎ An intensive property depends only on intensive variables, whereas extensive properties depend
upon both intensive and extensive variables.

4.1.4 State Function or State Variable


A physical quantity is a state function if its value depends only upon the state of the system and not upon the
path by which state is reached, e.g., temperature, pressure, volume, enthalpy, entropy, internal energy, etc.

4.1.5 Path Function and Path Variables


A quantity which depends not only on the state of the system but also on the path or route by which the
state is reached, e.g., work done by heat supplied, etc.

4.1.6 Thermodynamic Process


(a) Isothermal (T = constant, i.e., DT = 0)
(b) Isobaric (P = constant, i.e., DP = 0)
(c) Isochoric (V = constant, i.e., DV= 0)
(d) Adiabatic (in which no heat enters or leaves the system, i.e., q = 0)
Reversible or quasistatic or pseudostatic process: Thermodynamic process in which driving force
is infinitesimally greater than that of restoring force and where direction of change can be reversed by
increasing the restoring force by infinitesimal amount is called reversible or quasistatic process.
All slow processes are considered as reversible; however, perfectly reversible process is that which
requires infinite number of steps for their completion.

4.1.7 Thermodynamic Equilibrium


Thermodynamic equilibrium in a system implies the existence of the following three equilibria
simultaneously:
(i) Thermal equilibrium, i.e., no flow of heat from one part to another, i.e., T = constant
(ii) Mechanical equilibrium, i.e., no flow of matter from one part to another, i.e., P = constant
(iii) Chemical equilibrium, i.e., no change in composition of any part of the system with time.

4.2 FIrst Law oF thermodynamIcs

According to this law, energy can neither be created nor it can be destroyed but it can be transformed from
one form to another. Let a system was having E1 as its internal energy and q amount of heat was supplied to
it. Now if w amount of work is done over it then, lets say final internal energy becomes E2.
E2 = E1 + q + w E2 – E1 = q + w DE = q + w

Chemistry at a Glance Final.pdf 39 4/1/2014 12:26:03 PM


4.34 Chemistry at a Glance

Alternative statement of first law of thermodynamics is ‘It is impossible to construct a perpetual motion
machine, i.e., a machine which can produce energy without expenditure of energy’.

4.2.1 Internal Energy


The energy stored within a substance is called internal energy. Its absolute value cannot be determined, for
it is the sum of various form of energies contained in the system.
i.e., E = E translational + E rotational + E vibrational + E bonding + E electronic + …..
In thermodynamics, we are concerned with energy change which occurs when a system moves from one
state to another, i.e., DE = E final (f) – E initial (i).
Internal energy is a state function and is an extensive property, as DE = nCv DT.

4.2.2 Work Done in Expansion or Compression


If a system changes its volume from V1 to V2 against external pressure, then DV = (V2 – V1)
W = –Pext D V
In case of expansion work done is negative, and in case of compression, work done is positive.
Work done appears at the boundary of the system.

4.2.3 Heat supplied


The energy which crosses the system boundary on account of temperature difference between the system
and its surrounding is called heat supplied. It is a path function quantity.

4.2.4 Enthalpy
Heat content of the system at constant pressure and constant temperature is called enthalpy.
It is represented by H.
H = U + PV ⇒ DH = DU + D(PV)
DH = DU + PDV and at constant pressure DH = DU + DngRT

4.3 moLar heat capacIty

It is defined as the amount of heat required to raise the temperature of one mole of substance
by 1°C. It can be at constant volume (Cv) or at constant pressure (Cp). If heat is supplied at
constant volume, then it causes change in the internal energy:
If dT rise in temperature is caused by heat supplied dE
\ 1° rise in temperature is caused by heat supplied = dE/dT
\ Cv = dE/dT
Similarly Cp = dH/dT
Meyer’s equation, Cp – Cv = R

Chemistry at a Glance Final.pdf 40 4/1/2014 12:26:03 PM


Thermodynamics 4.35

4.3.1 Special Case of First Law of Thermodynamics:


Isothermal Expansion of an Ideal Gas
In isothermal expansion heat is allowed to flow in or out of system so that the temperature remains
constant and if temperature is constant then DT and DE are zero. As there will not be any change in
internal energy.
\ From first law of thermodynamics, DE = q + w
0 = q + w ⇒ q = –w
\ Work will be done at the expense of heat absorbed but their magnitude depends upon whether the
process is carried out reversibly or irreversibly.

4.3.2 Work Done in Reversible Isothermal Expansion


Let an ideal gas is enclosed in a cylinder fitted with a weightless and
frictionless piston. It is not insulated and initially Pext = P.
If external pressure fall by dP, then the gas will expand by small
volume dV, till its pressure also becomes equal to external pressure
(P – dP) and infinitesimally cooling produced by this expansion is
GY
compensated by absorption of heat from outside. The small work done
in this expansion will be
dw = –(Pext – dP)dV = –Pext dV + dPdV
dPdV can be neglected as it is very small.
Therefore, dw = –PdV
If the gas expands from V1 to V2 then the total work done can be
3R[Wĺ3F[W±GS
V2
nR T
given by w = − ∫ PdV ; We know that PV = n R T, i.e., P = ;
V1 V
V2 V2
n RT dv V P
w= ∫
V1 V
dv = −nRT ∫
V1 V
; w = – 2.303 n R T log 2 = –2.303 n RT log 1
V1 P2

4.3.3 Work Done in Irreversible Isothermal Expansion


Irreversible isothermal expansion can be free expansion (in vacuum) or intermediate expansion (when
external pressure is less than the pressure of gas). In free expansion, the work done is zero as there is no net
V2

− ∫ Pext dV =
pressure. In intermediate expansion, from volume V1 to V2, the work done is w = −Pext (V2 − V1 )
V1
Work done in irreversible isothermal expansion is less than reversible isothermal expansion as Pext is
less than gas.

4.3.4 Adiabatic Expansion


In adiabatic expansion, no heat is allowed to flow into or out of the system. Therefore, q = 0.
\ From DE = q + w; We have DE = w

Chemistry at a Glance Final.pdf 41 4/1/2014 12:26:03 PM


4.36 Chemistry at a Glance

\ Work done accompanies the change in internal energy of the system, dE = CV dT


\ w = DE = CVDT
(a) Reversible Adiabatic Expansion: If P is external pressure then work done will be CV dT = –P dV
RT RT
For 1 mole of gas P = ; C V dT = − dV
V V
⇒ T1V1g–1 = T2 V2g–1 ⇒ TVg–1 = Constant; P1V1g = P2V2g
γ 1−γ
 T1   P2 
\ PVg = Constant ⇒   =  We know that work done
 T2   P1 
nR
=
w (T2 − T
=1) nC v (T2 − T1 )
(γ − 1)
(b) Irreversible adiabatic expansion: In free expansion, work done is zero.
\ DE = 0 and thus DT = 0, w = 0 and DH = 0.
 PT −P T 
For intermediate expansion, w = – Pext(V2 – V1); w =
C v (T2 − T1 ) =
−Pext × R  1 2 2 1 
 P1P2 

Note:
Comparison between reversible isothermal and adiabatic expansion. 3L
3
⇒ PISO > PADIA ⇒ VISO > VADIA ,VRWKHUPDOSURFHVV

Area under P–V curve gives us work done. Therefore, work done $GLDEDWLFSURFHVV
during reversible isothermal expansion is greater than that of during
adiabatic expansion. 9L 9

4.4 JouLe–thomson eFFect


The phenomenon of producing lowering of temperature 3RURXVSOXJ
when a gas is made to expand adiabatically from a region
of high pressure into a region of low pressure is known as 9 '7v'3 9
Joule–Thomson effect. The gas is compressed on the left-
hand side. Thus, work is done on the gas. It is equal to P1V1. 3 3
The work done on the right-hand side by the gas is 7 7
equal to P2V2. Total work done by the gas = P1V1 – P2V2.
As q = 0, the work done by the gas lowers its internal
energy and consequently temperature falls. [ \
DE = P1V1 – P2V2
E2 – E1 = P1V1 – P2V2
(E2 + P2V2) – (E1 + P1V1) = 0 or H2 – H1 = 0 or DH = 0.

Note:
Joule–Thomson effect occurs at constant enthalpy; therefore, it is also called isoenthalpic process. When an ideal gas
undergoes expansion under adiabatic condition in vacuum, no change takes place in its internal energy.
Alternatively, the internal energy of a given quantity of an ideal gas at a constant temperature is independent of its
volume, i.e., (∂U / ∂V )T = 0

Chemistry at a Glance Final.pdf 42 4/1/2014 12:26:03 PM


Thermodynamics 4.37

4.4.1 Joule-Thomson Coefficient


The number of degrees of temperature change produced per unit drop in atmospheric pressure under
constant enthalpy condition when a gas is allowed to expand from a region of high pressure to a region of
 dT 
low pressure is known as Joule–Thomson coefficient. µ π = 
 dP H
If m is positive then gas cools on expansion and if m is negative then gas warms on expansion. Every
gas has a definite value of temperature where m changes sign from negative to positive (as there is a
temperature above which the forces of attraction among molecules become negligible) and that temperature
2a
is called inversion temperature. Ti = ; where a and b are Van der Waal constants.
Rb

4.4.2 Carnot Engine


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Work done output W 4
Thermodynamic efficiency, (h) = = rev
Heat input Q input
:UHY
&DUQRW
T Q Q 6XUURXQGLQJ
η = 1− 2 = 1− 2 = = Constant HQJLQH
T1 Q1 T
4

4.4.3 Spontaneous Process 6LQN 7

A process which proceeds of its own accord without any external help is known as spontaneous process, e.g.,
1. Flow of heat from higher temperature to lower temperature
2. A ball rolling down the hill
3. Diffusion of various gases
It is considered that a process takes place because of its tendency to minimize energy but if it is so then
exothermic reaction should only be spontaneous, but it is not so because endothermic reactions are also
spontaneous. Therefore, decrease in energy is not the sole criteria for spontaneity. There is another criteria
and it is increase in entropy (disorder) of system.

4.4.4 Second Law of Thermodynamics


Statement I: It is impossible to convert heat completely into equivalent amount of work done without
compensation.
Statement II: Heat cannot transfer by itself from a cold body to a hot body.
Statement III: When-ever a spontaneous process takes place, then it is accompanied by total increase
of entropy.

4.4.5 Entropy of the System


Entropy is the measurement of randomness or disorder of the system. It is a state function quantity and
can be formulized as follows.
Q2 Q1 Q − Q1 Q
∆S = S2 − S1 = − ; ∆S = 2 if process is isothermal, ∆S = rev .
T2 T1 T T

Chemistry at a Glance Final.pdf 43 4/1/2014 12:26:03 PM


4.38 Chemistry at a Glance

(a) Physical significance of entropy:


(i) In case of isothermal process, increase in entropy is directly proportional to amount of heat
supplied.
(ii) If heat supplied is kept constant, then increase in entropy is greater at lower temperature as
compared to that at higher temperature.
(b) Change in entropy of reversible process:
Heat taken by system = Heat given by surrounding
DS universe = DS system + DS surrounding.
Qrev Q
∆Ssystem = ; ∆Ssurrounding =− rev
T T
Entropy for a spontaneous process increases till it reaches maximum and at equilibrium the change
in entropy is zero, i.e., DS = 0; DS universe = 0 and for a reversible process, change in entropy of universe
must be equal to zero.
(c) Change in entropy of irreversible process: In case of irreversible process, change in entropy of
universe must be positive. DS universe = DS system + DS surrounding > 0
Qrev
(d) Determination of change in entropy: If dS = and Qrev = dU – Wrev
T
dU = nCvdT for ideal gas and Wrev = –pdV
nC v dT + pdV
⇒ dS =
T
nC v dT dV nRT

= dS + nR For ideal gas P =
T V V
 T2 V   T P 
=⇒ ∆S 2.303n C v log10 = + R log10 2  2.303n  C p log10 2 + R log10 1 
 T1 V1   T1 P2 

V P
Case I: For isothermal=
process: ∆S 2.303nR
= log10 2 2.303 nR log10 1
V1 P2
T2
Case II: For isochoric process: ∆S =2.303nC V log10
T1
T2
Case III: For isobaric process: ∆S =2.303nC p log10
T1
Qrev
Case IV: For adiabatic process: ∆S = 0 = Q Qrev = 0
T
In case of adiabatic process, change in entropy = 0. It is also called isoentropic process.

4.4.6 Entropy of Physical Changes

(a) In case of fusion :


∆H fusion Q fusion
Solid ⇌ liquid, Tmp = melting point, ∆S fusion= =
Tmp Tmp

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Thermodynamics 4.39

(b) Sublimation:
∆Hsub Qsub

Solid  Gas ∆Ssub= = ; Tsub < Tmp
Tsub Tsub
(c) Vaporization:
∆H Vap Q Vap

Liquid  Gas ∆S Vap= =
Tbp Tbp
(d) Transition: Conversion of one allotropic form of a substance into another form is called
transition.

S Monoclinic  S Rhombic

Diamond  Graphite

Red phosphorous  White Phosphorous
∆HTrans Q Trans
∆STrans= =
TTrans TTrans

4.4.7 Helmholtz Free Energy Change


Helmholtz free energy, A = U – TS
It is a state function quantity.
Decrease in Helmholtz free energy change = Maximum work done = Work function of process.
(a) Gibb’s free energy change: Gibbs free energy, G = H – TS
It is a state function as DG = DH – TDS.
DG = Useful work done.
(b) Maxwell’s equations:
(i) dU = TdS – PdV (ii) dH = TdS + VdP
(iii) dA = –SdT – PdV (iv) dG = –SdT + VdP
If V is constant, then dV is zero. Then, equation (i) yields
 ∂U   ∂U 
⇒   = T . If S is constant, then  ∂V  = −P .
 ∂S  V  S

4.5 thermochemIstry

Thermochemistry is the branch of physical chemistry that deals with energy changes accompanying
chemical reactions. In a chemical reaction, old bonds get broken with the absorption of energy and the
formation of new bonds takes place with the release of energy. If there is net absorption of energy, then the
reaction is called endothermic. Then, at constant pressure HP > HR; ⇒ DH = HP – HR = +ve;
If there is net release of energy, then the reaction is called exothermic.
Then, HP < HR; at constant pressure, DH = HP – HR = –ve;

Note:
Most of the reactions are carried out in open vessels so that the pressure remains constant during that process.
So heat evolved or absorbed during the reaction will be equal to the enthalpy change in the reaction.

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4.40 Chemistry at a Glance

4.5.1 Heat of Reaction or Enthalpy of Reaction


It is defined as the amount of heat absorbed or evolved when the quantities of the substance indicated by
balanced chemical equation have completely reacted, e.g.,
H2(g) + Cl2(g) → 2HCl(g); DH = – 44 kcal
C(s) + H2O(g) → CO(g) + H2(g); DH = + 31.4 kcal

4.5.1.1 Factors which influence the heat of reaction

(i) Physical state of reactant and product: Heat of reaction depends on the physical state of reactant
and product.
e.g., Consider the following reaction H2(g) + 1/2O2(g) → H2O(g); DH = –57.8 kcal
H2(g) + 1/2O2(g) →H2O(l); DH = –68.32 kcal
More heat is released when water formed is in liquid state. It is because of the reason that heat is
released during condensation of steam.
(ii) Allotropic forms of the element: The heat of reaction depends upon the allotropic forms of the
element
e.g., C (S) + O2(g) → CO2(g) ; DH = –394 KJ/ mol

Diamond

C (S) + O2(g) → CO2(g) ; DH = –393.5 KJ/ mol



Graphite

This difference in the heat of reaction in two allotropic forms is due to the difference in the arrange-
ment of atoms in these allotropic forms.
(iii) Enthalpy of solvation: The amount of enthalpy change when the substance reacts with each other
in dry state will be different than when they react in solution
e.g., H2S(g) + I2(g) → 2HI + S; DH = –17.2 kcal
H2S(g) + I2(Solution) → 2HI + S; DH = –21.93 kcal
This difference is because of the reason that in solution there is involvement of energy in the form
of solvation.
(iv) Temperature: The amount of enthalpy change depends upon temperature as the heat capacities
of system varies with temperature. The standard temperature for the calculation of enthalpies of
various reaction is 25° C or 298 K.

4.5.2 Enthalpy of Formation or Heat of Formation


It is defined as the amount of heat evolved or absorbed when 1 mole of a compound is formed from its
constituent elements.
e.g., C(s) + O2(g) → CO2(g); DH = –97.5 kcal/mol
H2(g) + Cl2(g) → 2HCl(g); DH = –44 kcal/mol
Since on formation of 2 moles of HCl, 44 kcal of heat is released. Therefore, in the formation of 1 mole
of HCl, 22 kcal of heat will be released or we can say that the heat of formation of HCl is 22 kcal. Heat
of a reaction can be calculated if the values of enthalpy of formation of reactants and products are
known by using
DH°(reaction) = S DH°f (product) – SDH°f ( reactants)

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Thermodynamics 4.41

Note:
If the reaction is carried out at standard conditions (i.e., at 25°C and 1 atm. pressure), then the heat of formation is
called standard heat of formation and it is denoted by DH°f. For the determination of enthalpy of formation of
compound, we take standard enthalpies of free elements as zero (arbitrarily).

4.5.3 Enthalpy of Combustion


It is defined as the amount of heat evolved when 1 mole of a substance is completely oxidized.
e.g., C(s) + 1/2 → CO(g); DH = –26 kcal
C(s) + O2(g) → CO2(g); DH = –94.3 kcal
The enthalpy of combustion of carbon is 94.3 kcal and not 26 kcal, as the complete oxidation of carbon
produces carbon dioxide.

4.5.4 Enthalpy of Solution


It is defined as the amount of heat evolved or absorbed when 1 mole of a substance is dissolved in that
much quantity of solvent that further dilution does not cause any heat change.
e.g., KCl + aq → K+(aq) + Cl–; DH = –4.4 kcal
KOH + aq → K+(aq) + OH–(aq); DH = –13.3 kcal

4.5.5 Enthalpy of Neutralization


It is defined as the heat evolved when 1 gram equivalent of an acid is neutralized by 1 gram equivalent of
base in dilute solution.
e.g., Consider the neutralization of HCl with NaOH
(aq)
HCl → H + (aq) + Cl − (aq)
NaOH + aq → Na+(aq) + OH–(aq)
H+ + OH– → H O 2

HCl + NaOH → Na+ + Cl– + H2O


Therefore neutralization reaction is the reaction between H+ ion and OH– ion and the heat evolved by
using a strong base and strong acid will always be the same as they will ionize completely in the solution.

Note:
The heat evolved during the neutralization of weak acid by strong base or weak base by strong acid or weak acid by
weak base will be less than 13.7 kcal as certain amount of heat is absorbed for the ionization of weak acid or weak
base.
HCl( aq ) + NH 4OH( aq ) → NH 4Cl + H 2O; ∆H =−12.3kcal
( strong ) ( weak )

HCN( aq ) + NaOH( aq ) → NaCN + H 2O; ∆H =−11.5kcal


( weak ) ( strong )

H+ + OH– → H2O; DH = –13.7 kcal

Chemistry at a Glance Final.pdf 47 4/1/2014 12:26:04 PM


4.42 Chemistry at a Glance

4.5.6 Enthalpy of Fusion


It is defined as the heat absorbed when 1 mole of a substance changes its state from solid to liquid at its
melting point.
melting
H2O(s)  → H2O(1); ∆H = +10.5kcal

4.5.7 Enthalpy of Sublimation


It is defined as heat absorbed when 1 mole of a substance changes into vapour state at a given temperature
below its melting point, e.g., I2 (s) → I2 (g); DH = +14.9 kcal.
It is equal to the sum of enthalpy of fusion and the enthalpy of vapourisation
DHSublimation = DHFusion + DHVapourization.

4.6 hess’s Law oF constant heat summatIon

It states that the enthalpy of a reaction is dependent only on the initial and final stages whether it takes
place in one step or in number of steps. Let us consider that a substance A is changed into B by two ways.
,

$ %

& '
__

By the Ist way A is converted into B in one step and in the IInd step it is first converted into C and
then into D and finally D is converted into B. Let us say that in the I step the heat evolved is more than
IInd way, then we can go from A to B through the Ist way and then return to A through the IInd step. In
this way the amount of energy released will be more than the energy absorbed in the cyclic process and
as a result of which there is net production of energy which is in contradiction with law of conservation
of energy.
Application of Hess’s Law: Hess’s law gave the following three indirect methods for the calculation of
heat of reaction: DH reaction = ∑ Bond energy of reactants – ∑ Bond energy of products.
DH reaction= ∑ Heat of combustion of reactants – ∑ Heat of combustion of products.
DH reaction = ∑ Heat of formation of products – ∑ Heat of formation of reactants.

4.7 Bond energy and Bond enthaLpy

The average bond dissociation energy required to break each bond in a compound is called bond energy.
e.g., H2O(g) → H(g) + OH (g); DH = 497.8 KJ mol–1
OH(g) → H(g) + O (g); DH = 428.5 KJ mol–1
497.8 + 428.5
Bond energy = = 463.15 KJ/mol
2
The same amount of energy is released when the bond is formed between hydrogen and oxygen.

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Thermodynamics 4.43

4.7.1 Applications of Bond Energy

(a) Determination of heat of reaction: In a chemical reaction old bonds get broken and formation of
new bonds takes place among the reactant molecules, and the energy is absorbed to break the bonds
and among product molecules the energy is released on the formation of new bonds. The net amount
of energy absorbed or evolved is know as heat of reaction.

Note:
Heat of reaction = ∑ Bond energy of reactants – ∑ Bond energy of products.

(b) Determination of resonance energy: A compound which shows resonance has more stability and
its heat of formation will be different than what we have calculated from bond energies. This differ-
ence is called resonance energy.

Note:
Resonance energy = Experimental or actual heat of formation or calculated heat of formation.

4.8 InFLuence oF temperature on the heat oF reactIon

Heat of formation of reactants. We know that DH = HP – HR


 d ∆ H   d HP   d HR 
=
Differentiating the above equation w.r.t. T at constant P  =    − 
 dT P  dT P  dT R
d∆H
= (C P )products − (C P )Reactants ....... (i)
dT
d D H = DCP dT
On integrating equation (i) we have
T2 T2

∫ d ∆ H = ∫ ∆ C P dT
T1 T1

∆HT2 − ∆HT1
⇒ = ∆C P ; Kirchoff ’s equation at constant pressure:
T2 − T1
Difference in the heat capacities of product and reactants is constant. If heat is supplied at
∆ET2 − ∆ET1
constant volume, then = DCv.
T2 − T1
Above equation is known as Kirchoff ’s equation at constant volume.

Chemistry at a Glance Final.pdf 49 4/1/2014 12:26:04 PM


Chapter 5 ChemiCal
equilibrium

5.1 CharaCteristiCs of equilibrium state

Chemical equilibrium: Chemical equilibrium is the most important characteristic property of a


reversible reaction. At equilibrium state, concentration of all reactants and all products do not change
with time chemical equilibrium is attained only when rate of forward reaction becomes equal to the rate
of backward reactions. Chemical equilibrium is dynamic in nature. Therefore, it is also called pseudo
steady state.

Considering a simple reversible reaction A + B C+D
Kf
For forward reaction, i.e., A + B  →C+D
Kb
For backward reaction, i.e., C + D  →A+B
If we plot a curve between rate of reaction versus time, we get

5DWHRIIRUZDUG
UHDFWLRQ
5DWH
(TXLOLEULXPVWDWH

5DWHRIEDFNZDUG
UHDFWLRQ
7LPH

5.1.1 Characteristics of Equilibrium State


(i) Equilibrium state can be achieved if a reversible reaction is carried out in closed space. However,
this condition holds only for gaseous phase reaction.
(ii) Chemical equilibrium is attained from either side, i.e.,

2SO3   2SO2 + O2 ; 
2SO3 + O2   2SO3

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Chemical Equilibrium 5.45

(iii) Chemical equilibrium is attained earlier by using a catalyst; however, the presence of the catalyst
does not alter the equilibrium state.
(iv) It is dynamic in nature, i.e., reaction does not stop but both forward and backward reactions take
place at equal rate.
(v) Change of pressure, concentration or temperature favours one of the reaction (forward or backward)
resulting in shift of equilibrium point in one direction. If we plot a curve between concentration
versus time, there are three possibilities.

5.2 law of mass aCtion

This law was proposed by Guldberg and Wage: According to this law, the rate of chemical reaction is
directly proportional to the product of the active masses of the reacting substances.

For a general reversible reaction, aA + bB   mM + nN
According to law of mass action
Rate of the forward reaction, rf α [A]a [B]b or rf = Kf [A]a [B]b
Rate of the reverse reaction, rb α [M]m [N]n or rb = Kb [M]m [N]n
At equilibrium, rate of forward reaction = rate of backward reaction
i.e., kf [A]a [B]b = Kb [M]m [N]n
kf [M]m[N]n
⇒ = k eq= k=
c
= equilibrium constant
kb [A]a [B]b
where kc is equilibrium constant in terms of concentration.

5.3 relationship between Various equilibrium Constants


Relationship between Kp and Kc:
Kp = kc RTDn, where Dn = np – nR = number of mole of gaseous product – number of mole of gaseous
reactant
Kp = Equilibrium constant in terms of prassure
Kc = Equlibrium constant in terms of conscentration
Kx = Equilibrium constant in terms of mole fraction
Kn = Equilibrium constant in terms of moles
Relationship between Kp and Kx:
kp = kX (Pt)Dn
∆n
 P 
Relationship between Kp and Kn: k P = k n  t 
 Σn 
 
a α [M] or a = g × [M]
Q [M] = molar concentration
α = active mass
g = activity coefficient
Activity coefficient for dilute solution g = 1.
Thus if rate µ active mass
⇒ Rate µ molar concentration.

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5.46 Chemistry at a Glance

5.4 effeCt of algebraiC operation on equilibrium Constant

(i) The equilibrium constant of a forward reaction and that of its backward reaction are reciprocal of
each other.
SO2  2 O2 
E.g., 
2SO3   2SO2 + O2; k f = 2
SO3 
SO3  2 1

2SO2 + O2  2SO3; k b = 2
⇒ kf =
SO2  O2  kb
(ii) If a chemical reaction is multiplied by a certain factor, its equilibrium constant must be raised to a
power equal to that factor in order to obtain the equilibrium constant for the new reaction.
2
1 [NO2 ] [NO2 ]
E.g., for NO + O2   NO2 ; k c1 = 1/2
; 2NO + O2   2NO2 ; k c2 = 2
2 [O2 ] [NO] [NO] [O2 ]

⇒ k c1 = (k c2 )2
(iii) If two or more reversible reactions are added to give a net reversible reaction, then the equilibrium
constant of net reaction is product of equilibrium constant of individual reversible step added.

S + O2  SO2 ,K1
1 
SO2 + O2  SO3 ,K 2
Example: 2
3 
S + O2  SO3 , k 3 =
k1 .k 2
2

Note:
(i) If number of moles of product is equal to number of moles of a reactant, i.e., Dn = 0
⇒ kP = Kc = kx = kn
f
(ii) For a mixture of real gases, γ i = i ⇒ f i = gi P i, where fi is fugacity of ith component.
Pi

5.5 mass aCtion ratio, i.e., reaCtion quotient


Reaction Quotient: At any point in a reversible reaction, ratio of the concentration terms in the same
form as in the equilibrium constant expression can be formulated. This ratio is referred to as reaction
quotient or mass action ratio (Qc).
4 F
.F 4F.F W P .F
HQ LX
W P P LOLEU
4 F HQ ULX H
RY X
Y H XLOLE
P 0 GHT
R DU
0 GHT
D U W RZ
Z
WR

5HDFWDQWVĺ3URGXFWV 5HDFWDQWVDQGSURGXFWV 5HDFWDQWVĸ3URGXFWV


4F!.F DUHDWHTXLOLEULXP4F!.F 4F!.F

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Chemical Equilibrium 5.47

5.6 spontaneity of a reaCtion


If the free energy change of a chemical reaction is negative, the reaction can take place spontaneously,
i.e., it is feasible. If the free energy change is zero, the reaction is in a state of equilibrium and if the free
energy change is positive, the reaction would not proceed. For a reaction to be spontaneous, DG must have
a negative value.
DG = DH – TDS for which DH should be negative and TDS should be positive.
Role of temperature: Temperature being a multiplying parameter for entropy factor (TDS) of a system,
plays an important role in controlling the spontaneity of a reaction.
(a) At high temperature, the entropy factor predominates: In the case of an endothermic reaction,
DH is always positive. Thus, the energy factor does not favour the reaction. But if the reaction is
accompanied by even a small increase of entropy, the high temperature will increase the entropy
factor TDS by a large extent. Hence, DG may become negative at a sufficiently high temperature. This
explains that endothermic reactions become feasible at increasing temperatures.
(b) At low temperature, energy factor predominates: In the case of an exothermic reaction, DH is
always negative. Thus, the energy factor always tends to favour the reaction. If such a reaction takes
place at a low temperature, then even if it is accompained by decrease of entropy, the opposing factor
TDS may remain very small and therefore the value of DG may still have a large negative value. This
points explain why exothermic reactions in many cases remain feasible at decreasing temperatures.
Standard free energy of formation of a compound: Standard free energy of formation of a compound is
defined as free energy change involved in the formation of a compound in standard state (25°C and 1 atm)
from its elements in their standard states. This is denoted by DGF°.
DGF° = DHF° – TDSF°
Standard free energy change of a reaction may be calculated with the help of standard free energy change
of formation of compounds involved in the reaction, DG° = [DGF°]Products – [DGF°]reactants.

5.7 heterogeneous equilibria


When reactants and products present in an equilibrium have more than one phase in such a case pure sol-
ids and pure liquids have essentially constant concentrations. Thus, we ignore pure solids and pure liquids
in writing equilibrium constant expression.
e.g., (i) 
CaCO3(s) 
 CaO(s) + CO2 (g)
P
=
K p p=
CO2 nCO2 ×
Σn


(ii) 3Fe(s) + 4H2O(g) 
 Fe3O4(s) + 4H2(g)
(=
p ) (n )
4 4 0
H2 H2  P 
=Kp ×
 Σ n 
(p ) (n )
4 4
H2 O H2 O  
As a general rule, the concentrations of pure solids and pure liquids are not included when writing an
equilibrium equation because their concentrations are constants that are incorporated into the value of
the equilibrium constant. We include only the concentrations of gases and the concentrations of solutes in
solutions because only those concentrations can be varied.

Chemistry at a Glance Final.pdf 53 4/1/2014 12:26:04 PM


5.48 Chemistry at a Glance

The equilibrium constant KP is related to standard free energy change (DG°) by the relation
DG° = –2.303 RT log10KP at standard state, T = 25°C; P = 1 atm.
When DG° = –ve, forward reaction is thermodynamically feasible (K > 1)
DG° = +ve or K < 1, reverse reaction is feasible.
DG° = 0, then k = 1, i.e., equilibrium condition.

5.8 Degree of DissoCiation

Degree of dissociation is defined as the fraction of one mole of a molecule dissociated. It is denoted by α. Its val-
ue is always less than 1. When the value becomes equal to 1, it is said that the substance is completely dissociated.
Experimental determination of degree of dissociation, is determined by measuring vapour density of
a reaction mixture at equilibrium. Considering a general reversible reaction
A 
 
 nB
Initial number of moles 1 0
Number of mole at equilibrium (1 – α) nα
Total number of moles at equilibrium = (1 – α) + nα = 1 + (n – 1)α.

5.8.1 Determination of Degree of Dissociation by Measurement


of Vapour Denisty
If d be the observed vapour density at a particular temperature when degree of dissociation is α and D be
D−d
the vapour density when there is no dissociation, then α =
(n − 1) d
M−m
In terms of molecular mass, α = , where M = initial molecular mass
(n − 1) m
m = molecular mass at equilibrium


e.g., (i) PCl5 
 PCl3 + Cl2, here n = 2
D−d D−d
=x =
(2 − 1) d d
Degree of dissociation by using pressure-temperature determination: Consider the following gaseous
reaction.

PCl5(g)  PCl3(g) + Cl2(g) temperature pressure
t=0 a 0 0 T1 P1
teq. a – aα aα aα T2 P2
T1 P2 − T2 P1
⇒ α=
T2 P1

5.9 le Chatelier’s prinCiple anD its appliCation


Le Chatelier’s Principle: According to this principle, if an equilibrium is subjected to a stress, the equi-
librium adjusts in such a manner that the effect of the disturbance is minimized.
(i) Effect of change of pressure: By increasing the pressure, equilibrium shifts in the direction in
which there is decrease in volume or less number of molecules and vice versa.

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Chemical Equilibrium 5.49

E.g., (i) N2 + 3H2  


 2NH3 ; By increasing the pressure, more NH3 will be formed.
(ii) PCl5  
 PCl3 + Cl2
By increasing the pressure less PCl5 will be dissociated.
(ii) Effect of change of temperature: By increasing the temperature the equilibrium shifts in the
direction in which heat is absorbed, i.e., in which direction reaction is endothermic.
E.g., (i) N2(g) + 3H2(g) 
 2NH3(g) DH = –92.38 kJ
By increasing the temperature, formation of NH3 decreases.
Effect of adding inert gases:
(i) If P is a constant and Dn, = 0, KP is unaffected by the addition of the inert gas.
(ii) If P is constant and Dng ≠ 0, and if we add an inert gas, equilibrium will shift in the direction
where Dng is positive.
(iii) If V is a constant and an inert gas is added, no change in equilibrium takes place.
(iii) Effect of change of concentration: In a chemical equilibrium increasing the concentration of
the reactants results in shifting the equilibrium in favour of the products while increasing the
concentration of the products results in shifting equilibrium in favour of the reactants.
Le Chatelier’s principle in case of physical equilibrium:
(i) Effect of pressure on boiling point:
Water  
 Vapour
An increase in pressure will favour backward reaction, i.e., the reaction in which volume
decreases (Vvapour > Vwater). Thus, more water will exist at equilibrium, i.e., boiling point of water
(solvent) increases with increase in pressure.
(ii) Effect of pressure on the freezing point of a liquid (or melting point of a solid)
(a) For ice  water equilibrium: An increase in pressure will favour forward reaction
because Vice is greater than Vwater. Thus, more and more ice will melt or the melting point of ice
is lowered with increase in pressure.

(b) For a solid   liquid equilibrium: An increase in pressure will favour backward reaction
because VLiquid > Vsolid and thus more solid will exist at equilibrium, i.e., melting point of solid
increases with increase in pressure.
(iii) Effect of pressure on solubility of gases:
Gas + Solvent  
 Solution
(VF) (Vb)
Since VF > Vb, an increase in pressure will favour forward reaction and thus solubility of gas
increases with increase in pressure.
Henry’s law: It states that the mass of a gas dissolved in a given mass of a solvent at any
temperature is proportional to the pressure of the gas above the solvent.
W(g) µ P(g) or W(g) = KP(g); where W(g) is amount of gas dissolved in solution and P(g) is the
partial pressure of the gas over the solution and K is Henry’s constant which is different for each gas.
(iv) Effect of temperature on solubility of solids:
(a) Solute + Solvent  
 Solution; DH = +ve
An increase in temperature always favours endothermic process and thus solutes having
endothermic dissolution (e.g., urea, glucose) show an increase in their solubility with increase
in temperature.
(b) Solute + Solvent  
 Solution; DH = –ve
Solutes having exothermic dissolution (e.g., lime, NaOH, acids, etc.) show a decrease in their
solubility with increase in temperature. Le Chatelier principle is not valid for solid–solid
heterogeneous equilibrium.

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Chapter 6 IonIC
equIlIbrIum

6.1 IntroductIon

Arrhenius theory: According to this theory, ‘Acids are the substances which give H+ on dissolution in
water while bases are the substances which give OH– on dissolution in water.’
Examples:
(i) HCl(g) + Water ⇌ H+(aq) + Cl–(aq)
(ii) CH3COOH + Water ⇌ H+(aq) +CH3COO–(aq)
(iii) Ca(OH)2 + Water ⇌ Ca2+(aq) + 2OH–(aq)
The high dielectric constant of water lowers the force of attractions between the oppositely
charged ions and thus causes the dissociations of the electrolyte. The greater the number of
H+ or OH- ions given by an acid or a base in water, the greater will be the strength of the acid
or the base.

6.1.1 Limitation of Arrhenius Theory


(a) It fails to explain the behaviour of acids and bases in non-aqueous solvents.
(b) It fails to explain the neutralization reactions giving rise to salt formation in absence
of a solvent.
E.g., (i) CO2(g) + CaO(s) → CaCO3(s)
(ii) NH3(g) + HCl(g) → NH4Cl(g) or (s)
(c) It fails to explain the acidic character of certain salts, e.g., AlCl3, BF3, etc. and basic character of
NH3,PH3, etc.

6.1.2 Proton Transfer Theory (Bronsted and Lowry Concept)


According to this theory, ‘An acid is a substance which has a tendency to donate a proton to other
substances, and a base is a substance which has a tendency to accept a proton from any other substances.’

E.g., Acid  +
 H + Base (Proton)

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Ionic Equilibrium 6.51

(a) Characteristic of Proton Transfer Theory:


(i) The proton donated by an acid is incapable of independent existence and is always
solvated.
CH3COOH + H2O ⇌ CH3COO– + H3O+
(ii) A cation may behave as an acid and an anion may behave as a base in water, however, some of
them behave as amphoteric.
E.g., Ag + + 2H2O  AgOH + H3O+ ;
CO23− + H2O  OH − + HCO3−
A substance which can act both as an acid as well as a base in different reactions is called
amphoteric.
An acid-base pair which differs by a proton is called conjugate acid-base pair.
HCO3− + H2O  H2CO3 + OH −
where HCO3– is amphoteric

6.1.3 Conjugate Acids and Bases


Pairs of the substances which can be formed from one another by the gain or loss of a proton are known
as conjugate acid–base pair.

+ +
Acid 
−H
→ Conjugate Base +H
Base  → Conjugate Base
HCl Cl –
NH3 NH4+
H2SO4 HSO4– C2H5– C2H6
NH3 NH2 –
H2O H3O+

The stronger an acid, the weaker must be its conjugate base and vice versa.
e.g., HCl + H2O → H3O+ + Cl − ;
Acid Conjugate base

CH3COOH + H2O → H3O+ + CH3COO− order of acidic strength is


Acid Conjugate base

HCl > CH3COOH and order of basic strength of conjugate bases are CH3COO– > Cl–.
All Arrhenious acids are Bronsted acids while all Arrhenious bases is not Bronsted bases,
e.g., NaOH, is an Arrhenious base as it furnishes OH– but is not a Bronsted base as it is not capable of
accepting a proton as such.
Leveling Effect: In a solvent like H2O, all strong acid are almost completely dissociated and
therefore their acidic strength cannot be compared. This phenomenon is termed as leveling
effect.

6.1.4 Lewis concept of Acids and Bases


According to this theory, ‘An acid is a species that is capable of accepting a pair of electrons to form
a dative covalent bond and a base is a species that is capable of donating a pair of electrons to form a
dative covalent bond’.

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6.52 Chemistry at a Glance

Example:
(a) BF3 + NH3 → F3B NH3

H F H F
| | | |
H − N : + B − F 
→ H − N 
→ B− F
| | | |
H F H F

(b) BF3 + F − → BF4−


Acid Base

(c) Cu + 4CN + → [Cu(CN)4 ]2−


2+
Acid Base

(a) Classification of Lewis Acid:


(i) Molecules in which central atom has an incomplete octet, e.g., BF3, AlCl3, etc.
(ii) Molecules which have a central atom with empty d-orbitals, e.g., SiX4, GeX4, PX3, TiCl4, etc.
(iii) Molecules having multiple covalent bond between atoms of dissimilar electronegativity,
e.g., CO2, SO2, SO3, etc.
= C O + OH − 
O = → HCO3−
(Lewise base) (Lewiseacid)

(b) Characteristics of Lewis Bases:


(i) Neutral species having at least one lone pair of electrons.
•• •• •• •• •• ••
e.g., N H3 , R − N H2 , R − O− H, R − N H − R, R 3 N :, R − S − R, R − O− R , etc.
•• •• ••

(ii) Negatively charged species, e.g., CN–, OH–, Cl–, SO42–, CO32–, etc.

6.1.5 Classification of Acids


(a) Hydroacids: Some example of hydroacids are HCN, H2S, H2Se, H2Te, HCl, HBr, HF, Hl,N3H, etc.
For hydroacids as we move down in the group the acidic strength increases as well as when we move
from left to right in a period acid strength increases.
e.g., (i) HF < HCl < HBr < Hl; (in group)
(ii) NH3 < H2O < HF; (in period)
(b) Acid anhydride and oxyacids: Oxides of non-metals having same oxidation number of a
non-metal in their respective oxyacids and themselves are known as acid anhydrides. The acid
anhydrides on dissolution in water give their respective oxyacids.
e.g., SO 3 + H2O → H2SO4
(+6)(anhydride) (+6) (oxyacid)

e.g., H4P2O3 is not an acid because there is no replacable hydrogen.


∎ For obtaining acid anhydride from any oxyacid, subtract H2O in such a way that no hydrogen
remains.
∎ If an acid anhydride can form more than one oxyacids (containing all the cen-
tral atom in each case in same oxidation state) then we must consider ortho, meta and
pyronotation.

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Ionic Equilibrium 6.53

6.1.5.1 Acidic strength of oxyacids


(a) Higher the oxidation number of common central atom in oxy acids, more will be the acidic character
if basicity is same.
e.g., HClO4 > HClO3 > HCLO2 > HClO
( +7) ( +5) ( +3) ( +1)

(b) If central atom is different but basicity is same then as the electronegativitty of central atom increases
acidic strength of oxyacid also increases HClO4 > HBrO4 > HIO4.

Notes:
 Ions of acids containing-ic suffix are written as-ate, while those containing-ous suffix can be
written as-ite
H2 SO3 SO32 − H2 SO4 SO42
e.g.,
Sulphurous acid Sulphite ion Sulphuric acid Sulphate ion
 Replaceable hydrogens in oxy acids are those which are directly attached to oxygen atoms.
e.g., Diprotic Mono protic
2
2
3
 +
3 2
2
+ 2 +
+ + +
RQHUHSODFDEOH+ WZRUHSODFDEOH+
+32 +32

6.2 ArrhenIus theory of electrolytIc dIssocIAtIon


According to this theory, ‘An electrolyte on dissolution in water furnishes two type of ions, positive
(cation) and negative (anion). A chemical equilibrium exists between undissociated electrolyte and
dissociated ions.’ If a is the degree of dissociation of an electrolyte AB, then
AB ⇌ A+ + B-
Before dissociation 1 0 0
after dissociation 1–a a a
Moles dossociated
where degree of dissocaition (α) =
Total moles present initially
The degree of dissociation of a strong electrolyte is assumed to be unity at infinite dilution, i.e., a = 1.

6.2.1 Strong and Weak Electrolytes


(a) Strong Electrolytes: Electrolytes which ionize almost completely when dissolved in water are
called strong electrolytes, e.g., (all salts except CdBr2, HgCl2), mineral acids like HCl, H2SO4, HNO3,
etc and bases like NaOH, KOH, etc.
(b) Weak Electrolytes: Substances which dissociate only to a small extent in aqueous solution are
weak electrolytes, e.g., all organic acids (except suphonic acids), inorganic acids like HCN, H3BO3
etc. and bases like NH3, amines, etc.

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6.54 Chemistry at a Glance

6.2.2 Factors Influencing Degree of Dissociation


The variation of ‘a’ of an electrolyte is governed by:
(a) Nature of solute: All ionic compounds, i.e., strong electrolytes have a ≈ 1 at normal dilution.
Most of the polar covalent compounds, i.e., weak electrolytes have a << 1.
(b) Nature of solvent: Solvents having high dielectric constants are themselves feebly ionized but an
electrolyte in such a solvent show higher degree of dissociation than in a solvent of low dielectric
constant (say methanol).
(c) Dilution: The extent of dissociation of an electrolyte increases with dilution of solution.
(d) Temperature: The extent of dissociation of an electrolyte increases with an increase in temperature.
(e) Common ion effect: Addition of another solute having ion common to that of weak electrolyte
shows a decrease in degree of dissociation of a weak electrolyte. This is known as common ion effect.

6.2.3 Ostwald Dilution Law


The application of law of mass action to weak electrolytes is known as Ostwald dilution law.
Considering a weak electrolyte HA in equilibrium
HA ⇌ H+ + A-
t=0 c o o
t = teq c (1-a) ca ca
+ −
[H ][A ] cα × cα cα 2
According to law of chemical equilibrium, K a = = = , where Ka is dissociation
[HA] c(1 − α) 1− α
constant of an acid.
Since for a weak electrolyte, a <<1
Ka
⇒ Ka = ca2 or α = Kb = dissociation constant of a base
c
c α2 Kb
Kb = and Kb = ca2 and α =
1− α c

Notes:
∎ Ostwald dilution law is not applicable for strong electrolytes.
∎ The smaller the value of Ka, the weaker the acid.

(a) Relative strength of weak acids and weak bases: Relative strength of two weak acids is a measure
of [H3O+] = [H+] when concentrations of two acids are same, i.e., c1 = c2.
Relative strength of acid 1 K a1
⇒ =
Relative strength of acid 2 K a2
Relative strength of two weak bases is a measure of [OH–]
Relative strength of base 1 K b1
⇒ =
Relative strength of base 2 K b2

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Ionic Equilibrium 6.55

(b) Dissociation of polyprotic acids: Substance which are capable of furnishing more than one
proton to water are known as polyprotic or polybasic acids.
e.g., Considering a triprotic acid, i.e., phosphoric acid (H3PO4)
[H PO− ][H + ][H2O]
H3PO4 +H2O ⇌ H3O+ +H2PO4–; K a1 = 2 4
[H3PO4 ][H2O]
[HPO24− ][H + ]
H2PO4– + H2O ⇌ H3O+ + HPO42–; K a2 =
[H2PO4− ]
[PO34− ][H + ]
HPO42– + H2O ⇌ H3O+ + PO43– ; K a2 =
[HPO24− ]
The value of the three ionization constants follow a decreasing trend K a1 > K a2 > K a3 .
The reason for the decrease in the dissociation constant of successive stages is that in the first stage of
dissociation, the proton comes from a neutral molecule while in the second stage of dissociation, the
proton is detached from a negatively charged ion and in the third dissociation, it is detached from a
doubly charged negative ion.
(c) Acidity and pKa: The dissociation constant of an acid (Ka) is usually expressed in terms of pKa,
i.e., negative logarithm of Ka.
pKa = –log Ka: similarly (pKb = –log Kb). For bases
The strength of a base is inversely related to pKb values of the base, i.e., the larger is the value of pKb
the weaker is the base.

Notes:
∎ Acidic strength ∝ Ka ∝
1
pK a
1
∎ Basic strength ∝ Kb ∝
pK b

(d) Ionic Product of Water: Since water is amphiprotic it gives H3O+ and OH- as a result of self
ionization (auto protolysis).
H2O + H2O ⇌ H3O+ + OH-
Acid 1 Base 1 Acid 2 Base 2
Applying the law of mass action, law of dissociation constant
[H3O+ ][OH − ] [H + ][OH − ]
= Kc =
[H2O]2 [H2O]
Since dissociation takes place to a very small extent, hence the concentration of undissociated
water molecules [H2O] may be regarded as constant.
Kw = [H+] [OH] = 1 × 10–14 at 25°C
The numerical value of Kw increases with increase in temperature.
Since in pure water, the concentration of H+ and OH- ions must be equal to one another, hence,
Hence [H+] = [OH–] = 1 × 10–7 mol dm–3.
(i) If [H+] > √KW, the solution is acidic.
if [H+] = √Kw, the solution is neutral.

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6.56 Chemistry at a Glance

if [H+] < √Kw the solution is basic.


Molarity and degree of dissociation of water
e.g., An aqueous solution in which [H+] is less than 1 × 10–7 mol/litre is said to be alkaline.
\ [H+] = ca = 10–7 and concentration or molarity of water = 55.6
10 −7
\ α − = 1.8 × 10−9 or % dissociation = 1.8 x 10–7.
55.6
(e) Relation between Kw, Ka and Kb:
For a conjugate acid, base pair HA and A- in aqueous solution.
HA ⇌ H+ + A–; Ka
A- + H2O ⇌ HA + OH–; Kb
On adding these two equations, we get
H2O ⇌ H+ + OH–; Kw = Ka × Kb.
This relationship shows that product of dissociation constant of an acid and the dissociation constant
of its conjugate base is the ionic product of water.
i.e., Kw = Ka × Kb
⇒ pKw = pKa + pKb = 14 at 25°C.

6.3 the ph vAlue And ph scAle

The concept of pH was introduced by Soren Sorensen. According to him, ‘the pH of a solution is the
negative logarithm (to the base 10) of the concentration of H+ ions which it contains.’
Thus, pH = –log10[H+] = – log10[H3O+]
⇒ [H+] = [H3O+] = 10–pH
⇒ pH + pOH = pKw = 14 at 25°C.

6.3.1 pH of Strong Acids or Strong Bases


When a strong acid is added to water, as in an aqueous solution of, HCl, in addition to the self-ionization
of water,
H2O + H2O ⇌ H3O+ + OH–
ionization of acid also occurs.
HCl + H2O → H3O+ + Cl–

The self-ionization of water occurs to a slight extent while ionization of HCl goes essentially to completion.
As a result, we conclude that.
(a) In calculating [H3O+] in an aqueous solution of a strong acid, the strong acid
is the only significant source of H3O+, unless the solution is extremely dilute
(e.g., less than 10–6 M).
Total [H3O+] = 10-7 + 10-8 M ⇒ pH < 7
(b) In calculating [OH–] in an aqueous solution of a strong base, the strong base is the only significant
source of OH- unless the solution is extremely dilute. (e.g., less than 10–6 M).
Total [OH–] = 10–7 + 10–8 = 11 x 10–8M ⇒ pOH < 7

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Ionic Equilibrium 6.57

Notes:

base  H 3O +  Σ=
∎ Total [H3O+] or [OH-] in two strong acids / = NV
; OH − 
Σ NV
ΣV ΣV
∎ The resultant solution of a mixture of a strong acid (Normality N1, volume V1) and a strong base (Normality N2,
volume V2)
(i) is neutral if N1 V1 = N2 V2
N 2 V2 − N1 V1
(ii) is basic if N2 V2 > N1 V1 and resultant [OH − ] =
V1 + V2

N1 V1 − N 2 V2
(iii) is acidic if N1 V1 > N2 V2 and resultant [ H 3O + ] =
V1 + V2

6.3.2 pH of weak acids and weak bases

(a) Considering a weak monobasic acid


HA + H2O ⇌ A– + H3O+
t=0 c 0 0
t = teq c(1–a) ca ca
1 1
\= pH [pK a − log c] ; pH =−14 pOH =−
14 [pK b − log c]
2 2
+
=
(b) Total [H3O+] in a mixture of two weak acids can be given as [H 3O ] K a1 c1 + K a2 c2

∎ Total [OH–] in a mixture of weak bases can be written as [OH


= −
]T K b1 C1 + K b2 C 2

6.3.3 Common Ion Effect


If a salt of a weak acid is added to a solution of the acid itself, the dissociation of the acid is diminished.
So, ‘The suppression of the dissociation of a weak acid or a weak base on the addition of its own ions is
called common ion effect.’
[CH3COO− ][H + ]
E.g., dissociation of acetic acid CH3COOH ⇌ CH3COO– + H+ ⇒ Ka =
[CH3COOH]
The equilibrium constant Ka has a definite value at a given temperature. If another electrolyte
containing CH3COO– or H+ ions can be added to the given solution, it will increase the [CH3 COO– ] and
[H+] ions, and in order to Ka remain a constant, the [CH3COOH] must increase, so that equilibrium will
shift to the left side.

S+ 6WURQJEDVH
6.4 Buffer solutIons :HDNEDVH
9ROXPHRI
Buffers are the solution which resists the change in their pH on addition DFLGDGGHG 
of a small amount of a strong acid or a strong base. 
In order for a solution to act as a buffer it must have two :HDNDFLG  9ROXPHRI
EDVHDGGHG
compounds, one of which is able to neutralize acids, and the other bas- 6WURQJDFLG
es. Common buffer solution are mixtures containing a 

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6.58 Chemistry at a Glance

(i) weak acid and its conjugate base (one of its salts), i.e., acidic buffer
(ii) weak base and its conjugate acid (one of its salts), i.e., basic buffer
(iii) salt buffer

6.4.1 Buffer of a Weak acid and its Salt with a Strong Base
It is possible to prepare a buffer solution by the addition of a weak acid and a salt of the acid. We shall
explain the buffer action by the following example, CH3COOH + CH3COONa
Applying law of mass action to the dissociation equilibrium of CH3COOH
CH3COOH ⇌ CH3COO– + H+
[CH3COO− ][H + ]
Ka =
[CH3COOH]
K a [CH3COOH]
⇒ [H + ] = ; where [CH3COO–] = [Salt] = Initial concentration of the salt
[CH3COO− ]
[CH3COOH] = [acid] = Initial concentration of acid; taking log of both sides and multiplying
by –ve sign we get.
[Salt]
⇒ pH
= pK a + log
[Acid]
This equation is known as Hendersen’ equation.

6.4.2 Buffer of a Weak base and its Salt with a Strong Acid
It consists of a weak base and its salt with strong acid, e.g., NH4OH + NH4Cl, and applying law of mass
action to the dissociation equilibrium of NH4OH.
NH4OH ⇌ NH4+ + OH–
[NH +4 ][OH − ]
⇒ Kb = ;
[NH 4OH]
K b [NH 4OH]
Hence, [OH − ] = ; where [NH4+] = [salt] = Initial concentration of the salt.
[NH 4+ ]
[NH4OH] = [base] = Initial concentration of base
[Salt]
⇒ pOH
= pK b + log .
[Base]
(a) Buffer Capacity: The capacity of a solution to resist alteration in its pH is known as its
buffer capacity.
Buffer capacity of a solution is defined as the change in the concentration of a buffer acid (or base)
required for changing its pH value by one unit keeping total concentration of acid + salt or base + salt
constant.
Considering an acidic buffer solution with concentration of acid and the concentration of salts
pH = pKa + log10S/a. To this buffer solution, if small amount of a strong base Db is added then the
 S + ∆b 
new pH becomes pH = 2 pK a + log   , change in pH of the solution.
 a − ∆b 

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Ionic Equilibrium 6.59

S + ∆b S
∆pH = pH2 − pH1 = log − log
a − ∆b a
 (S + ∆b)a   1 + ∆b / S  1  1 + ∆b / S 
==
log10  =
 log 10   ln  
 (a − ∆b)S   (a1 − ∆b / a  2.303  1 − ∆b / a 
∆b
Q << 1 and <<
S
1  ∆b ∆b  ∆b  a + S  ∆b  a ×S 
⇒ =
∆pH  +  ⇒ ∆pH =  ×  ⇒ ∆= 2.303 ×  + 
2.303  S a  2.303  a S  pH a S

(b) Buffer Range: The range of pH over which a buffer is most effective is termed as the buffer range.
(i) An acidic buffer will be effective with the pH range (pKa – 1) to (pKa + 1), i.e., (pKa ± 1).
(ii) A basic buffer will be effective over the pH range (pKw – pKb ± 1).

Note:
To make a buffer solution of a given pH, first it is necessary to choose a weak acid or weak base whose pKa or pKb
value is as close as possible to the required pH.

6.4.2.1 Salient features of buffer solutions


(i) It has definite pH, i.e., it has reserve acidity or alkalinity.
(ii) Its pH does not change on standing for long.
(iii) Its pH does not change on dilution.
(iv) Its pH is slightly changed by the addition of small amount of acid or base.
(v) More efficient buffers are those which have pH between 3 and 11.
(vi) No strong acid or base should remain till the end after their addition in a buffer solution.

6.4.2.2 Uses of buffer solution


(a) Qualitative analysis of a mixture, e.g., removal of phosphate.
(b) Industrial process such as manufacture of paper, dyes, inks, paints, drug, etc.
(c) Digestion of food.
(d) Preservation of foods and fruits.
(e) Agriculture and dairy products preservations.
Blood as a Buffer Solution: The normal pH value of blood plasma is 7.4. Severe illness or death can
result from sustained variations of a few tenths of a pH unit. Dissolved ratio of HCO3– to H2CO3 is helpful
in controlling pH of blood.

6.5 volumetrIc tItrAtIons


6.5.1 Indicators
An indicator is a substance which is used to determine the end point of a reaction or a substance which
indicates the completion of a reaction.

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6.60 Chemistry at a Glance

The nature of an indicator depends upon the nature of a titrant used. There are many types of
indicators known.
(i) Acid-base indicaors, e.g., phenolphthalein, methyl orange, etc.
(ii) Redox indicators, e.g., KMnO4, K2Cr2O7, etc.
(iii) Adsorption indicators, e.g., Starch paper with I2.
Acid-Base Indicators: An acid–base indicator is a substance which possesses one colour in acid solu-
tion and different colour in alkaline medium or the substances whose colour changes with change in pH.

6.5.2 Theory of Indicators


Ostwald Theory: According to this theory
(i) Indicators are either weak acids or weak bases.
(ii) Their unionized molecules posses different colour from those of the ions which they give in the
solution.
(iii) An acidic indicator yields a coloured anion while a basic indicator gives coloured cation in
solution.
(iv) Since they are weak electrolytes, they are not sufficiently ionized in solution. But in presence of
strong acid or base, their degree of ionization is considerably high and they produce a large number
of coloured ions.
(v) An indicator changes colour when the concentration of [H+] in solution is equal to dissocaition
constant of the indicator, i.e., indicator is 50 per cent dissociated.
[In − ]
=pH pKIn + log10
[HIn]
For a person to observe both colour of a solution, minimum change in pH must be equal to 2 units.
Range of Indicators: It is the range of pH in or which indicator does not work.
Lower and higher values of pH between which exact colour of indicator cannot be seen are known as
range of indicator. Range of indicator is from pKln – 1 to pKln + 1.

6.6 sAlt hydrolysIs

The phenomenon of the interaction of anions and cations of the salt with H+ and OH– ions furnished by
water yielding acidic or alkaline (or sometimes even neutral) solutions is known as salt hydrolysis.
Salt are strong electrolytes, here when dissolved in water, they dissociate almost completely into cati-
ons and anions.
In salt hydrolysis, cation or anion or both of a salt react with water to produce acidity or alkalinity. The
process of hydrolysis is actually the reverse of neutralization.
Salt + Water ⇌ Acid + Base

Note:
 Only that component of a salt can participate in hydrolysis which is derived from a weak electrolyte.
 The nature of a solution depends upon the component of a salt which is derived from a strong electrolyte.
 Depending on the nature of an acid or a base there can be four types of salts.

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Ionic Equilibrium 6.61

6.6.1 Salt of a Strong Acid and a Weak Base


The cation of a salt which comes from a weak base take part in hydrolysis.
e.g., NH4+ + H2O ⇌ NH4OH + H+
Initially c 0 0
Finally c(1–h) ch ch
⇒ pH = 7 - 1/2 pKb – 1/2 log c.

6.6.2 Salt of a Weak Acid and a Strong Base


The anion of a salt which comes from a weak acid takes part in hydrolysis, e.g., CH3COONa
CH3COO– + H2O ⇌ CH3COOH + OH–
Initially c 0 0
Finally c(1–h) ch ch
⇒ pH = pKw – pOH = 7 + 1/2 pKa + 1/2 log c

6.6.3 Salt of a Weak Acid and Weak Base


Both the anion and cation of a salt take part in hydrolysis
e.g., CH3COO– + H2O ⇌ CH3COOH + OH–
NH4+ + H2O ⇌ NH4OH + H+
Combined these two, we get
CH3COO– + NH4+ + H2O ⇌ CH3COOH + NH4OH
Initially c c 0 0
Finally c(1–h) c(1–h) ch ch
⇒ pH = 7 + 1/2pKa – 1/2 pKb

6.6.4 Salt of a strong acid and a strong base


Salt of a strong acid and a strong base do not undergo hydrolysis because both the ions are not reactive.

Note:
Degree of hydrolysis always increases with increase in temperature because at elevated temperature, increase in Kw is
greater as compared to Ka and Kb.

6.7 soluBIlIty And soluBIlIty Product

6.7.1 Solubility Product


The solubility product of a sparingly soluble salt forming a saturated solution in water is given by the prod-
uct of the concentrations of the ions raised to a power equal to the number of times of ions occur in the
equation representing the dissocaition of the electrolyte.

Chemistry at a Glance Final.pdf 67 4/1/2014 12:26:05 PM


6.62 Chemistry at a Glance

Considering a sparingly soluble salt, AmBn ⇌ mAn+ + nBm–


Ksp = [An+]m [Bm–]n
If molar solubility of this salt is S moles/litre, then Ksp = (ms)m (ns)n
Ksp = (mmnn) sn+m.

6.7.2 Applications of Solubility Product Principle

(a) Predicting Precipitation Reaction: A substance gets precipitated when the ionic product, i.e., the
product of concentration of its ions present in a solution exceeds the solubility product of the sub-
stance. When
(i) Ionic product (IP) > Ksp; Precipitation takes till IP equals Ksp.
(ii) Ionic product (IP) < Ksp; A precipitate will not be formed and the solution will be unsaturated.
(iii) Ionic product (IP) = Ksp; A precipitate will not form and the solution is saturated in that salt.
(b) Preferential Precipitation of an Insoluble Salt: It can be explained on the basis of their
respective solubility product. ‘As a rule, the compound with the lower solubility product get
precipitated in preference’.
Since Ksp of Agl < Ksp of AgCl
\ Agl gets precipitated in preference to AgCl.
(c) Salting out of Soap: The saturated solution of soap (RCOONa), the sodium salt of higher fatty
acids show precipitation of soap on addition of NaCl. This is because of the fact that an increase in
Na+ concentration helps in crossing over ionic product to their Ksp value.
C17H35COONa(s) ⇌ C17H35COO–(aq) + Na+(aq)
Ksp= [C17H35COO–] [Na+].
When NaCl is added, [Na+] increases due to which ionic product also increasess which results in
precipitation of soap:
(d) Cationic analysis: Cation analysis is based on the principle of Ksp and common ion effect.
The decrease in the ionization (solubility) of a weak electrolyte in the presence of a common ion
from a strong electrolyte is called common ion effect, e.g., ionization of H2S (weak acid) decreases in
presence of HCl (H+ is the common ion).
Group I: Cations (Ag+, Hg2+, Pb2+) are precipitated as chlorides since their Ksp values are low.
Group II: Cations (Pb2+, Cu2+, Cd2+, Hg2+, Bi3+, Sb3+) are precipitated as their sulphides since their IP
values are decreased due to low [s2–] because of common ion effect.
Group III: Cations (Al3+, Fe3+, Cr3+) are precipitated as their hydroxides, since their IP values are
decreased by the addition of NH4Cl to NH4OH.
Group IV: Cations (Zn2+, Mn2+, Ni2+) are precipitated as their sulphides, since their IP values are
decreased due to increased [S2–] because of common ion effect.
(i) CH3COONa, NaCN, Na2CO3, Na3PO4, etc.
(ii) NH4Cl, CuSO4, Al(NO3)3, NH4NO3, etc.
(iii) CH3COONH4, Mg(CN)2, CaCO3, (NH4)3PO4, etc.

Chemistry at a Glance Final.pdf 68 4/1/2014 12:26:05 PM


Solution and
Chapter 7
Colligative propertieS

7.1 Definition

A solution is defined as a homogeneous mixture of two or more components having uniform properties
throughout and constitute a single phase.

7.1.1 Components of a Solution


Solutions have two components.
(i) Solute: Component of a solution which is present in a small amount is known
as a solute.
(ii) Solvent: Component of a solution which is present in a large amount and is present in same
physical state as a solution will be known as a solvent.

7.2 ConCentration measurement units


Concentration measurements units are of two types.
(i) Volume independent concentration measurement units
(a) Weight fraction and weight percentage:
w
Weight fraction (w) = (ω) =
W
Weight percentage = w × 100
(b) Mole fraction and mole percentage:
nA
Mole fraction of A(x A ) =
n A + nB
Mole percentage = XA × 100
(c) Molality: It is the number of moles of a solute dissolved in 1 kg of a solvent.
WB
m= ×1000 moles kg–1 i.e., molal
MB × WA

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7.64 Chemistry at a Glance

(ii) Volume dependent concentration measurement units


(a) Volume fraction and volume percentage:
Wt. of solute
(i) For a solid in liquid % by volume = × 100
Volume of solution
Volumeof solute
(ii) For a liquid in liquid and gas in gas, % by volume = × 100
Volumeof solution
(b) Molarity: It is the number of moles of a solute dissolved in one litre of a solution.
It is represented by M.
wB
= M × 1000 ; v is volume of the solution in ml, n is the number of moles of solute, wB is
MB × v
the weight of solute in grams and MB = is the molecular mass of the solute.
(c) Normality: It is defined as the number of gram equivalent of a solute present in one litre of a
solution.
gm equivalent of solute w
= N =
volume of solution in litre E V
where w = Wt. of the solute; E = equivalent weight and V = Volume of the solution in litre.
(d) Strength: Amount of solute in grams present in 1 litre of a solution
w
⇒ S = ; where w = weight of solute in gm and V = volume of the solution in litre.
V
(e) Formality: It is the number of formula units of an ionic species present in one litre of a
solution and it is represented by (F).
Number of formula mass of ion
F=
Volumeof solutionin litre
(f) Parts per million (ppm): Number of parts by mass of solute per 106 parts of the solution.
Mass of solute
Parts per=
million (ppm) × 106
Mass of solution
amount of solute in gram
=ppb × 109
amount of solution in gram
amount of solute in gram
=ppt × 1012
amount of solution in gram

7.2.1 Relationship between various concentration measurement units


X A m.MB x × d × 10
⇔ N = M × n – factor ⇔ = ⇔ N=
X B 1000 EA
x × d × 10 1000M
⇔ M= ⇔ S = M × MA ⇔ m=
MA 1000d − MM A
where N is normality; M is molarity; m is molality; d is density in g/ml; x is % by mass of solute
MA is molecular mass of solute; EA is equivalent weight of solute and S is strength of
solution in g/litre.

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Solution and Colligative Properties 7.65

7.3 solubility

The solubility of a solid in a liquid depends upon ‘lattice energy’ and ‘hydration energy’. Lattice energy is
the amount of energy required to dissociate one mole of an ionic crystal into its ions. Hydration energy
is the amount of energy released when one mole of ions undergo hydration. If hydration energy > lattice
energy, the solid dissolves otherwise not.
S × 10
⇔ m= , where S is solubility.
MA
⇔ Solubility is the maximum amount of solute dissolved in 100 g of the solvent.

7.4 faCtors affeCting solubility of gases in liquiD

(a) Nature of the gas: More liquefiable gases possess higher solubility.
(b) Nature of the solvent:
(c) Effect of Temperature: On the basis of the effect of temperature on solubility in water, the various
ionic substances are divided into three categories.
(a) Those whose solubility increases continuously with increase of temperature.
For example, NaNO3, KNO3, NaCl, etc.

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(b) Those whose solubility decreases continuously with increase of temperature. For example, cerium
sulphate, lithium carbonate, sodium carbonate monohydrate (Na2CO3H2O), etc.

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Chemistry at a Glance Final.pdf 71 4/1/2014 12:26:05 PM


7.66 Chemistry at a Glance

(c) Those substances whose solubility does not increase or


decrease continuosly. There are some substances which 
1+12

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on heating change at a particular temperature from one 
polymorphic form to another (like a to b-form as in the

case of ammonium nitrate) or from one hydrated form &D&O+2
to another (like CaCl2.6H2O → CaCl2.4H2O → 
CaCl2.2H2O) or from hydrated to anhydrous form (e.g., &D&O+2

Na2SO4.10H2O → Na2SO4) Such substances do not show &D&O+2
a continuous increase or decrease of solubility. For  1D62
1D 62 + 2
  
example, in case of sodium sulphate, the solubility first 
increase upto 32.4°C and then begins to decrease. The
    
temperature at which one form of the substance changes
ƒ&
into another is called transition temperature. Thus, in 7HPSHUDWXUH ƒ&
case of sodium sulphate,
Above 32.4° C
 Na 2SO4
Na 2SO4 ⋅10H2O 
Below 32.4° C

On increasing temperature, solubility of a gaseous solute in liquid decreases


CO2(g) + H2O(l) → CO2(l) + H2O(l) DH = –ve
 S  ∆Hsoln  1 1 
Clausius–Clapeyron Equation: =
log10  2   − 
 S1  2.303 R  T1 T2 
where S1 and S2 are solubilities of gas at temperature T1 and T2.
(d) Effect of Pressure: The relationship between the solubility
and pressure is given by Henry’s law.
1
Henry’s Law: The solubility of a gas at a given temperature is
directly proportional to the pressure of the gas in equilibrium with
the liquid at that temperature 3UHVVXUH 2
+H
⇒ S α P ⇒ S = kP
Alteranatively, mole fraction of the gas dissolved in the solution ;$
is directly proportional to the partial pressure of the gas over the
solution Pgas × Xgas

⇒ PA = KH XA.
where KH is known as Henry’s constant. Its unit is the unit of pressure. The value of KH depends only on
temperature as its value increases with temperature.
As the liquification tendency of a gas increases, its solubility in liquid also increases.

7.4.1 Applications of Henry’s Law


(i) High pressured bottles of soft drinks and soda water.
(ii) Deep sea divers dilute O2 with He instead of N2 because of less solubility of He in blood over N2 at
high pressure.
(iii) Storage of acetylene in acetone.
Vapour pressure is independent from volume and surface area of a container.

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Solution and Colligative Properties 7.67

7.4.2 Limitations of Henry’s Law


(i) The pressure is not too high.
(ii) The temperature is not too low.
(iii) The gas is not highly soluble and does not participate into chemical combination with the solvent.
(iv) The gaseous molecule do not dissociate or associate during the process.

7.5 Vapour pressure


The vapour pressure or saturated vapour pressure is defined as the pressure exerted by the vapours of a
solvent when they are in dynamic equilibrium with its liquid at a given temperature.

7.5.1 Factors Affecting Vapour Pressure


(i) Temperature: The vapour pressure increases non-linearly with increasing temperature.
(ii) Nature of solvent: A solvent with higher boiling point, i.e., one having higher attraction among
their molecules (i.e., high Van der Waal’s constant) possesses less tendency for evaporation and thus
has low vapour pressure.
(iii) Addition of a non-volatile solute: A non-volatile solute added to the liquid solution reduces
the capacity of the solvent molecules to move from liquid phase to gas phase as it occupies a part
of surface area available for evaporation. So, rate of evaporation decreases due to which vapour
pressure decreases.

7.5.2 Ideal and non-ideal solution


An ideal solution of the components A and B is defined as the solution in which the intermolecular
interactions between A and B are of the same magnitude as between the pure components or it is a solution
in which there is no volume change and enthalpy change on mixing (DVmixing = 0, DHmixing = 0) or it is a
solution in which each component obeys Raoult’s law at all temperatures and concentrations.

7.5.3 Raoult’s law


The partial pressure of any volatile component at a given temperature is directly proportional to the mole
fraction of a component present in the solution. If pA is the partial pressure of component A
⇒ pA = XA PA° and pB = XB P°B
Raoult’s law in terms of mole fraction of a liquid: If the
vapour of a liquid behaves like an ideal gas, then according
S 3ƒ%
to Dalton’s law of partial pressures, the total vapour pressure S S $î %
P is given by P = xA pA° + xB pB° ⇒ P = pB° + xA (pA° - pB°).
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If A is a more volatile component, then the composition [ %î
S%
of the liquid and vapour that are in mutual equilibrium is S
not necessarily the same. $ [î
$ S
$
ƒ
Let the mole fractions of vapours A and B be yA and yB,
respectively. Let pA and pB be the partial pressures of vapours
[$  0ROHIUDFWLRQ [$ 
A and B, respectively and total pressure P. [%  [% 
1 yA y
⇒ = + B
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7.68 Chemistry at a Glance

Non-ideal solution: The solutions which deviates from ideal behaviour are called non-ideal solutions
or real solutions.
For non-ideal solutions
1. Raoult’s law is not obeyed.
2. DHmixing ≠ 0.
3. DVmixing ≠ 0.

Positive Deviation from Raoult’s law Negative Deviation from Raoult’s law
(i) DHmix > 0, i.e., heat is absorbed. (i) DHmix < 0, i.e., heat is evolved.
(ii) DVmix > 0, i.e., volume is increased after (ii) DVmix < 0, i.e., volume is decreased during
dissolution. dissolution.
(iii) For a binary solution having component (iii) For a binary solution having component (A + B).
(A + B). pA > p°A XA and pB > pB° XB pA < p°A XA and pB < p°B XB
p > p°A × A + PB° × B ⇒ p < pA° XAB + p°B XB
(iv) Attractive force between A – B should be (iv) Attractive force between A – B should be
weaker than A – A and B – B. stronger than A – A and B – B.
(v) Escaping tendency of both components (v) Escaping tendency of both components A and
A and B is high, so vapour pressure is B is low, so vapour pressure is lower than the
higher than the expected. expected.
(vi) Plot between vapour pressure and mole (vi) Plot between vapour pressure and mole
fraction. fraction.
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e.g., acetone + ethanol; acetone + CS2; H2O e.g., acetone + aniline; acetone + CHCl3; CH3OH +
+ methanol; H2O + ethanol; CCl4 + toluene; CH3COOH; H2O + HNO3, CHCl3.+ diethyl ether;
CCl4 + CHCl3; acetone + C6H6; CCl4 + CH3OH; water + HCl; CH3COOH + pyridine; Chloroform +
cyclohexane + ethanol. benzene.

7.5.4 Fractional Distillation


The process of separation of one liquid from another liquid having different boiling point by distillation
is termed fractional distillation. The separation is possible only when the vapour phase has a composition
different from that of the boiling liquid mixture.

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Solution and Colligative Properties 7.69

Note:
T × y is known as tie line at which, a liquid with composition x will be in equilibrium with a vapour of composition y at
the temperature T.
Vapour

T
Boiling temperature
x y
Liquid

Pure B Pure A
Mole fraction

Azeotropic mixture: For a non-ideal solution there does exist a composition at which equilibrium com-
position of vapour and liquid becomes same. This mixture is called azeotropic mixture. At this point,
distillation becomes useless because no separation is possible. Azeotropic mixtures have a constant boiling
point. Azeotropic mixtures are of two types.
(i) Minimum boiling azeotropic mixture and
(ii) Maximum boiling azeotropic mixture
(i) Minimum boiling azeotropic mixture:

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7

796;

e.g., (a) water–ethanol mixture (95.6 per cent ethanol) at 78.15°C


(b) pyridine–water mixture (57per cent pyridine) at 92.6°C
(c) Ethanol–benzene mixture (32.4 per cent ethanol) at 67.8°C
%RLOLQJ7HPSHUDWXUH ƒF

(d) Acetic acid–toluene mixture (28 per cent acetic acid) at 105.4°C. <9V7
9DSRXU
(ii) Maximum boiling azeotropic mixture.
79V;
e.g., (a) Nitric acid–water mixture (68 per cent nitric acid) at 125.5°C
/LTXLG
(b) Acetic acid–pyridine mixture (65 per cent pyridine) at139.0°C.
(c) Chloroform–acetone mixture (80 per cent chloroform) at 65.0°C
3 DWP
(d) Hydrochloric acid–water mixture (79.8 per cent water) at 108.6°C  0ROHIUDFWLRQ 

Chemistry at a Glance Final.pdf 75 4/1/2014 12:26:06 PM


7.70 Chemistry at a Glance

7.6 ColligatiVe properties

Colligative properties are those which depend entirely upon the number of particles of the solute con-
tained in a known volume of a given solvent and not at all upon the nature (i.e., chemical composition) of
the solute.
The various colligative properties are:

(i) Relative lowering in vapour pressure.


(ii) Osmotic pressure
(iii) Elevation in boiling point.
(iv) Depression in freezing point.
 In colligative properties solute is invariably taken as non-volatile. Colligative properties are essentially
the properties of the dilute solutions, i.e., ideal solutions.

Relative Lowering in Vapour Pressure

According to Raoult’s law, ‘The relative lowering in vapour pressure of a dilute solution is equal to mole
fraction of the solute present in the solution’.
If n is the number of moles of a solute and N is the number of moles of the solvent,
p − ps n
then, from Raoult’s law, o= = X solute .
p0 n+N
If m is the molality of the solution and M2 is the molecular mass of the solvent, then for a dilute solution.
p o − ps mM2
= X= ; where X is the mole fraction of the solute.
p0 1000

Experimental determination of relative lowering in vapour pressure


(i) Static method: In this method, differential manometer is used.
(ii) Dynamic method: This method is also known as Ostwald and Wacker method.

7.7 osmotiC pressure

Osmosis is defined as the spontaneous flow of solvent molecules through a semi-permeable membrane
from a pure solvent to a solution or from a dilute to a concentrated solution.
‘The extra pressure developed on the solution side as a result of the solvent flow is called osmotic
pressure’. It is represented by p.
(a) Determination of osmotic pressure
(i) Berkeley and Hartley’s method: The best known method for measurement of osmotic
pressure was given by Berkeley and Hartley. In this method, a porcelain tube containing copper
ferrocyanide membrane in its walls is enclosed in a metallic jacket. This technique permits quick
determinations of osmotic pressure. Here instead of measuring developed as a result of the entry
of the solvent into the solution gradually increasing pressure is applied on the solution itself and
the pressure which is just enough to prevent the entry of the solvent into the solution is known
as osmotic pressure.

Chemistry at a Glance Final.pdf 76 4/1/2014 12:26:06 PM


Solution and Colligative Properties 7.71

(ii) Townsend’s porous disc method


(iii) Morse and frazer’s method
(b) 1. Comparison of solutions in terms of osmotic pressure:
(i) Hypotonic solution: A solution of low osmotic pressure is termed a hypotonic solution.
(ii) Hypertonic solution: A solution of high osmotic pressure is termed a hypertonic
solution.
(iii) Isotonic solution: Solutions having same osmotic pressures are termed isotonic
solutions.
2. Biological importance of osmosis:
(i) The pressure developed inside a cell due to the inflow of water is called turgor.
(ii) If the cell comes in contact with a solution of higher osmotic pressure, the cell would
shrink due to flow of water from the cell through the cell memtrane. This shrinking of the
cell is called plasmolysis or crenation (Osmotic Pressure (p) = CRT, where C is the molar
concentration).

7.7.1 Applications of Osmotic Pressure


Osmosis is the phenomenon in which there is a net flow of solvent molecules from the solvent to the
solution or from a less concentrated solution to a more concentrated solution through a semi-permeable
membrane.

Osmotic pressure is the equilibrium hydrostatic pressure of the column set up as a result of osmosis or it
is the minimum pressure that must be applied on the solution to prevent the entry of the solvent into the
solution through the semi-permeable membrane.
Molecular masses of polymers are best determined by osmotic pressure method firstly because other
colligative properties give so low values that they cannot be measured accurately and secondly, osmotic
pressure measurements can be made at room temperature and do not require heating which may change
the nature of the polymer.

7.8 eleVation in boiling point

The boiling point (Tb) of a liquid is the temperature at which its vapour pressure is equal to the atmospheric
pressure. When a non-volatile solute is added to a liquid, the vapour pressure of the liquid is decreased.
Hence, it must be heated to a higher temperature in order that its vapour pressure becomes equal to that
of the atmospheric pressure.
Elevation of boiling point (DTb) = Boiling point of the solution(Tb) - Boiling point of pure
solvent (Tb°).
DTb = Kb × m; Kb is also known as ebullioscopic constant.
Method for the determination of elevation of boiling point is known as ebullioscopy.
RTb°2
Kb = , where LV is the latent heat of vapourization per gram of the solvent.
1000L v

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7.72 Chemistry at a Glance

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7.9 Depression in freezing point


Freezing point of a substance is defined as the temperature at which the vapour pressure of the liquid is
equal to the vapour pressure of the corresponding solid.
When a non-volatile solute is added to a liquid, the escaping tendency of solvent molecules from
liquid to solid phase diminishes, whereas the reverse escaping tendency from solid to liquid phase remains
unaffected.
Depression in freezing point (DTf ) = freezing point of the solvent-freezing point of the solution.
RTf°2
DTf = Kfm; K f = where kf is also known as cryoscopic constant.
1000L f

7.10 abnormal ColligatiVe properties

When the molecular mass of a substance is determined by using colligative properties, does not come out
to be same as expected theoretically, it is said to show abnormal molecular mass.
Abnormal molecular mass is obtained when the substance in the solution undergoes dissociation
(e.g., NaCl in water) or association (e.g., organic acids in benzene). Dissociation results in the increase in
the number of particles and hence increase in the value of colligative property and decrease in the mo-
lecular mass. Association results in the reverse.

7.10.1 Van’t Hoff Factor


This is the ratio of the experimental value of the colligative property to the calculated value of the colliga-
tive property, i.e.,
1
As molecular mass ∝
Colligative property
Experimental value of the colligative property Calculated molecular mass MC
i= = ; i =
Calculated value of the colligative property Observed molecular mass M0
Modified formulae for substances undergoing dissociation or association in the solution are
DTb = iKbm; DTf = i Kf m and p = icRT.

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Solution and Colligative Properties 7.73

7.10.2 Degree of Dissociation


If one molecule of a substance A dissociates to form n molecules or ions and a is the degree of dissociation,
then starting with one mole of A
(A)n ⇌ nA
t=0 1 mole 0
t = teq 1–a na
Total number of moles at equilibrium = 1 – a + na
1 − α + nα i −1
i= or α =
1 n −1
In n molecules of a substance A associate to form An and a is the degree of association then starting
with one mole of A
nA → (A)n
t=0 1 mole 0
t = teq 1–a α/n
α
Total number of moles at equilibrium = 1 − α +
n
α
1− α + n
i= n or α= (1 − i)
1 n −1

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Chapter 8 Solid State

8.1 Definition

The solid state represents the physical state of matter in which the constituent molecules, atoms or ions
have no translatory motion although they vibrate about the fixed position that they occupy in a crystal
lattice.

8.2 ClassifiCation of soliDs

They are of two types: Crystalline and Amorphous solids

8.2.1 Comparative Study Between Crystalline and


Amorphous Solids

S. No. Property Crystalline solids Amorphous solids


1 Shape They have definite and regular They do not have definite and
geometrical form regular geometrical form. They are
considered as super cooled liquid.
2 Melting point They have definite and sharp Gradually softer over a range of
melting point temperature
3 Heat of fusion They have a definite heat of They do not have definite heat of
fusion fusion
4 Compressibility They are rigid and They may be compressed to any
incompressible appreciable extent.
5 Cutting with They can break into two pieces They can break into two pieces with
a tool with plane and smooth surface irrregular surface
6 Range order They have a long-range order They have a short-range order
in terms of arrangement of
constituents

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Solid State 8.75

S. No. Property Crystalline solids Amorphous solids


7 Isotropy and They are anisotropic in nature They are isotropic in nature
anisotropy
8 Examples Quartz, diamond, NaCl, KCl, etc. Glass, rubber, plastics, etc.

8.2.2 Classification of Crystalline Solid

S. Types of Contituent Bonding/ Examples Physical Electrical Melting


No. solids particles attractive nature conductivity point
forces
1. Molecular solid
(i) Non-polar Molecules Dispersion Ar, CCl4, Soft Insulator Very low
forces H2, I2, CO2
(ii) Polar Dipole- HCl, SO2 Soft Insulator Low
dipole
interactions
(iii) Hydrogen Hydrogen H2O (ice) Hard Insulator Low
bonding bonding

2. Ionic solid Ions Coulombic NaCl, Hard but Insulators in High


or MgO, ZnS, brittle solid state but
electrostatic CaF2 conductors in
molten state
and in aqueous
solutions

3. Metallic solids Positive ions Metallic Fe, Cu, Ag, Hard but Conductors Fairly
in a sea of bonding Mg malleable in solid state high
delocalized and as well as in
electrons ductile molten state

4. Covalent or Atoms Covalent SiO2 Hard and Insulator and Very high
network solids bonding (quartz), soft conductor
SiC, (exception)
(diamond),
AlN, Cgraphite

1. By heating and cooling, amorphous solid acquires some crystalline characteristic; due to this fact, old
window glass panels look milky.
2. Amorphous solids show fluidity under the influence of gravity; due to this fact, old window glass
panels become thick at the bottom.
3. Amorphous silicon is one of the best photovoltaic material used for converting sunlight into
electricity. nm

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8.76 Chemistry at a Glance

8.3 analysis of Crystalline soliD

8.3.1 Crystal
A regular arrangement of the constituent particles of a crystal in the three-dimensional space is called
crystal lattice or space lattice.
Unit cell: The smallest three-dimensional portion of the space lattice which when repeated over and over
again in different directions produces the complete space lattice is called the unit cell.

8.3.2 Types of Unit Cells

(i) Simple. Here, the particles are present only on the corners. It is represented by P.
(ii) Face-centred. Here in addition to the particles on the corners, there is one particle present on the
centre of every face. It is represented by F.
(iii) End centred. Here in addition to the particles on the corners, there is one particle in the centre of
two opposite faces. It is represented by C.
(iv) Body-centred. Here in addition to the particles on the corners, there is one particle present with
in the body of the unit cell. It is represented by I.

8.3.3 Types of Crystal system and Bravais Lattice

S. No. System Length Angle Parameter Bravais Examples


Parameter Lattice

1. Cubic a=b=c α = b = g = 90° P,I,F NaCl, KCl, ZnS, diamond,


alums, CaF2, Pb, Ag, Hg.

2. Orthorhombic a≠b≠c α = b = g = 90° P,I,F,C KNO3, BaSO4, K2SO4,


rhombic sulphur, PbCO3

3. Tetragonal a=b≠c α = b = g = 90° P,I TiO2, PbWO4, SnO2,


NH4Br, NiSO4

4. Monoclinic a≠b≠c α = g = 90° , b ≠ 90° P,C Monoclinic sulphur,


KClO3, CaSO.2H2O,
Na2B4O7.10H2O,
Na2SO4.10H2O

5. Triclinic a≠b≠c α ≠ b ≠ g ≠ 90° P CuSO4.5H2O, H3BO3,


K2Cr2O7

6. Hexagonal a=b≠c α = b = 90°, g ≠ 120° P ZnO, CdS, HgS, SiC, Agl,


Pbl2, Mg, graphite

7. Rhombohedral a=b=c α = b = g ≠ 90° P NaNO3, ICl, quartz,


or Trigonal CaCO3

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Solid State 8.77

8.4 Bragg’s equation

2d Sin θ = n λ
where d = distance between successive atomic planes
θ = angle of the incident X-rays with the crystal surface i.e., glancing angle
λ = wavelength of the X-rays used
n = 1,2,3.... called the order of diffraction

Note:
The diffracted beam makes an angle of 2θ with the direction of the incident beam.

8.5 lattiCe point anD their ContriBution per unit Cell

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Note:
Number of atoms present per unit cell is called rank of unit cell.

8.6 analysis of Bravais lattiCes Belonging to


CuBiC system

In cubic arrangement, three kinds of Bravais lattices are there.


(i) Primitive or simple cubic lattice: In a simple cubic lattice, constituents are present
only at the corner of each unit cell. Let the length of edge of cube is a and radius of each
atom is r.
Therefore, radius of atom (r) = a/2
Rank of unit cell = 8 × 1/8 = 1
Percentage occupied space = 52.4 per cent

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8.78 Chemistry at a Glance

(ii) Body centered cubic(BCC) lattice:


In a body centered cubic lattice arrangement, constituents are present at the corners as well as at the
centre of each cube.

a 3
Therefore, radius of atom r =
4
1
Rank of unit cell = 8 × + 1× 1 =2
8
Percentage occupied space = 68 per cent
(iii) Face centered cubic (FCC) lattice:
In a face centered cubic arrangement, constituents are present at the corners as well as at the centre
of each of the six faces of the cube.
A ∆ C
C B A
B

A
A Unit cell: Face centered cubic (FCC)
Coordination number = 12
% Space occupied = 74
Therefore, radius of atom (r) = a/2√2
Rank of unit cell = 8 × 1/8 + 6 × 1/2 = 4
Percentage occupied space = 74 per cent

8.7 Closest paCking of sphere

In crystals, the atoms, ions or molecules are arranged in a regular way in three-dimensional space.
The arrangement has minimum energy and hence, maximum stability. For maximum stability,
a constituent in the aggregate must be surrounded by the maximum of neighbours. This is called the
close packing.
In a two-dimensional plane, each sphere is in contact with six other spheres (all are
uniform in size) in close packing. Let us denote this layer of spheres by A. Around a sphere x,
six vacant sites are leveled as 1, 2, 3, 4, 5 and 6. Let us denote the second layer of spheres by B.
We can prepare the second layer by putting spheres either on vacant sites 1, 3, 5 or on vacant
sites 2, 4 and 6.
Two dimensional bravais lattices passes five types of unit cell such as square, rectangular,
parallelogram, hexagonal and rhombic.

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Solid State 8.79

8.7.1 Two-dimensional lattice


A B

A A
A B
A A

Square closed packing Hexagonal closed packing

8.7.2 Three-dimensional lattice


Octahedral
2 void
1 3
Tetrahedral
void 6 4
5

8.8 hexagonal CloseD- paCkeD struCture

In this arrangement constituents are present at corner and at face centre and three constituents are present
at midway of unit cell in the form of an equilateral triangle.

A
A

C
B
B

A A

2r sin 60°
2r

1 1
Rank of unit cell = 12 × + 2 × + 3 × 1 =;
6 Number of octahedral void/unit cell = 6
6 2
Number of tetrahedral void/unit cell = 12; Volume of unit cell = Base area × height of unit cell
2
Base area = 6 3r 2 ; Height of unit cell = 4 × ×r
3
Volume of unit cell = 24 2r 3 ; Packing fraction = 74 per cent
Layered structure ABABAB…..type; e.g., He, H2, Cr, Be, Mg, Ca, Mo, V, Zn, Co, Cd, etc.

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8.80 Chemistry at a Glance

8.9 analysis of voiDs


8.9.1 Coordination Number
It is defined as the number of nearest neighbours that an atom has in a unit cell. In a crystal, there exists
two types of coordination number.
1. Primary coordination number 2. Secondary coordination number

8.9.2 Primary Coordination Number.


Number of nearest oppositely charged constituents in surrounding of a given constituent is called primary
coordination number. Primary coordination number depends upon the type of voids present inside the
crystal which inturn is governed by the radius ratio value.

8.10 raDius ratio


An ionic compound will have more stability if each cation is surrounded by maximum anions and vice
versa because the magnitude of electrostatic force of attraction will be maximum. The number of oppositely
charged ions surrounding each ion is known as coordination number and it depends upon the size of
cation and anion or the ratio of their radii which is known as radius ratio.
Radius of cation(r+ )
Radius ratio =
Radius of anion(r− )

Primary Radius Type of Geometry


Co-ordination Number Ration r+/r– Void
2 0–0.155 Linear

3 0.155–0.225 Triangular

4 0.225–0.414 Tetrahedral

6 0.414–0.732 Octahedral

8 0.732–1.0 Cubic

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Solid State 8.81

8.10.1 Secondary Coordination Number

Number of nearest like constituents in surrounding of a given constituent is called second-


ary coordination number. Secondary coordination number depends upon the type of Bravais
lattice present.

Unit Cell Secondary Coordination Number


Simple cubic 6
Body centered cubic 8
Face centered cubic 12
Hexagonal closed packed 12

8.11 Density of soliD

Z× M
ρ= g / cm3
a 3 × N 0 × 10 −30
where Z = No. of atoms present per unit cell
M = Atomic mass of the element
a = Edge of the cubic crystal in pm.
N0 = Avogadro’s number

8.12 analysis of various ioniC struCtures

S. No. Types of Brief Examples Co-ordination Rank of % Occupied


Crystal Description Number Crystal Space
Structure
Type Rock salt Chloride ions Halides of Li, Na, Na = 6 4 79.34%
AB (i) type (Cl) has FCC K, Rb, AgF, AgBr, Cl– = 6
arrangement in NHCl, NHBr, NHl
which sodium oxides and sul-
ions (Na) phides of alkaline
occupy all the earth metal except
octahedral sites BeO and BeS.
(ii) Caesium Chloride ions CsCl, CsBr, Csl, Cs+ = 8 1 72.93%
chloride (Cl) adopts a CsCN, TlCl, TlBr, Ci– = 8
type simple cubic Tll, TlCn, Ticl,
lattice in which TiBr, Til
caesium ions
(Cs) are present
at body centres
(cubic sites)
(Continued)

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8.82 Chemistry at a Glance

S. No. Types of Brief Examples Co-ordination Rank of % Occupied


Crystal Description Number Crystal Space
Structure
(iii) Zinc Sulphide ions CuCl, CuBr, Cul, Zn2+ = 8 4 74.84%
blende type (S) adopts a Agl, BeS, BeO S2– = 8
FCC arrange-
ment in which
zinc ions (Zn)
are present
in alternative
tetrahedral
sites.
Type Fluorite Cation BaF2, BaCl2, SrF, Ca2+ = 8 4 75.7%
AB2 type occupies FCC SrCl2, CdF2, PdF2, F– = 4
lattice whereas etc.
anion occupies
all the tetrahe-
dral voids.
Type Anti- Oxide ions (O2) Na2O, Li2O, K2O, Na+ = 8 4 75.7%
A 2B fluorite adopts FCC Na2S, Li2S, K2S, etc. O2– = 4
type arrangement in
which sodium
ions (Na+) are
present in all
the tetrahedral
sites.

1. Corundum structure
The closest packing of anions is hexagonal rather than cubic. Not all the octahedral holes are
occupied, only 2/3 of them contain cations. There are 6 octahedral holes per unit cell in HCP anions.
Number of anions = 12 (at corner) × 1/6 + 2 (at face center) × ½ + 3 (within unit cell) × 1 = 6.
Number of cations = 6 (octahedral void) × 2/3 × 1 = 4.
General formulae = A4X6 or A2X3. e.g., Fe2O3, AlO2O3, Cr2O3 etc.
2. Spinel structure
Oxide ions are arrangement in CCP whereas 1/8 tetrahedral void are occupied by Zn2+ and 50 per
cent of octahedral holes are occupied by Fe3+ ions.
Formulae of the compound number of O2– ions = 8 (at corner) × 1/8 + 6(at face centre) × 1/2 = 4
Number of Zn2+ ions = 8 (at tetrahedral void) × 1/8 × 1 = 1
Number of Fe3+ ions = 4(at octahedral void) × ½ × 1 = 2
i.e., ZnFe2O4
3. Diamond structure
The unit cell of diamond is made of 8 atoms. Four carbon atoms occupy CCP lattice while remaining
four atoms occupy half of the tetrahedral voids alternately.

8.13 imperfeCtion or DefeCts in soliDs


The term imperfection or defect is generally used to describe any deviation of the ideally perfect crystal
from the periodic arrangement of its constituents.

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Solid State 8.83

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Classification of imperfection:
1. Point defects or atomic defects:
If the deviation occurs at a particular point because of missing atoms, displaced atoms or extra atoms
then imperfection is termed as point defect. They are of two types as discussed here under.
(a) Stoichiometric defects: In this type of defect the ratio of cation and anion remains same as
represented by molecular formulae. These are of two types as discussed here under.
(i) Schottkey defects: When a cation and anion are missing from normal position in the
crystal lattice, we get voids or vacancies in the crystal.
This sort of defect occurs mainly in strong ionic compounds, i.e., where the positive and negative
ions are of comparable size and with high cordination number, e.g., KCl, KBr and NaCl, etc.
Due to Schottkey defect in a crystal
(i) density of crystal decreases. (ii) electrical conductivity increases.
(iii) stability of crystal decreases. (iv) LE of the crystal decreases.
(ii) Frenkel defects : In this defect an ion is not completely missing but shifts to an interstitial
position in the lattice leaving a vacancy in its own position. This type of defect is favoured
by a large difference in size between the positive and negative ions and low coordination
number. e.g. ZnS, AgCl, AgBr, AgI, etc. Due to frenkel defect in a crystal.
(i) Density of crystal does not change. (ii) Electrical conduction increases.
(iii) Stability as well as L.E. decreases. (iv) Leading to high dielectric constant.
2. Non-stoichiometric defects :
This defect results in change in the ratio of cations to that of anions. It can be of two types.
(i) Metal excess (ii) Metal deficiency
Metal excess: Metal excess defects occur in two different ways.
(a) Anionic deficiency or F centres: When crystals of NaCl are heated in an atmosphere of
sodium vapour, the sodium atoms are deposited on the surface of the crystal. The Cl– ions diffuse
to the surface of the crystal and combine with Na atoms to give NaCl. This happens by loss of
electron by sodium to form Na+ ions. The released electrons diffuse into the crystal and occupy
anionic sites. As a result, the crystal now has an excess of sodium. The anionic sites occupied by
unpaired electrons are called f-centres (from the German word Farbenzenter for colour centre).
Due to f centres solids are
(i) colored (f means farbe means colour)
(ii) paramagnetic

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8.84 Chemistry at a Glance

(iii) capable of becoming photoconductors


(iv) such that capable of becoming n-type semiconductors
(v) their density of crystal decreases
(b) Cationic excess: In this type of metal excess defects, an extra +ve ion occupies an interstitial
position in the lattice and electrical neutrality is maintained by the inclusion of an interstitial electron.
This kind of metal excess defect is much more common than the first and is generally formed in
crystals which would be expected to form Frenkel defects, e.g., ZnO, CdO, Fe2O3 and Cr2O3.
Due to this type of defect solids are:
(i) colored
(ii) paramagnetic
(iii) capable of becoming photoconductors
(iv) such that the density of crystal decreases
e.g., ZnO is white when cold but yellow when hot.

Soln. ZnO  → Zn2+ + 1/2O2 + 2e–.
Metal deficiency: This type of defect is common among metals showing variable valency. In this
defect a metal cation is missing from lattice site and some other cation of higher oxidation state ac-
quire vacancy in order to maintain electrical neutrality. E.g., FeO, FeS, NiO.
Due to metal deficiency
(i) density decreases (ii) lattice energy as well as stability decreases
Impurity defect: If molten NaCl containing a little amount of SrCl2 is crystallized, some of the
sites of Na+ ions are occupied by Sr2+ and each Sr2+ replaces two Na+ ions. It occupies the site of one
ion and the other site remains vacant. The cationic vacancies thus produced are equal in number to
that of Sr2+ ions. Another similar example is the solid solution of CdCl2 and AgCl. Whenever we add
elements of group 13 such as Ga or Al and the elements of group 15 such as P or As to the covalent
solid of group 14 such as Si or Ge, then impurity defect is obtained.
Addition of group 13 element results in the electron deficiency in the crystal and creates holes. This
type of semiconductor is called p type semiconductor.
On the other hand, the addition of elements of group 15 produces excess electrons, in the crystal, due
to which n-type semiconductors are formed.

8.14 magnetiC properties of soliDs

(i) Diamagnetic substances: These substances are weakly repelled by the magnetic field and do not
have any unpaired electron. e.g., NaCl, N2, Zn, Cd, Cu+, TiO2, V2O5, etc.
(ii) Paramagnetic substances: The substances which are weakly attracted by external magnetic field, are
called paramagnetic substances. This property is exhibited by solids due to the presence of unpaired
electrons. The unpaired electrons show magnetic moment due to spin of electrons but their random
orientation cancel each other’s effect. However, in the presence of an external magnetic field, these
unpaired electrons are aligned and show the temporary magnetism.
e.g., Cr., Mn, Ni, Co, VO2, CuO, Cu2+, Ni2+, Fe3+ etc.
(iii) Ferromagnetic substances: ↿↿↿↿↿
Strong magnetic field generated by group of paramagnetic atom also called domain is known as
ferromagnetism and such substances are termed as ferromagnetic substances. These substances are
attracted by the magnetic field and show permanent magnetism even in the absence of a magnetic
field. E.g., Fe, Co, Ni, CrO2, etc.

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Solid State 8.85

(iv) Anti-ferromagnetic Substances: ↿⇂↿⇂↿⇂


The domains explained as above cancel each other due to an exactly antiparallel allignment and
therefore the net magnetic moment is zero. E.g., MnO, MnO2, Mn2O3, CrO3, FeO, Fe2O3, CoO, Co3O4,
NiO V2O5 etc.
(v) Ferrimagnetic Substances: ↿↿⇂↿↿↿⇂
The domains are not aligned in a specific pattern, some are antiparallel while others are parallel thus
the net magnetic moment is not zero but a small value. E.g., Fe3O4, ferrites (MFe2O4) where M is any
divalent cation such as Mg, Zn, Cu, etc.

8.15 DieleCtriC properties of soliDs


A dielectric is a substance in which an electric field gives rise to no net flow of electric charge. This is due
to the fact that electrons in a dielectric are tightly held by individual atoms. However, under the effect of
an applied field displacement of charges takes place, resulting in the creation of dipoles.
The alignment of these dipoles in different ways, i.e., compensatory way (zero dipole or
non-compensatory way (net dipole) impart certain characteristic properties to solids.
1. Piezoelectricity: A dielectric crystal which has a resultant dipole moment can produce or show
electrical property when external pressure, i.e., mechanical stress is applied. Such a crystal is known
as piezoelectric crystal and this property is called piezoelectricity or pressure electricity. Piezoelectric
crystals are used in record players where electrical signals are produced on applying pressure. They
are also used in microphones, ultrasonic generators and sonar detectors. E.g., BaTiO3, PbTiO3, lead
zirconate (PbZrO3), ammonium dihydrogen phosphate (NH4H2PO4) quartz etc.
2. Pyroelectricity: Some polar crystals upon heating produce small electric current. This
phenomenon is known as pyroelectricity. In this process, actually certain atoms or ions get displaced
upon heating, e.g., Tourmaline.
3. Ferroelectricity: In certain piezoelectric crystals, the dipoles are permanently polarized even in the
absence of applied electric field. However, the direction of polarization may change on applying cur-
rent. This phenomenon is known as ferroelectricity and the effect involved is called ferroelectric effect.
e.g., KH2PO4, Rochelle salt [NaOOC CH(OH)CH (OH) COOK] and BaTiO3 (barium titanate).
4. Anti-ferroelectricity. When the dipoles in an alternate lattice point up and down, the two
dipoles cancel one another so that there is no resultant dipole moment. Such crystals are known as
anti-ferroelectric crystals and the phenomenon is called anti-ferroelectricity, e.g., PbZrO3.

8.16 siliCates
Silicates are the compounds having SiO2 tetrahedra as the basic building units.They are linked by corners
and never by edges.

8.16.1 Types of silicates


(i) Orthosilicates which contain discrete SiO4–
4
tetrahedra, e.g., zircon(ZnSiO4) and forestrite(Mg2SiO4).
(ii) Pyrosilicates in which two SiO44– tetrahedra share one corner, e.g., thorteveitite, Se2(Si2O7),
hemimorphite, Zn3(Si3O7), Zn(OH)2, H2O, etc.
(iii) Cyclic/Ring silicates in which two corners are shared to form a closed ring, e.g., beryl, Be3Al2Si6O18.
(iv) Chain silicates in which two corners are shared to form a long chain, e.g., pyroxenes and asbestos.
(v) Sheet silicates in which three corners are shared to form a two-dimensional sheet.
(vi) Three-dimensional silicates in which all the four corners are shared to form a three-dimensional
lay network, e.g., quartz.

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Chapter 9 ChemiCal kinetiCs
9.1 IntroductIon

Chemical kinetics is the branch of science that deals with rate of reaction, the factors affecting the rate of
reaction and mechanism of the reaction.

9.2 rate of reactIon

‘The change in the molar concentration of any reactants or product per unit time is known as rate
of reaction.’
Rate of reaction of reactant A, i.e., rate of disappearance of A

1 dN A  mol 
−rA =−  
V dt  litre sec. 
Rate of reaction of product P, i.e., rate of formation of p

1 dN P  mol 
rP =  
V dt  litre sec. 
• –ve sign means disappearance while +ve sign indicates the formation rate. Units of the
rate of reaction are mol L–1 time–1. Rate of reaction does not remain constant during the
complete reaction because rate depends upon the concentration of reactants which decreases
with time.

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chemical kinetics 9.87

Rate of disappearance of A
1 dN A  mol 
−rA =−   ; –ve sign means disappearance while +ve sign indicates the
V dt  litre second 

formation rate.
Change in conc of one of the reactant or products ∆x
Average rate of reaction: raverage = =
Time taken for the change ∆t

9.3 average and Instantaneous rate of reactIon

The rate measured as average over a long time interval is called average rate and the rate measured
at a particular instant of time (or average rate for an infinitesimally small time interval) is called
instantaneous rate.

9.3.1 Graphical method for determination of rate of reaction


The rate of reaction at any instant of time may be calculated by drawing a tangent to the curve at a point
corresponding to that time and then calculating the slope of the tangent.

9.3.2 Dependency of Rate Equation on Stoichiometry


Considering a single phase reaction aA + bB → rR + sS
rA r r r
The rate of reaction of all reactants and products are related by − =
− B =R =S
a b r s

9.4 factors affectIng rate of reactIon

Reactions involving cleavage of strong bond in reactant molecules are slower when compared to reactions
involving weak bond in reactants molecules
2NO(g) +O2(g) → 2NO2(g) .............(i)
CH4(g)) +2O2 → CO2(g) + H2O .............(ii)
Reaction (ii) is faster, than reaction (i).

9.4.1 Concentration of the Reactants


An increase in the concentration of the reactants increases the reaction rate because increase in concen-
tration brings more frequent collisions between the reactant molecules, thereby increasing the number of
effective collisions which results in a faster chemical change.

9.4.2 Surface area of the reactants


Larger the surface area of the reactants, greater will be the rate of reaction.

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9.88 Chemistry at a Glance

9.4.3 Catalyst
Presence of a catalyst increases as well as decreases the rate of a reaction depending upon the nature
of the catalyst.

9.4.4 Temperature
Reaction rates are normally favoured by increasing temperature.

9.5 elementary and non-elementary reactIons

9.5.1 Elementary Reactions


Reactions in which the rate equation corresponds to a stoichiometric equation are called elementary or
simple reactions. In elementary reactions, only one reaction step is involved.
e.g., for a reaction A + B → R
if –rA = kcA cB
i.e., here rate expression is corresponding to stoichiometry and for elementary reactions order of reac-
tion is equal to its molecularity.

9.5.2 Non-elementary Reaction


When there is no direct correspondence between stoichiometry and rate then we have non-elementary
or complex reactions. Two or more elementary reactions when added give a complex or non-elementary
reactions. The set of elementary reactions which on addition gives a complex reaction is said to be the
mechanism of that reaction.
Example:
Step–I: Slow
N 2O5  → NO2 + NO3

Step–II: N 2O5 + NO3 →


Fast
3NO2 + O2

Step I: is known to be the rate determining step


Rate = K [ N2O5]
If first step of the reaction is the slowest step then molecularity of the slowest step is the order of the
overall reaction. All the reaction steps which appear, before the slowest step must be reversible.
Final rate law must be independent from the concentration of reaction intermediate.

9.6 order of reactIon

The order of a reaction is defined as the number of molecules whose concentrations determine the rate of
the chemical reaction at a given temperature. Alternatively, we may define the order of the reaction as the
sum of powers to which the concentration terms are raised in rate law equation in order to determine the
rate of the reaction.

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chemical kinetics 9.89

e.g., for a reaction aA + bB → Products


Rate α [A] m [B]n
Then, order of reaction with respect to A = m
Then, order of reaction with respect to B = n
\ Overall order of reaction = m + n

9.7 molecularIty of reactIon

The molecularity of an elementary reaction is defined as the minimum number of molecules, atoms or ions
of reactants required for the reaction to occur. Molecularity is a theoretical value and is derived from the
mechanism of the reaction.
e.g., for a reaction aA + bB → Products
Molecularity = a + b
So, if a + b = m + n, then the reaction is called elementary.
Difference between order and molecularity of reaction

Order of Reaction Molecularity of Reaction


(i) Order is an experimental property and it is (i) Molecularity is a theoretical concept which
concerned with kinetics of the reaction. concerned with mechanism of the reaction.
(ii) Order may be any number, integral or (ii) Molecularity is always an integer except zero.
fraction including zero.
(iii) It is defined for both elementary and (iii) Defined only for elementary reaction.
non-elementary reactions.
(iv) Reaction with order ≥3 are rare. (iv) Reaction with molecularity >2 are rare.

9.8 rate constant of the reactIon

The rate constant or velocity constant or specific reaction rate of a reaction, in general, is equal to the rate
of reaction when the concentration of each of the reactants is unity.
e.g., For an elementary reaction
aA + bB + cC → Products
Rate of reaction r = k cAa cBb cCc
If cA = cB = cC = 1, then r = k.
The value of k is independent from concentration; it depends only on the temperature and catalyst used.
unit of rate
=
units of rate constant for nth order reaction, kn = conc1−n time −1
unit of (C n )

9.9 dIfferentIal rate law of a reactIon

It is the differential equation which gives rate of reaction as a function of concentration. For rate
of formation, formation step is +ve while disappearance step is –ve and vice versa for rate of
disappearance.

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9.90 Chemistry at a Glance

RUGHU RUGHU  RUGHU! RUGHU 

U U U U

&ĺ &ĺ &ĺ &ĺ

9.10 Integrated rate law of a reactIon

9.10.1 First-order Reactions


Consider the reaction, A → Products VORSH ±N
F$ OQF$
dc F$ OQF$
Rate of reaction, −rA = − A= kc A
dt
W W
dc
or −r =− =kc c A = c A0 e − kt
ln c A =− kt + ln c A0
dt
Separating and integrating, we get
cA t
dc A c
−∫ =k ∫ d t − ln A =kt ⇒ ln c A =− kt + ln c A0
c A0 cA 0 c A0

2.303 CA
⇒ t= log10 0 ⇒ c A = c A0 e − kt
k CA

9.10.2 Second-order Reactions


Consider an elementary, reaction, A → Products
t=0 c A0
at t cA
dc dc
−rA =− A= kc2A or−r =− =kc2
dt dt
1 1 1 
Rearranging and integrating we =
get t  − 
k  c A c A0 

9.10.3 nth-order Reaction


dc A
Considering an elementary reaction, A → Products, −rA =− =kcnA
dt
dc A
or −r =− =kcn 
dt
&Q±
1  1 1 
=
Integrating, we get t  n−1 − n−1  n ≠ 1  VORSH Q± N
(n − 1)k  c c0  &Q±
For completion of reaction CA = 0 if n > 1, t = ∞. W
Reaction with order n > 1 can never go to completion in finite time.
Reaction with order less than 1 requires finite time for its completion.

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chemical kinetics 9.91

9.10.4 Zero-order Reaction


A reaction is said to be zero order when the rate of reaction is independent of the
concentration of reactants. F
Consider of reaction, A → Products
&
dc c −c
Rate of reaction, −r =− =k ; Integrating on both sides, we get t = 0 .
dt k
W
9.11 half lIfe tIme of a reactIon
The half-life (t1/2) of the reaction is the time needed for the concentration of reactants to drop to one-half
of the original value.
A zero oroler reaction can never he elementary lecause molecularity of a reaction can never be zero.
Fine of complation of zero order reaction is double of its half life time

9.11.1 t1/2 for a First-order Reaction


c A0 1 cA ln2 0.693
When t = t1/2 ; c A = t1/2 =
− ln 0 = =
2 k 2c A0 k k W

For a first-order reaction, half life time is independent from initial concentration &

9.11.2 t1/2 for a Second-order Reaction


1 1
For a second-order reaction, − =
kt .
c A c A0
W
c A0 1
When t = t1/2; c A = ; t1/2 = .
2 c A0 k &

9.11.3 t1/2 of a Zero-order Reaction


For a zero-order reaction, c A0 − c A =
kt
c A0 c A0 W
When t = t1/2 ; c A = ; t1/2 = .
2 2k
&
9.11.4 t1/2 of a nth-order Reaction
For an nth order reaction, c1A−n − c1A−n = k(n − 1)t
0

c A0 6ORSH ±Q
2n−1 − 1
When t = t1/2 ; c A = ; t1/2 =
2 k(n − 1)cnA−01
ORJW 2UGHU
Taking log of both sides, we get RUGHU!
 2 −1  n−1 2UGHU 
log t1/2 =
(1 − n)log c A0 + log  
 k(n − 1)  ORJF$

If we plot a graph of log t1/2 vs. log c A0

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9.92 Chemistry at a Glance

Some important relationship between time for different fraction of reaction of first order
to complete
t75% = 2t1/2; t87.5% = 3t1/2; t93.75% = 4t1/2; t96.87% = 5t1/2; t99.9% = 10t1/2

9.12 experImental method for determInatIon of rate law

9.12.1 Volumetric Method


In this method, a known volume of the reaction mixture is removed at various times and to a larger volume of
ice cold water is rapidly added, which effectively stops the reaction or at least slows it down considerably. This
is widely used in cases where reactants or products are acids or bases or species undergoing a redox reaction.

9.12.1.1 Decomposition of H2O2


H2O2 → H2O + 1/2O2 Volume of KMnO4 used
t=0 c A0 v0
At time t CA v∞
Volume of KMnO4 used is α concentration of H2O2 present
2.303 c A 2.303 V
=k = log 0 log 0 .
t cA t Vt
Acid hydrolysis of ethyl acetate
+
H
CH3 COOC2H5 + H2O  → CH3COOH + C2H5OH Volume of alkali used
t=0 c A0 0 0 v0
At time t cA c A0 − c A c A0 − c A vt
At t = ∞ 0 c A0 c A0 v∞
2.303 V − V0
Volume of alkali used is µ concentration of acid present, k = log ∞ .
t V∞ − Vt

9.13 pressure change method


This is to be used in a gaseous phase reaction. As reaction proceeds, there may be a change in final pressure.
By measuring initial and total pressure at the start and after time t, value of c A0 and cA can be determined
in terms of total pressures for the reactions.
A(g) → yB(g)
At t = 0 P0 0
At time t p0 – x yx
2.303 P ( y −1)
k= log 0
t y P0 − Pt
e.g., CH3COCH3 (g) → CO(g) + CH3 - CH3 (g) here y = 2
2.303 P0
k= log
t 2P0 − Pt

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chemical kinetics 9.93

9.14 volume measurement method

This method is to be used where we can measure the volume of one of gaseous substances evolved.
N2O5(g) → 2NO2(g) + 1/2 O2(g)
At t = 0 a 0 0
At time t a–x 2x x/2
At t = ∞ 0 2a a/2
2.303 V∞
k= log .
t (V∞ − Vt )

9.14.1 In Terms of Rotation of Optically Active Species


Angle of rotation is directly proportional to the concentration of optically active substance present.
Hydrolysis of sucrose:

C12H22O11 + H2O  → C 6H12O6 + C 6H12O6


sucrose (Dextro) Glucose fructose

(Laevo)

Angle of rotation of plane polarized light at:


(i) t = 0 q0
(ii) t qt
(iii) t = ∞ q∞
Angle of rotation (q) is µ total concentration of optically active substance present
2.303 θ −θ
k= log ∞ 0
t θ∞ − θ t

9.15 temperature-dependent term of a rate equatIon


9.15.1 Effect of Temperature on Reaction Rates
It is a common experience that increase of temperature has marked effect on the rate of a
chemical reaction.
‘The ratio of the rate constants of a reaction at two temperatures differing by 10°C is known as the tem-
perature coefficient of the reaction. The temperatures usually selected for this purpose are 25°C and 35°C.’
Rate constant at (T + 10)°C K T2
= µ = 2 to 3 ; = µ (T2 −T1 )/10
Rate constant at T°C K T1

9.16 collIsIon theory


Increase in rate of a reaction with temperature can be explained by collision theory. This theory was
proposed by Arrhenius and vant Hoff. Important features of this theory are listed hereunder:
(i) For chemical reactions to occur, there must be collisions between the reactant molecules.
However, most of the collisions taking place between the reactant molecules are ineffective.

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9.94 Chemistry at a Glance

(ii) Only those collisions result in chemical reactions in which the colliding molecules are associated
with a certain minimum energy called the threshold energy.
(iii) Reactant molecules having energy equal or greater than the threshold are called active molecules
and those having energy less than the threshold are called passive molecules.
(iv) At a given temperature there exists a dynamic equilibrium between active and passive molecules.
The process of transformation from passive to active molecules being endothermic, increase of
temperature increases the number of active molecules and hence the rate of reaction.
Passive molecule ⇌ Active molecules; DH = +ve.

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9.16.1 Activation energy


The extra energy that the reactant molecule required in order to cross the energy barrier is known as
activation energy (Ea). (Ea) = Threshold energy–average energy.

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9.16.2 Energy Barrier


The minimum amount of energy that the reactant molecule has in order to convert into product is known
as threshold energy and this state is termed as energy barrier.
• DH = Eaf – Eab
• Whether given reaction is slow or fast at a given temperature depends upon the activation energy of the
reaction. A reaction which has lower activation energy will proceed at a faster rate at a given temperature.

9.16.3 Effective Collision


According to the collision theory, effective collision is one which results into the product.

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chemical kinetics 9.95

9.16.4 Collision Frequency


Number of collisions that taken place per second per unit volume of the reaction mixture is called
collision frequency.

9.17 the arrhenIus theory

Arrhenius proposed an empirical equation for calculating the energy of


OQ$
activation of a reaction having rate constant at temperature T. ±(D
VORSH
−E a 5
=
ln k + ln A
RT OQN
− Ea /RT
K = Ae ; where Ea is activation energy of the reaction.
Where a is Arrhenius constant or pre-exponential factor or frequency
7
factor.
• Both Ea and A are independent from temperature.
• Arrhenius equation cannot be used for nuclear reactions.
k 2 Ea  T2 − T1 
• ln =   . This equation is known as the integrated Arrhenius equation.
k1 T  T1T2 

9.18 photochemIcal reactIons


Photochemical reactions are those reactions which take place only in the presence of light but not in the
dark. Red light has lowest energy. Hence, photochemical reactions which can be initiated by red light can
be initiated by all other radiations of visible light.

9.18.1 Characteristic of Photochemical Reactions


(i) Temperature has very little effect on the rate of a photochemical reaction. Instead, the intensity of
light has a marked effect.
(ii) Free energy change (DG) of a photochemical reaction may not be negative. This is because a part
of the light energy absorbed by the reaction is coverted into free energy of the products.
(iii) A photosensitizer is a substance which when added to a reaction mixture helps to start the photo-
chemical reaction but itself does not undergo any chemical change. e.g., chlorophyll in photosyn-
thesis and Hg vapours in dissociation of H2.
(iv) Quantum yield or quantum efficiency of a photochemical reaction is
Number of molecules reacting in a given time
ϕ=
Number of quanta of light absorbed in the same time
(v) Photosynthesis of HCl has high quantum yield, whereas photosynthesis of HBr has low quantum
yield. This is because after the primary process (Cl 
hv hv
→ 2Cl or Br  → 2Br) , the first step of
2 2

the secondary process of photosynthesis of HCl (Cl + H2 → HCl + H) is exothermic, whereas that
of HBr (Br + H2 → HBr + H) is endothermic.
(vi) Vision is a fast photochemical reaction in which the compound, retinal, present in the eye under-
goes geometrical isomerization by absorbing a photon of light.

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Chapter 10eleCtroChemistry
10.1 IntroductIon

Electrochemistry is a branch of science which deals with chemical changes caused in matter by passage of
electric current and conversion of chemical energy into electrical energy and vice versa.
All electrochemical reactions involve transfer of electrons and are therefore redox reactions.
Substances which allow the passage of electric current through them are called electrical conductors
while those which do not are called insulators.

10.2 ElEctrIcal conductIon

The property which allows the flow of electricity through a body is called conduction, and the body which
allows passage of electricity through it is called a conductor. Conductor is of two types as listed hereunder.
(i) Metallic conductor and
(ii) Electrolytic conductor.
Comparative study between metallic and electrolytic conductors:

Metallic conductor Electrolytic Conductor


(i) Electric current flows by movement of (i) Electric current flows by movement
electrons of ion
(ii) No chemical change occurs (ii) Ions are oxidized or reduced at the
electrodes
(iii) It does not involve the transfer of any (iii) It involves transfer of matter in the
matter form of ions
(iv) Ohm’s law is followed (iv) Ohm’s law is followed
(v) Resistance increases with increase of (v) Resistance decreases with increase of
temperature temperature
(vi) Faraday’s law is not followed (vi) Faraday’s law is followed

∎ The average kinetic energy of the solute ions increases as the temperature is raised and therefore,
the resistance of electrolytic conductors generally decreases.

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Electrochemistry 10.97

∎ In case of metallic conduction on increasing temperature the kernels in the metal start vibrating
which hinders the mobility of electrons and thus resistance increases and conductance decreases.
Factors affecting electrolytic conductivity:
(a) The nature of the electrolyte added.
(b) Size of the ions produced and their solvation.
(c) The nature of the solvent and its viscosity.
(d) Concentration of the electrolyte.
(e) Temperature.

10.3 ElEctrolytIc cEll and ElEctrolysIs


In an electrolytic cell, electrons are received from the negative end of the battery by the negative electrode
of the cell, these are used up at the cathode in the form of a reduction reaction. The number of electrons
received at the negative electrodes is given back to the positive end of the battery from the positive elec-
trode of the cell where electrons are released as a result of oxidation.
 ±
H ±
H± ±


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10.3.1 Electrolysis
Faraday’s first law of electrolysis: According to Faraday’s first law of electrolysis, the weight of a sub-
stance deposited is directly proportional to the charge passed through an electrolytic solution.
W = Z × Q;
where ‘Z’ is Electrochemical equivalent of a cell
W=Z×I×t ∵Q=I×t
Faraday’s second law of electrolysis: If same quantity of electricity is passed through two different
electrolytes, then the amount of different substance discharged is proportional to their equivalent masses.
That is, w µ E if Q is constant.
Charge of 1 mole e– = charge of 1 gram equivalent e– = 1 F
\ If 1 gram is passed, then 1 gram equivalent of a substance is discharged.
⇒ If Q = 1 F., then w/E = 1 ⇒ w = E
⇒ E=Z×F ⇒ Z=E/F
EIt MIt
\ = w =
F nF

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10.98 Chemistry at a Glance

10.3.2 Prediction of product of Electrolysis


10.3.2.1 Preferential discharge theory

According to this theory if more than one type of ions are present inside the solution then discharged ion is
the one which requires least amount of energy for their deposition. Amount of energy needed for deposi-
tion is expressed in terms of deposition potential.
1
∎ Deposition potential of a metal ∝ 0
Ered value
∎ Deposition potential of a non-metal ∝ E0red value

(i) Electrolysis of molten sodium chloride


Molten sodium chloride contains Na+ and Cl– ions.
NaCl(l) ⇌ Na+ (l) + Cl– (l)
On passing electricity, Na+ ions move towards cathode while Cl– ions move towards anode.
At cathode: Na+ + e– → Na (reduction, primary change)
At anode: Cl– → Cl • + e– (oxidation, primary change)
Cl• + Cl• → Cl2(g) (secondary change)
(ii) Electrolysis of an aqueous solution of NaCl: Sodium chloride and water ionize as under
NaCl(aq) → Na+(aq) + Cl–(aq)
H2O(l) ⇌ H+(aq) + OH–(aq) (only slightly ionized)
On passing electricity, Na+(aq) and H+(aq) move towards the cathode while Cl–(aq) and OH–(aq) ions
move towards the anode.
At cathode: Both Na+(aq) and H+(aq) are present near the cathode. Since the discharge potential of
H+ ions is lower than that of Na+ ions, therefore, H+ ions are discharged in preference to Na+ ions.
H+ + e– → H• (reduction, primary change)
H• + H• → H2 (g) (secondary change)
Thus, H2 gas is evolved at the cathode while Na+ ions remain in the solution.
At anode: Both Cl– and OH– ions are present near the anode, Since the discharge potential of
Cl– ions is lower than that of OH– ions, therefore, Cl- ions are discharged in preference to OH– ions.
Cl– → Cl• + e– (oxidation, primary change)
Cl• + Cl• → Cl2(g) (secondary change)
Thus, Cl2 gas is evolved at the anode while OH– ions remain in the solution.
(iii) Electrolysis of aqueous CuSO4 using Cu electrode
On passing electricity, Cu2+ and H+ move towards cathode while OH– and SO42– ions move
towards anode. Both Cu2+ and H+ ions are present near the cathode. But the discharge potential
of Cu2+ ions is lower than that of H+ ions, therefore, Cu2+ ions are discharged in preference
to H+ ions.
Cu2+(aq) + 2e– → Cu(s) (reduction, primary change)
At anode: Unlike electrolysis of CuSO4 using platinum electrodes, no ions are liberated here.
Instead, anode itself undergoes oxidation (i.e., loses electrons) to form Cu2+ ions which go into the
solution. This is due to the reason that Cu is more easily oxidised than both OH– and SO42– ions.
Cu(s) → Cu2+(aq) + 2e– (oxidation, primary change)
Thus the net result of electrolysis is that copper is deposited at the cathode from the solution and
an equivalent amount of copper from the anode dissolves into the solution to form Cu2+ ions. This
principle of electrolysis is widely used in electroplating and purification of less reactive metals such
as Pb, Cu, Ag, etc.

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Electrochemistry 10.99

10.4 conductancE MEasurEMEnt

Electrolytic Conductance: The reciprocal of the electrical resistance is called conductance. It is usually
represented by C or G.
1
Thus C =
R
Specific Conductance: ‘The reciprocal of resistivity is known as specific conductivity or simply con-
ductivity’. It is denoted by (kappa) or k. Thus, if k is the specific conductivity and C is the conductance of
the solution, then
R =r (ℓ/A); (where r is a constant of proportionality, called specific resistance or resistivity. Its value
depends upon the material of the conductor.)
R = 1/C and r = 1/k
1 1 
\ = ×
C κ A

κ= C ×
A
Unit of k is W–1 m–1 or W–1 cm–1 or S cm–1 or Sm–1.
∎ Conductance of an electrolyte inside a solution depends upon the following three factors.
(i) Number of ions present inside the solution.
(ii) Magnitude of charge present on each ion.
(iii) Ionic mobility.
Equivalent Conductance: Equivalent conductivity of a solution at a dilution V is defined as the conduct-
ance of all the ions produced from one gram equivalent of the electrolyte dissolved in V cm3 of the solution.
∧eq = k × f
where f is volume of solution in cm3 containing 1 gram equivalent of electrolyte.
1000
= ∧ eq = κ× its unit is Ω–1 cm2 geq–1 or S cm2 geq–1.
N
κ
In terms of W–1 m2 geq–1; Λ eq =
1000 × N
Molar Conductance: The molar conductivity of a solution at a dilution V is the conductance of
all the ions produced from one mole of the electrolyte dissolved in Vcm3 of the solution. It is usually
represented by ∧m.
∧m = k × V
1000 1000
or ∧ m = κ× = κ× ; Ω–1 cm2 mol–1 or S cm2 mol–1
c Molarity
where k is the specific conductivity and V is the volume of the solution containing one mole of the electro-
lyte and c is the molar concentration, i.e., mol L–1 (or mol dm–3).
κ
In terms of W–1 m2 mol–1; Λ m =
1000 × M

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10.100 Chemistry at a Glance

Relationship between molar conductivity and equivalent conductivity


Λm
= n − factor
Λ eq

Note:
Specific conductance depends upon the number density of ions whose value decreases with increase in dilution;
therefore, value of specific conductance also decreases with increase in dilution.

10.5 VarIatIon of Molar conductancE wIth concEntratIon

(i) Strong Electrolytes: For strong electrolytes, ∧m increases ȁ P


slowly with dilution and can be represented by Debye-
Hückel-Onsager equation which gives the variation in molar
conductance with concentration as under:
ȁP
Λ m =Λ 0m − (A + BΛ 0m ) c
0ROWHQ
where A and B are called Debye-Hückel-Onsager constant, 1D&O
¥&
which depends on temperature coefficient of viscosity and
dielectric constant of medium. The limiting molar conductance or the molar conductance at infinite
dilution ∧m0 of a strong electrolyte can be determined by extrapolating the graph of
Debye-Hückel-Onsager equation.
(ii) Weak Electrolyte: The change in ∧m with dilution is due to increase in the
degree of dissociation and consequently the number of ions in total volume
ȁP
of solution that contains 1 mol of electrolyte.
∎ The limiting molar conductance or the molar conductance at infinite
dilution ∧°m of a weak electrolyte cannot be determined by extrapolating the ¥F
graph between molar conductance (∧m) and square root of concentration
(√c) because the curve becomes parallel to the molar conductance axis on extrapolation.

10.6 Kohlrausch’s law

According to this law each ion makes a definite contribution to the total molar conductivity of an electro-
lyte at infinite dilution, irrespective of the nature of the other ion of the electrolyte. This individual contri-
bution of an ion towards the total molar conductivity of the electrolyte is called molar ionic conductivity.
The limiting molar conductivity of an electrolyte at infinite dilution is the sum of the limiting ionic
conductivities of the cations and the anions each multiplied with the number of ions present in one for-
mula unit of the electrolyte.
∧0m Al 2 (SO4 )3 = 2λ 0A3+ + 3λ 0SO2− ;
4

1 1
∧ 0
= × λ 0A3+ + × λ 0SO2− ; where λ 0Al3+ and λ SO
eq A 2 (SO4 )3
0
2− are molar ionic conductance of Al3+ and
3 2 4 4

SO42–, respectively.
Applications of Kohlrausch’s Law: This law is used to calculate the molar conductance at infinite
dilution for weak electrolytes which can be further used for calculation of other quantities. Thus, there are
many applications of Kohlraush’s law, For example,

Chemistry at a Glance Final.pdf 106 4/1/2014 12:26:07 PM


Electrochemistry 10.101

^Cm
1. Calculation of degree of dissociation, (a): α= , where ^0m is the limiting molar conductance
^0m
and ^cm is the molar conductance at any concentration (c).
2
 ^c 
c  0m 
cα 2
^
2. Calculation of dissociation constant (Ka): Ka = , K a =  m c
(1 − α)  ^m 
1 − 0 
 ^m 
κ× 1000
3. Calculation of solubility (S): S= , where S is solubility and k is specific conductance.
^0m
κ× 1000
4. Calculation of ionic product of water, (KW): H +  = , where [H+] is molarity
^0m
of H+ ions [H+] = [OH–]
\ KW = [H+] × [OH–]
Ionic mobility: Distance travelled by an ion per second under a potential gradient of 1 V/cm is
called ionic mobility.
Ionic velocity
Ionic mobility =
Potential gradient
Transport number: The fraction of total current carried by each ion is called transport number.
u+
Transport number of cation, t + = , where u+ and u– are ionic mobility of cation and
u+ + u−
anion, respectively.

10.7 ElEctrochEMIcal or GalVanIc cEll

Electrochemical or galvanic cell is a device for converting chemical energy into electrical energy.
The electromotive force (EMF) of such a cell is directly proportional to the intensity of chemical reaction
taking place in it.
The chemical reaction responsible for production of electricity takes place in two separate
compartments; these compartments are called half-cells.
The galvanic cells usually consist of two electrolytic solutions into which two electrodes of different
material are dipped. The Daniel cell is a well-known example in this regard.
When the two compartments are connected by a ‘Salt bridge’ and electrodes are joined by a wire
through a galvanometer, electricity begins to flow.
Types of Electrochemical Cells: Two main types of electrochemical cells are listed hereunder.
1. Chemical cell: In these cells, electrical energy is produced from the energy change accompanying
a chemical reaction or a physical process.
2. Concentration cell: In these cells, electrical energy is produced from the energy change
accompanying the transfer of solute or material from one concentration to another.
Daniel Cell: When zinc electrode dipped in ZnSO4 solution and copper electrode dipped in CuSO4
solution are joined by a wire, the following observations are made:

Chemistry at a Glance Final.pdf 107 4/1/2014 12:26:07 PM


10.102 Chemistry at a Glance

(a) There is a flow of current through the external circuit.


(b) The Zn rod loses its mass, while the Cu rod gains its mass.
(c) The concentration of ZnSO4 solution increases, while the concentration of CuSO4 solution
decreases.
(d) The solution in both the compartments remains electrically neutral.
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The indirect redox reaction that takes place in the cell will be
Anode or LHS compartment: Zn → Zn2+ + 2e– (aq.)
Cathode or RHS compartment: Cu2+ + 2e–→ Cu(s)
Net cell reaction is Zn(s)+Cu2+(aq) → Zn2+(aq) + Cu(s)
Salt Bridge: Salt bridge is usually an inverted U-tube filled with a concentrated solution of inert electro-
lyte (viz. KCl, KNO3, NH4NO3 etc.)
Gelatin or agar-agar (plant gel) is dissolved in a hot concentrated aqueous solution of an inert
electrolyte and the solution thus formed is filled in the U-tube. The ends of the U-tube are plugged with
cottonwool as to minimize diffusion.

Significance of Salt Bridge:


(a) It connects the solutions of two half-cells and completes the cell circuit.
(b) It prevents transference or diffusion of the solutions from one half-cell to the other.
(c) It keeps the solutions in two half-cells electrically neutral.

Note:
Inert electrolyte is one whose ions are neither involved in any electrochemical change nor do they react chemically
with the electrolytes in the two half-cells.

Representation of a Galvanic Cell: We require two half-cells to produce an electrochemical cell, which
can be represented by the following few rules
(a) The separation of two phases (state of matter) is shown by a vertical line.
(b) Various materials present in the same phase are shown together with the help of commas.
(c) Two half-cells are joined with the help of double vertical lines.
(d) The significant features of the substances, viz. fugacity (pressure) of gas, activity (concentration)
of ion, etc., are indicated in brackets immediately after writing the substance.
∎ Daniel cell can be represented as Zn | ZnSO4 (1M) | | CuSO4(0.1 M) | Cu
∎ Gas electrode cell will be represented as Pt | H2(g) | NaOH (aq.) | | Ni2+(aq.) | Ni

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Electrochemistry 10.103

Electromotive Force or EMF: We will represent EMF of the cell by the symbol Ecell.
°
or E cell = E°red, cathode – E°red, anode
°
E cell = E°oxi, anode – E°oxi, cathode or E°cell = E°oxi, anode + E°red, cathode
E=
cell Eright − E left

Free energy change in galvanic cells


(i) When a cell operates, work is done on the surroundings as electrical energy flows through
an external circuit. By convention, such work done by the cell is negative.
(ii) The quantity of electrical work done is measured in terms of free energy change, DG. This value is
equal to the product of number of moles of electrons and emf of the cell to DG = –nFEcell. If reactants
and products are in the standard states, then DG° = – nFE°cell.

10.8 ElEctrodE
It is a metallic conductor dipped inside the solution of its own ions. Electrodes are of two types.
(i) Electrode of 1st kind and
(ii) Electrode of 2nd kind.

10.8.1 Electrode Potential


When a metal rod is placed inside the solution of its own ions, then the metal acquires either a +ve
or –ve charge with respect to the solution; under such conditions a potential difference is developed.
This potential difference is termed as electrode potential. It is of two types.
(i) Oxidation potential and
(ii) Reduction potential.
Dependency of Electrode Potential: It depends upon the following factors.
1. Nature of the conductor.
2. Concentration of the metallic ions in solution.
3. Temperature.

10.8.2 Types of Electrodes


10.8.2.1 Gas-ion electrode

(a) In such an half-cell, an inert collector of electrons (Pt of graphite) is in contact with gas and a solu-
tion containing a specified ion, e.g., standard hydrogen electrode (SHE).
(b) Half-cell reaction is EH+ /H /Pt 1/2H2 ⇌ H++e–
2

°
E H + /H2 /Pt
= 0.00 (assumed)
2. Metal-Metal ion Electrode: This cell consists of a bar (electrode) of metal ‘M’ in contact with a
solution containing Mn+ ions. E.g., ZnZn2+ ion, CuCu2+ ion, Ag, Ag+ ion, etc., Half-cell reaction is
M2+(aq) + 2e– → M(s)

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10.104 Chemistry at a Glance

3. Metal Amalgam-Metal ion Electrode: In this half-cell, metal amalgam is placed in contact
with a solution containing metal ion. Electrical contact is made by a Pt wire dipping into the
amalgam pool.
The schematic diagram of normal calomel electrode is given below, represented as
Cl–/Hg2Cl/Hg(Pt) Half cell reaction is 1/2 Hg2Cl2 + e– ⇌ Hg + Cl–
4. Metal-metal insoluble Salt Electrode: In this half-cell, a metal coated with its insoluble salt is in
contact with a solution containing the anion of the insoluble salt, e.g., AgCl+ e– ⇌ Ag(s) + Cl–(aq)
5. Redox Electrode: An oxidation reduction half-cell has an inert metal collector (Pt) immersed in a
solution which contains two ions of the same element in different states of oxidation, e.g.,
Fe3+, Fe2+ half-cell; represented as Fe3+, Fe2+ |Pt and the equilibrium reaction is, Fe3+(aq) + e– ⇌ Fe2+(aq)

10.9 nErnst EquatIon

(i) For a general reaction such as; lL + mM --- ⇌ pP + qQ -----; occurring in a cell, the Gibbs free
energy change is given by, ∆G =∆G° + 2.303RT log10 Q
Since DG = –nFEcell and DG° – nFE°cell;
2.303RT
E=
cell E0cell − log10 Q at T = 25°C
nF
0.0591
E=
cell E°cell − log10 Q
n

10.9.1 Applications of Nernst Equation


1. Determination of Equilibrium constant: According to Nernst equation
0.0591
E = E° − log10 Q at 25°C
n
But E = 0 and Q = Keq.
 n E° 
So, K eq = antilog  
 0.0591 
2. Work done by a cell: work done by a cell = Decrease in free energy
So, –DG = nFE or Wmax= +n FE° where E° is standard emf of the cell.
3. Heat of Reaction in a Electrochemical cell:
• Let ‘n’ faraday charge flow out of a cell of emf ‘E’;
then, –DG = n FE ......(i)
Gibbs-Helmholtz equation from thermodynamics may be given as
∂ ∆G 
∆G = ∆H + T   .....(ii)
 ∂ T  P
From equation (i) and (ii), we get
 ∂ (−nFE)   ∂ (E) 
−nFE =∆H + T  =∆H − nFT  
 ∂ T   ∂ T  P

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Electrochemistry 10.105

 ∂ (E) 
or ∆H =−nFE + nFT  .
 ∂ T 
 P
 ∂ (E) 
Here,  = Temperature coefficient of the cell.
 ∂ T 
 P

10.10 coMMErcIal cElls

Some of the electrochemical cells which are commonly employed as a source of electrical energy can be
classified as listed hereunder.
1. Primary Cells: Such cells can be used only as long as the reactive materials are present. Once they
are exhausted, the cell cannot be recharged by passing current through it.
(i) Leclanche dry cell: The cell representation is Zn | NH4Cl (20 per cent), ZnCl2 | MnO2 | Graphite.
The reactions involved are, provided hereunder.
Anode: Zn(s) → Zn2+ + 2e
Cathode: 2MnO2(s) + H2O(l) + 2e → Mn2O3 (s) + 2OH
The OH– further causes the following secondary reactions, NH4Cl + OH- → NH3 +Cl- + H2O
Zn2+ +2NH3+2Cl- → Zn(NH3)2Cl2
The emf of the cell is 1.25 to 1.5 Volts.

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(ii) Button cell:


Mercury cell, suitable for low current devices like hearing aids, watches, etc. consists of
zinc–mercury amalgam as anode and a paste of HgO and carbon as the cathode reactions for the
cell are given hereunder.
Anode: Zn(Hg) + 2OH − → ZnO(s) + H2O + 2e
Cathode: HgO + H2O + 2e → Hg(l) + 2OH −
The overall reaction is represented by Zn(Hg) + HgO(s) → ZnO(s) + Hg(1)
2. Secondary cells (Secondary Batteries): They are also called storage cells or accumulator cells.
Energy efficiency of the secondary cell is represented by (h).

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10.106 Chemistry at a Glance

energy produced during discharging amp hour × Eavg during discharging


η =
energy consumed during charging amp hour × Eavg during charging
As overall reactions do not involve any ion whose concentration may change, therefore this cell gives
a constant potential of 1.35 V throughout its life.
(i) Lead storage battery:
(a) Such type of cells can be used again and again by recharging the cell. One of the example in
this regard is lead storage battery.
(b) In lead storage battery, Pb acts as anode and lead impregnated with lead oxide (PbO2) acts
as cathode. The electrolyte is a solution of approximately 38 per cent H2SO4 with specific
gravity of about 1.30 at 298 K.
(c) The relevant reactions provided hereunder.
Anode: Pb(s) + SO42- → PbSO4(s) + 2e–
Cathode: PbO2(s) + 4H+(aq.) + SO42– + 2e → PbSO4(s) + 2H2O(l)
Net reaction: Pb(s) + PbO2 (s) + 2H2SO4 → 2PbSO4(s) +2H2O(l)
From the above reaction, it is clear that H2SO4 is used up during discharging. Therefore,
the density of H2SO4 falls. When its density falls below 1.20 g/cm3, the battery needs
recharging.
(d) To recharge the cell, it is connected with a source of potential higher than that of the cell
in such a way, that the cell now acts as the electrolytic cell, where Pb is deposited on the
cathode. PbO2 is hence formed at the anode and H2SO4 is regenerated. Specific gravity of
the solution rises due to the increase in H2SO4 concentration.

Note:
Due to some electrolysis of H2O, H2 and O2 gases are evolved. This makes the periodic supplement of H2O necessary
in lead storage battery.

3. Fuel cell
(i) Fuel cells are electrochemical devices, which convert the energy of fuel by oxidation reaction
into electrical energy. A fundamental example of a fuel cell is the hydrogen–oxygen cell.
Anode – + Cathode

H2 O2
Porous
H nickel Aqueous
O
electrodes KOH
H2O 200° C H2O
20 –40atm

(ii) Fuel cells based on combustion of hydrocarbons are also in operation. e.g.,
hydrogen–oxygen cell.
(iii) Another example of fuel cell is hydrocarbon–oxygen fuel cell. In such cells, hydrocarbons and
their oxygenated derivatives such as CH4, C2H6,C3H8, alcohols, etc., are used.
(iv) Schematic diagram of hydrogen: Oxygen cell is given above. It consists of two electrodes
made of porous graphite. Platinum is coated on the surface of the electrodes. The electrodes are
placed in an aqueous solution of KOH or NaOH. H2 and O2 are bubbled into the cell under high
pressure. The operating temperature is 400–525 K.

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Electrochemistry 10.107

Anode: H2 + 2OH- → 2H2O + 2e–


Cathode: 1/2 O2 + H2O + 2e- → 2OH–
Net equation: 2H2(g) + O2(g) → 2H2O(l).The emf of the cell is 1.23 V.

Thermodynamic efficiency: If DH is the heat of combustion and DG is the useful work done i.e.,
∆G nEF
electrical energy produced, then thermodynamic efficiency (h) of a fuel cell is η = =−
∆H ∆H

10.11 ElEctrochEMIcal sErIEs

When the elements are arranged in the order of their standard reduction potentials on the hydrogen scale,
we get electromotive series or electrochemical series (ECS) of the elements.
(i) The elements occupying the higher position in the ECS are able to reduce the lower metal ions in
the same series. Thus, Zn can reduce Cu2+ ions and Fe can reduce Ag+ ions.
(ii) The metals with more negative potentials can displace those with positive or less negative potentials
from their solutions.
(iii) The metals high up in the series are strong reducing agents and their ions are stable, where as those near
the bottom of the series are inactive stable elements and their ions are easily reduced to the metals.
(iv) Any element above hydrogen will displace hydrogen from a dilute acid solution and will reduce the
oxidized form of any metal lying below it in the series.
(v) The –ve sign of E°red indicates that an electrode when joined with standard hydrogen electrode acts
as anode. Similarly, the +ve sign of E°red indicates that the electrode when joined with standard hy-
drogen electrode acts as cathode.

10.12 applIcatIons of ElEctrochEMIcal sErIEs


10.12.1 Reactivity of Metals
(i) The activity of a metal depends on its tendency to lose electrons. This tendency depends on
the magnitude of SRP (Standard reduction potential). The metal which has high –ve value
(or smaller +ve value) of SRP, readily loses the electrons and is converted into cations. Such a metal
is said to be chemically active.
(ii) The chemical reactivity of metals decreases from top to bottom in the series. e.g.,
(a) Alkali metals and alkaline earth metals having high –ve values of SRP are chemically active.
These react with cold water and evolve H2 gas. These readily dissolve in acids forming their
corresponding salts and combine with those substances which accept electrons.
(b) Metals like Fe, Pb, Sn, Ni, Co, etc., which lie just below in the series do not react with cold water
but react with steam to evolve hydrogen.
(c) Metals like Cu, Ag, Au, etc., which lie below hydrogen are less reactive and do not evolve
hydrogen from water.

10.12.2 Electropositive Character of Metals


The electropositive character also depends on the tendency to lose electrons, like reactivity, the
electropositive character of metals decrease from top to bottom. On the basis of SRP values, metals are
divided into three groups.

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10.108 Chemistry at a Glance

A strongly electropositive metals have an SRP near about –2.0 Volt or more negative.
Moderately electropositive metals have an SRP between 0.0 and –0.2 V.
Weakly electropositive metals lie below hydrogen and have +ve SRP.

10.12.3 Displacement Reactions


(i) A metal higher in the series displaces the metal from its salt solution which is lower in the series.
(ii) A non-metal having high value of SRP will displace another non-metal with lower SRP (i.e., occu-
pying position above in the series). E.g., Cl2 can displace Br and I2 from bromides and iodides.
(iii) Fe and the metals above Fe are capable of liberating H2(g) from water. The tendency decreases from
top to bottom in ECS.
(iv) In case two or more types of positive and negative ions are present in solutions during electrolysis
certain ion are discharged or liberated at the electrodes in preference to other.
‘In general, in such competitions the ion which is a stronger oxidizing agent (high value of SRP)
K + ,Ca 2 + ,Na + ,Mg 2 + ,Al 3+ , Zn2 + ,Fe2 + ,H + ,Cu 2 + ,Ag + ,Ay 3+
is discharged first at cathode’ i.e., → (increasing order of
deposition).
Similarly, the anion which is a stronger reducing agent (low value of SRP) is liberated first at the
anode.
SO − ,NO− ,OH − ,Cl − ,Br − ,I−
i.e., 
4 3
→ (increasing order of deposition).

10.13 corrosIon

(i) Corrosion is an electrochemical process. When iron is in contact with air, even with a microscopic
drop of water the iron tends to oxidize and give up electrons.
Anode: Fe → Fe2+ + 2e-
The electrons pass through the iron to the edge of the drop, where they reduce oxygen from the air
to hydroxide ion.
Cathode: O2 + 2H2O + 4e– → 4OH–
The iron (II) ions and hydroxide ions diffuse together and form insoluble iron (II) hydroxide.
Fe2+(aq) + 2OH-(aq) → Fe(OH)2 (s)
Fe(OH)2 + O2 + H2O → Fe(OH)3 → Fe2O3.x H2O
This precipitate is rapidly oxidized by oxygen to rust, an iron (III) compound with the approximate
composition Fe2O3.H2O

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(ii) Many methods and devices have been employed to prevent corrosion. We protect iron by coating it
with paint, lacquer, grease or asphalt; with another metal such as zinc, copper, nickel chromium or
tin; with a ceramic enamel or with an adherent tough coating of Fe3O4.

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Electrochemistry 10.109

(iii) Another means of preventing the corrosion of iron or steel is called cathodic protection. Cathodic
protection is used such as in underground pipeline that is in contact with soil. The iron is connected
by a wire to a more active metal, such as Zn, Al or Mg and the iron becomes cathode at which
oxygen is reduced rather than an anode where iron is oxidized. The difference in activity of the two
metals causes a current to flow between them producing corrosion of the more active metal and
protecting the iron with magnesium as the more active metal. The following reactions occur in this
process.
Anode: 2Mg → 2Mg2+ + 4e-
Cathode: O2 + 2H2O + 4e- → 4OH-
Sum: 2Mg + O2 + 2H2O → 2 Mg2+ + 4OH-
In this series of reactions, no iron is oxidized. The active metal is slowly consumed and must be
replaced periodically, but this is less expensive than replacing a pipeline.
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(iv) Some of the more active metals such as aluminium and magnesium, which might be expected to
corrode rapidly, are protected by a tightly adhering oxide coat of the metal oxide that forms when
the metal is exposed to air. The metal is made passive by this coating.

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Chapter 11 NUCLear
CheMIStrY

11.1 Nuclear chemistry

Nuclear chemistry is that branch of chemistry which deals with the phenomena involving the nuclei of
the atoms.
Radioactivity is the phenomenon of spontaneous emission of certain kinds of radiations by some elements.
The elements emitting such radiations are called radioactive elements. The phenomenon of radioactivity
was discovered by Henry Bacquerel (in 1896).
Two most important elements isolated from pitchblende(an ore of uranium, mainly U3O8) by Marie
Curie and her husband Piere Curie (in 1898) were polonium and radium, the latter being the most
radioactive element. Polonium was named after Poland the native place of Marie Curie and radium was so
called because of its exceptionally high radioactivity (about 2 million times more than uranium).
Radiations emitted from radioactive elements and their characteristics:

S. No. a-rays b-rays g-rays


(i) Deflected towards negative Deflected towards positive Remains undeflected.
plate, but the deflection is small plate, but the deflection is large
(ii) Each particle has charge =+2 Each particle has charge and They have no charge and
units and mass = 4 units, mass ≈ that of electrons, i.e., no mass. They are simply
i.e., they are helium nuclei they are same as electrons electromagnetic radiations
(iii) Their velocity is 1/10th to Their velocity is 3% to 99% of Their velocity is same as
1/20th of that of light that of light that of light
(iv) Their penetrating power Their penetrating power Their penetrating power
is low is 100 times greater than is 100 times greater than
a-rays b-rays
(v) Ionizing power is very high It is 1/100th of a-rays Ionizing power is very
poor
(vi) Affect photographic plate and Effect on photographic plate Little effect on both
produce fluorescence on ZnS is more but very low on ZnS
screen screen

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Nuclear Chemistry 11.111

Note:
(i) g-rays are not produced simultaneously with a and b-rays but are produced subsequently through
secondary effect.
(ii) Radioactivity of solids and liquids is detected and measured with the help of Geiger-muller counter or a device
called Proportional counter and that of gases by Ionization chambers.

11.2 Nucear FOrce


The force which holds the neutrons and protons (nucleons) together within is called the nuclear force.
The origin of this force has been explained by Yukawa by discovery of a new fundamental particle
called meson. The nuclear forces (unlike electrostatic forces) operate over very small distance (10–15 m,
i.e., 1 fermi) and are called short range forces. Further, these forces are nearly 1021 times stronger than
electrostatic forces.
A meson has mass between that of electron and proton and its charge +1, –1 or o.(p+, p–, p0).
This particle was discovered by Yukawa in 1935. The nucleons are held together due to their fast
exchange into one another through mesons:
p → n + p+
n + p+ → p
Some other fundamental particles:
(i) Positron or antielectron (charge = +1, mass = that of electron) represented as +le0.
(ii) Neutrino(n), has almost no charge but very small mass.
Isotopes, Isobars, Isotones, Isomers, Isosters and Isodiaphers: (Z = Atomic number No., A = Mass
Number, N = Neutrons, P = Protons)

S. No. Term Characteristics Examples


(i) Isotopes Z = Same, A = Different 1
1 H, 12H, 13H; 92
235
U, 238
92
35
U; 17 37
Cl, 17 Cl

(ii) Isobars Z = Different, A = Same 228


88 Ra, 228
89 Ac, 228
90
40
Th; 18 40
Ar, 19 K

(iii) Isotones N = Same, A = different, Z = different 39


18
40
Ar, 19 30
K; 14 31
Si, 15 P

(iv) Isomers N = Same, Z = Same U–X(t1/2 = 1.4 min); U–Z(t1/2 = 6.7 hr)
(v) Isosters No. of atoms = Same, number of CO2, N2O; N2, CO; HCl, F2
e = same physical properties = same
(vi) Isodiaphers Isotope number = Same, 235
U, 231 39
Th; 19 K, 19
F
92 90 9
isotope number = N–P

Notes:
(i)Nuclear radius is 10–15 m, atomic radius is 10–10 i.e., nuclear radius is 1/10,000th of atomic radius.
(ii)Nuclear radius (r) of any atom is related to its mass no. A as r = R0A1/3 where R0 =constant = 1.4 × 10–15 m
(iii)Area of cross section of nucleus is expressed in barns (1barn = 10–24 cm2)
(iv) Loss of a or b-particle is to change N/P ratio so that it lies within the stability belt, loss of a-particle increases N/P
ratio while loss of b-particle decreases N/P ratio.
(v) Parent and daugther element which are related through a–emission are isodiaphers.

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11.112 Chemistry at a Glance

Group Displacement Laws (put forward by Soddy, Fajan and Russell)


(i) When an a-particle is emitted, the new element has atomic number less by 2 units and mass num-
ber less by 4 units, i.e., new element is two positions on the left in the periodic table
e.g., 238 234
92 H → 90 Th + 2 He
4
(a-particle)
(ii) When a b-particle is emitted, the new element has atomic number greater by 1 units but mass num-
ber is same, i.e., new element is one position on the right in the periodic table
e.g., 14 14
6 C → 7 N + −1e
0
(b-particle)

Notes:
(i) b-particle (electron) is not present in the nucleus, yet it is emitted from the nucleus because a neutron changes
into a proton, increasing atomic number by 1 units.
n → p + –1e0
(ii) To find a and b particles emitted in the reaction ab A → cd B , we write
b
a A → cd B + x 42α + y − 0
−1 β
Then, b = d + 4x + 0y and a = c + 2x – y, solving for x and y.

11.2.1 Magic Numbers


Nuclides containing 2, 8, 20, 28, 50, 82 and 126 protons or neutrons or both are highly stable due to high
binding energy per nucleon.

Number of protons Number of neutrons Number of nuclides known


Even Even 165
Even Odd 55
Odd Even 50
Odd Odd 5

11.3 KiNetics OF raDiOactiVe DisiNteGratiON

All radioactive disintegration follows first-order kinetics. Starting with N0 atoms of the radioactive element
A, if N is the number of atoms after time t
dN
Rate of disintegration, − = λ N ; where l is called disintegration constant
dt
dN
Rewriting, − = λdt
N
2.303 N
Expression for the disintegration constant λ = log 0
t N
n
−λt 1
=
or N N=
0e N0  
2

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Nuclear Chemistry 11.113

t
where n = is the number of half-lives in time t.
t1/2
Hence, disintegration constant may be defined as the fraction of the total number of atoms which
disintegrate in 1.

Note:
Rate of disintegration (activity of a radioactive element) is directly proportional to the amount of the substance. It does
not depend upon temperature, pressure, state of combination, etc.

11.4 halF-liFe PeriOD

Half-life period of a radioactive element is the time in which half of the original substance disintegrates:
0.693
Expression for half-life period is t1/2 =
λ

11.4.1 Average Life Period


It is the sum of the periods of existence of all the atoms divided by the total number of atoms of the radio-
active substance present initially, or time during which 63.21 per cent of the substance undergoes decay is
called average life. It is represented by tav or t.
Total life time of all the atoms
Average life =
Total number of atoms

∫ t dN 1 t1/2
= 0
= = = 1.44 t1/2
N0 λ 0.693
1
τ= t av= = 1.44 t1/2
λ
N
per cent remaining amount at =
τ × 100
= 36.79 per cent
N0
per cent decayed amount at t = 100 - 36.79 = 63.21 per cent

11.4.2 Units of Radioactivity


Units of disintegration rate is Curie or Becquerel or Rutherford. Curie is the amount of a radioactive
substance which undergoes 3.7 × 1010 disintegrations per second.
i.e., 1 Curie (1 Ci) = 3.7 × 1010 ds–1. Similarly, 1 Becquerel (1 Bq) = 1 ds–1 and 1 Rutherford
(1 Rd) = 106 ds–1.

11.5 raDiOactiVe DisiNteGratiON series


Radioactive disintegration series is the series of spontaneous changes that take place starting from the
parent element (with unstable nucleus) upon to formation of stable nucleus.

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11.114 Chemistry at a Glance

Four important disintegration series along with their starting elements and stable end products
are as under

Series Name of the series Starting element Stable end product


4n Thorium series 232
90 Th 208
Pb
82

4n + 1 Neptunium series 241


94 Pu 209
Bi
83

4n + 2 Uranium series 238


92 U 206
Pb
82

4n + 3 Actinium series 235


92
227
U( Ac)
89
207
Pb
82

They are so called because mass numbers of atoms belonging to these series when divided by 4 give a re-
mainder of 0, 1, 2 and 3, respectively. Among these four series, (4n + 1) is artificial while the other three
are natural.
Radioactive equilibrium: Though radioactive changes are irreversible still equilibrium is
λA λB
established for intermediate daughter element at equilibrium A  → B  →C
NA NB NC

At equilibrium rate of formation of B = rate of disintegration of B, lANA = lB NB


N A λ B τA (t1/2 )A
⇒ = = =
N B λ A τB (t1/2 )B

11.5.1 Parallel Path Decay


Overall decay constant, l0 = ly + lz
λy λy O\ \
Fractional yield of =
y =
λ0 λ y + λz ;
O] =
λz λz
Fractional yield of =
z =
λ0 λ y + λz
λx λ
Series path decay: X  → Y  y
→Z
t=0 N0 0 0
t Nx Ny Nz
Number of nuclei of daughter element y remaining at time t.
Nλ e −λ x t − e −λ y t  .
NY = 0 x
λy − λx  
If maximum activity of daughter element is observed at time tmax
2.303  λy 
t max = log10  
λy − λx  λx 

Nuclear stability: Stability of a nucleus can be determined by the following three methods.
1. n/p ratio
2. Packing fraction
3. Binding energy (BE) per nucleus.

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Nuclear Chemistry 11.115

11.5.1.1 n/p ratio

By plotting the number of neutrons (n) against the number of protons (p) for nuclei of various elements,
it has been observed that most of the stable nuclei lie in a well-defined belt called stability belt or
zone of stability.

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11.5.1.2 Analysis of curve

(i) Nuclei whose n/p ratio lies outside the stability belt are unstable and therefore undergo spontaneous
radioactive disintegration.
(ii) Nuclei having z ≤ 20 for which number of neutrons is equal to number of protons are stable.
e.g., 24 He 12 16 28 40
6 C, 8 O, 14 Si, 20 Ca .

(iii) If z > 83, then nuclei has no stable isotope at all and are radioactive.
(iv) for z > 20, because of increasing repulsive forces between protons large number of
neutrons must be present due to which size of nucleus increases and force of repulsion
decreases and so nucleus stabilizes and hence n/p ratio increases. E.g., for Bi the n/p ratio is
about 1.5 : 1.

11.5.2 Packing Fraction


The concept of packing fraction was introduced by Aston.
 
+H
It has been observed that mass of an isotope of an element 
obtained experimentally using mass spectrograph is
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&
(i.e., the sum of mass of proton, neutrons and electrons. This 
mass difference is termed as mass defect. 
This lost mass is converted into energy that is released 
during the nuclear reaction and is thus a direct measurement  
$U

of the binding energy holding the nucleus. Larger the BE, the

more stable will be the nucleus. 
mass defect (Dm) = isotopic mass (m) - mass    
number (A) 0DVVQXPEHU$

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11.116 Chemistry at a Glance

∆m
Packing fraction = × 10 4
A
Packing fraction may have a negative or a positive sign. Packing fraction does not have any precise
theoretical significance but it gives an indication about the stability of the nucleus.

11.5.2.1 Significances of packing fraction

(i) The negative value of packing fraction shows that the isotopic mass is less than the mass number.
In such cases, some mass gets transformed into energy in the formation of that nucleus. Hence the
more negative the packing fraction of an element, the more stable should be the nucleus.
(ii) A positive fraction indicates that the concerned nuclear is less stable.

11.5.2.2 Analysis of curve

A plot of packing fraction against the corresponding mass number of the various elements gives the
following results.
(a) The packing fractions of the stable nuclides lie more or less on a smooth curve.
(b) The curve passes through a minima in the mass number range 50–60, implying the maximum
stability.
(c) After the minima, packing fraction steadily increases and ultimately becomes positive for elements
of high mass number.

11.5.3 Binding Energy per Nucleon


The energy released in the formation of a nucleus from its constituent nucleons is called the
binding energy (BE) of the nucleus.
The binding energy of nucleus when divided by the number of nucleons gives the mean
binding energy per nucleon ( B ). The binding energy per nucleon is a measure of the stability of
the nucleus.
Binding energy (BE) = Dm × c2 = Dm (in amu) × 931 MeV 
B total binding energy
Binding energy per nucleon (B) = =
A Total number of nucleons
%
 $
11.5.4 Significance of Binding Energy per Nucleon
(i) The greater the binding energy per nucleon, the more stable is the nucleus.
(ii) If we plot a graph between binding energy per nucleon versus mass numbers, following results are
observed.
(a) The value of B is maximum for mass number (56). Thus, nucleus of iron is thermodynamically
most stable.
(b) It is also seen that the points for He(A = 4), C(A = 12), O(A = 16) lie quite high in the graph.
This shows that the nuclei of these elements are exceptionally stable.
(c) The maximum value of B is equal to 8.7 MeV.

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Nuclear Chemistry 11.117

11.6 artiFicial traNsmutatiON

Artificial transmutation of elements means the process of converting one element into another by
bombardment of 10 n, 11H, 12H respectively,
4
2 He + 14
7 N 
→ 17
8 O + 11H
1
1 H + 73 Li 
→ 74 Be + 10n
1 27 28
0 n + 13 Al 
→ 13 Al
The first artificial transmutation was carried out by Rutherford in 1919 according to the first reaction
given above.

Representation of a nuclear reaction: Reactant nucleus (bombarding particle, particle emitted) Product
nucleus e.g., the above reactions may be represented as 147N (a, p) 178O
Some Important Points
(i) The best bombarding particles are neutrons because they have no charge (and hence not repelled by
the nucleus being bombarded) but have considerable mass (one unit).
(ii) Cyclotron is a machine used for accelerating the particles. The machine used for accelerating
protons is called synchrotron. Another machine used for accelerating particles is
called bevatron.
(iii) Reactions of the above type are called nuclear reactions. Total charge and total mass on the two
sides must be same. A nuclear reaction is called (n, p) or (n, a) or (p, a), etc. depending upon the
bombarding particle (named first) and the particle emitted (named later).
(iv) Artificial radioactivity or induced radioactivity (first studie by Irene Curie) is the phenomenon
in which the artificial disintegration of a stable nucleus leads to the formation of a radioactive
t1/2 =2.55 min °
isotope, e.g., 13
27
Al + 24 He 
→ 10n + 15
30
p   30
→ 14 Si + +1e(Positron)
(stable) (Radioactive)

11.7 Nuclear FissiON


Nuclear fission is the splitting of a heavier atom like that of Uranium-235 into a number of fragments of
much smaller mass by bombardment with subatomic particles with liberation of huge energy, e.g.,
235
92 U + 10n 
→ 140 93 1
56 Ba + 36 Kr + 30 n

Neutrons emitted during first fission bombard more uranium atoms and the reaction goes on. It is
called a chain reaction.
(i) The minimum size which the fissionable material must have so that one of the neutrons released in
every fission hits another nucleus and causes fission so that chain reaction continues at a constant
rate is called critical mass. For U-235, it is 1–100 kg. Critical mass is inversely proportional to
square of density.
(ii) Naturally occurring uranium is 99.3 per cent U–238 which is not fissionable. Only U-235 is
fissionable.
(iii) If chain reaction is not controlled, It can be used for destructive purposes, i.e., in atomic bomb.
(iv) Transuranic elements are the elements coming after uranium, i.e., with atomic numbers greater,
than 92. These have been prepared by artificial disintegration. Hence, they are also called synthetic
elements.

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11.118 Chemistry at a Glance

11.8 Nuclear reactOr

Nuclear reactor is an arrangement in which the energy produced (in the form of heat) in a nuclear fission
can be used in a controlled manner to produce steam which can run the turbine and produce electricity.
(i) In the reactor core, the fuel rods are of U-235, control rods are of Cd or B (because they can absorb
the neutrons), moderator (to slow down the speed of neutrons) and coolant (to carry away the
heat). Lead aperns are used by workers because they absorb harmful radiations.
(ii) Breeder reactors are those reactors in which the neutrons produced from fission of U-235 are partly
used to carry on the fission of U-235 and partly used to produce some other fissionable material
e.g., PU-235 from U-238

11.9 Nuclear FusiON

Nuclear fusion is the process in which lighter nuclei fuse together to form heavier nucleus. These take
place at extremely high temperature (∫106 K), i.e., in the sun. Hence, these are called thermonuclear
(
reactions 411 H  → 24 He + 2 + 10e + γ + Energy )
(i) Hydrogen bomb has fissionable material in the centre and deuterium ( 12H) and 63Li isotopes
surrounding it. Heat produced in the centre gives the required high temperature and neutrons
emitted convert Li-6 isotope into tritium ( 13H) for fusion.
(ii) Hydrogen bomb is much more powerful than atom bomb because for the same mass of deuterium
or tritium undergoing fusion and uranium undergoing fission. The number of atoms present in the
former is much more than in the latter. Moreover, there is no restriction of critical mass in the
fusion reactions.
Applications of Radioactivity
(i) In medicines-radiotherapy, e.g., Co60 for cancer, I131 for thyroid disorders and P32 for leukaemia.
(ii) In geological dating, i.e., in predicting the age of the earth and rocks.
(iii) In radiocarbon dating, i.e., in predicting the age of a fallen tree or dead animal.
(iv) In tracer technique, i.e., following the path taken up by a particular radio isotope, e.g., circula-
tion of blood by injecting saline solution containing Na24 isotope, uptake of a fertilizer containing
P32 isotope, etc.
(v) In neutron activation analysis. It is a technique of finding the trace of one element present in
another by activating the trace element by bombarding with neutrons. E.g., traces of Ag present in
a lead painting.
Radio Carbon Dating: It is used to determine the age of a dead plant or a dead animal. This method is
based upon the fact that in a living organism, ratio of C14 to C12 is always fixed. However, in dead organism,
this ratio decreases because C14 is radioactive in nature and therefore undergo spontaneous disintegration.
C14 2.303 N t1/2
If N 0 = =
ratio in living organisms, then t = log10 0
C12 λ N 0.3010
Rock Dating: It is used to determine the age of a planet or a star. This method is based upon natural
2.303 N 2.303  N + NU 
=
disintegration series, e.g., uranium series t = log 0 log10  Pb 
λ N λ  NU 

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SurfaCe
Chapter 12
ChemiStry

12.1 Definition

The term catalysis was introduced by Berzilius in 1836. A catalyst is defined as a substance which in-
creases the rate of reaction without undergoing any change and can be recovered as such at the end of
the reaction. The phenomenon of increase in the rate of a reaction with the help of a catalyst is known as
catalysis. Catalysis are of two types:
1. Positive catalysis: The phenomenon in which presence of a catalyst accelerates the rate of
a reaction.
2. Negative catalysis: The phenomenon in which presence of a catalyst retards the rate of a reaction.
Such substances are also known as inhibitors or negative catalysts.

12.1.1 Characteristics of Catalysis


(i) A catalyst remains unchanged chemically at the end of a reaction, however, its physical state may
change. E.g., MnO2 is used as a catalyst in granular form for the decomposition of KClO3, and is left
in powder form at the end of reaction.
(ii) A catalyst never initiates a chemical reaction. It simply influences the rate of reaction. Exception:
combination of H2 and Cl2 takes place only when moisture (catalyst) is present.
(iii) A small quantity of a catalyst is sufficient to influence the rate of a reaction. E.g., 1 g atom of Pt is
sufficient to catalyse 108 litre of H2O2 decomposition.
(iv) A catalyst does not influence the equilibrium constant of a reaction. It simply helps
in attaining equilibrium earlier. It alters the rate of forward and backward reactions
equally.
(v) A catalyst does not affect the heat and free energy change of a reaction.
(vi) Catalyst’s activity is more or less specific. A catalyst for one reaction is not necessary to catalyse the
another reaction.
(vii) A catalyst is poisoned by certain substance. It has been found that impurities of any type,
even if present in small amount, inhibit or retard the rate of catalysed reactions to a large ex-
tent. These impurities are called catalytic poisons. E.g., the rate of combination of SO2
and O2 may be slowed down considerably if some arsenic compound are present even
in traces.

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12.120 Chemistry at a Glance

12.1.2 Classification of Catalysis


Catalysis is classified into two broad types:

12.1.2.1 Homogeneous catalysis

The reactions in which catalyst and the reactants are in same phase. Homogeneous catalysis are of
two types:
1. Gaseous phase catalysis: When reactants and catalyst are in gaseous phase.
[NO]
e.g., 2SO2(g) + O2 (g) → 2SO3(g)
Catalyst

2. Solution phase catalysis: The reactions in which catalyst and reactants are in solution phase or
H+
liquid phase and are completely miscible, e.g., RCOOR’(l) + H2O(l) 
(aq )
→ RCOOH + R’OH

12.1.2.2 Heterogeneous catalysis

The reactions in which catalyst and reactants have more than one phase.
1. Solid–solid catalysis: Reactions in which reactants and catalyst both are in solid phase.
MnO2 (s)
e.g., 2KClO3(s) 
Catalyst
→ 2KCl(s) + 3O2(g)

2. Solid–liquid catalysis: Reaction in which reactants are in liquid phase and catalyst are in solid
Pt(s)
phase and both are immiscible, e.g., 2H2O2(l) 
Catalyst
→ O2(g) + 2H2O(e)

3. Liquid–liquid catalysis: Reaction in which both reactants and catalyst are in liquid phase and are
Pg(  )
miscible to each other, e.g., 2H2O2(l) 
Catalyst
→ 2H2O(e) + O2(g)
4. Solid–gas catalysis: Reactions in which reactants are in gaseous phase and catalyst is in
solid phase.
Some example of solid–gas catalysis are
Pt absetos or
(i) Contact process for H2SO4: 2SO2 + O2 
V2 O5

→ 2SO3
Pt gauge
(iii) Ostwald process for HNO3: 4NH3 + 5O2 →
Catalyst
4NO + 6H2O.

Two properties of a solid catalyst is most important, one is activity and the other is selectivity.
Activity: Activity is the ability of a catalyst to accelerate a chemical reaction; the degree of acceleration is
as high as 1010 times in certain reactions.
Selectivity: Selectivity is the ability of a catalyst to direct a reaction to yield particular reaction product
excluding others.
Ni
CO(g) + 3H2(g)  → CH4(g) + H2O(g)
Cu/ZnO−Cr2 O3
CO(g) + 2H2(g)  → CH3OH(g)
Cu
CO(g) + H2(g)  → HCHO(g).

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Surface Chemistry 12.121

12.1.3 Effect of a Catalyst


A catalyst is a substance that takes part in a reaction system by providing a new path way with a
lower activation energy between the two fixed points of reactants and product. By the addition of a
catalyst the activation energy for the reverse reaction is lowered by exactly the same amount as for
the forward reaction. Thus, a catalyst speeds up both the forward and the backward reactions by the
same amount.

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12.1.4 Catalytic Poisoning or Inhibitor for Catalyst


The phenomenon in which presence of a substance in small amounts even decreases or ruins the
activity of a catalyst. The poisoners are preferentially adsorbed on the surface of catalyst to make it inert,
e.g., CO for Fe catalyst in Haber process.
Clasification of Poisoning:

Temporary Poisoning Permanent Poisoning


(i) The poisoners are held at active centres (i) The poisoners are held on active centres by
by weak forces. free valencies.
(ii) Catalyst surface is regenerated by (ii) Catalyst surface is regenerated only by
scratching the surface. chemical treatment.

12.2 AciD–BAse cAtAlysis

Acid–base catalysis includes reactions in solutions which are catalysed by acids or bases or both. An
acid donates a proton to a reactant to a form an intermediate, which then loses the proton to a base to
give a product.
(a) Mutarotation of glucose: The phenomenon in which optical activity of a freshly prepared
a-glucose solution in water rapidly decreases with time till equilibrium is reached between a and b
form and similarly rotation for b-glucose solution increases with time.
+
Base
H
HG →
acid HGH+ 
− H+
→ GH
a-glucose intermediate b-glucose

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12.122 Chemistry at a Glance

(b) Hydrolysis of ethyl acetate:


+
H
CH3COOC 2H5 + H2O  → CH3COOH + C 2H5OH
(c) Inversion of cane sugar:
+
H
C12H22O11 + H2O  → C 6H12O6 + C 6H12O6
glucose fructose

12.3 enzyme cAtAlysis

The phenomenon in which reactions are catalysed by enzymes is called enzyme catalysis. Enzymes are
proteins with high relative molar mass of the order of 10,000 or even more and are derived from living
organisms.

12.3.1 Characteristics of an Enzyme Catalyst


(i) Enzyme-catalysed reactions are highly specific, i.e., one enzyme for one reaction.
Diastase
e.g., (i) 2(C 6H10O5 )n + nH2O → nC12H22O11
Starch Maltose
Maltase
(ii) C12H22O11 + H2O → 2C 6H12O5
Maltose Glucose
Zymase
(iii) C 6H12O6  → 2C 2H5OH + 2CO2
Glucose Ethyl alcohol

Urease
(iv) NH2CONH2 + H2O → 2NH3 + CO2.
(ii) Enzyme-catalysed reactions are normally hydrolytic in nature.
(iii) Enzyme-catalysed reactions take place with evolution of gases.
(iv) The rate of reaction depends upon enzyme concentration.
(v) Enzyme-catalysed reactions are highly susceptible to pH of medium. Favorable range of pH is
5 to 7.
(vi) The optimum temperature for an enzyme-catalysed reaction is nearly 30°C.
(vii) Enzymes are colloidal in nature and thus their action is ruined by electrolytes.
(viii) The activity of an enzyme is increased in the presence of certain substances known as coenzymes or
activators.
E.g., non-protein (vitamins).

12.3.2 Mechanism of Enzyme-Catalysed Reactions


The mechanism of enzyme-catalysed reactions is due to specific shapes of enzymes. The reac-
tant molecules having a complementary shape to an enzyme fit into these cavities just like a
key fits into a lock. This results in the formation of the intermediate which then decomposes to
give products.
Step 1: Binding of enzyme to substrate to form an activated complex, E + S → ES.
Step 2: Product formation in an activated complex ES → EP.
Step 3: Decomposition of an activated complex to products, EP → P + E

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Surface Chemistry 12.123

12.4 tHeoRy of cAtAlysis

12.4.1 Intermediate Compound Formation Theory


A catalyst combines with one or more of the reactants to give an intermediate product which either decom-
poses or reacts with other reactants to give a product along with regeneration of catalyst.
E.g., catalytic decomposition of KClO3:
2KClO3 + 2MnO2 
→ 2KMnO4 + Cl 2 + O2
intermediate 1

2KMnO4 → K 2MnO4 + MnO2 + O2


intermediate 2

K2 MnO4 + Cl2 → 2KCl + MnO2 + O2

12.4.1.1 Adsorption theory


The term adsorption was first used by Kayser. The phenomenon of attracting and retaining the molecules
of a substance on the surface of a solid or a liquid resulting in the higher concentration on the surface is
called adsorption. The substance adsorbed on the surface is called an adsorbate and the substance on
which it is adsorbed is called an adsorbent.

12.4.1.2 Desorption

The reverse process, i.e., removal of an adsorbed substance from the surface is called desorption.

12.4.1.3 Occlusion
The adsorption of gases on the surface of metals is called occlusion.

12.4.1.4 Sorption
If absorption and adsorption occur simultaneously, then the phenomenon is called sorption. Adsorption
is a surface phenomenon, whereas absorption is a bulk phenomenon.

12.4.1.5 Positive adsorption


When the concentration of the adsorbate is more on the surface of the adsorbent than in the bulk, then it
is called positive adsorption.

12.4.1.6 Negative adsorption


When the concentration of an adsorbate is less relative to its concentration in the bulk, then it is called
negative adsorption.

12.4.2 Characteristics of Adsorption


(i) Adsorption is specific and selective in nature. However, physical adsorption is less specific and
chemical adsorption is more specific.

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12.124 Chemistry at a Glance

(ii) Adsorption is accompanied with decrease in free energy (i.e., DG = –ve). Therefore, adsorption is a
spontaneous process.
(iii) Factors which influence the extent of adsorption are:
(a) Nature of adsorbent: Transition metals are good adsorbents for gases because of vacant or
half-filled d orbitals and high charge–size ratio.
(b) Nature of adsorbate: Easily liquefiable gases (e.g., HCl, NH3, CO2 etc.) are adsorbed to a
greater extent than others (e.g., H2, N2, O2 etc.).
(c) Surface area of adsorbent: Larger the surface area of an adsorbent, more is the adsorption.
The surface area per gram of the adsorbent is called specific surface area of the
adsorbent.
(d) Pressure: An increase in pressure at constant temperature increases the rate of adsorption.
(e) Temperature: An increase in temperature decreases physical adsorption, whereas
chemisorption first increases and then decreases. This is because chemisorption requires some
activation energy like a ordinary chemical reaction.

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Physical Adsorption Chemical Adsorption


(i) Reactant molecules are adsorbed on surface by (i) Reactant molecules are adsorbed on
weak Van der Waals forces. the surface by free valancies.
(ii) Reversible with temperature, usually occurs at low (ii) Invertible with temperature, usually
temperature. occurs at high temperature.
(iii) Exothermic, about 20–40 kJ-mol heat energy is (iii) Exothermic, about 200–400 kJ-mol
given out. and heat is liberated.
(iv) Does not require activation energy. (iv) Require a activation energy.
(v) Weak, multilayer, non-directional and (v) Strong, unilayer, non-directional and
non-specific. specific.

12.5 fReUnDlicH ADsoRPtion isotHeRm

Freundlich studied the influence of pressure on adsorption and obtained the following results. x/m = k
p1/n. By taking log of both side, we get, log x/m = log k + 1/n log P; where x is the amount of adsorbate on
m gram of adsorbent.

Note:
The plots of extent of adsorption (x/m) vs P at constant temperature are called adsorption isotherm.

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Surface Chemistry 12.125

12.5.1 Analysis of Adsorption Isotherm


x
(i) At lower pressure = kP. The graph is nearly straight line with slope k.
m
x x
(ii) At higher pressure, =k; is found to be independent of pressure.
m m
x x
(iii) At intermediate range of pressure, = kP1/n ; is proportional to pressure raised to some
m m
fractional value between 1 and 0.
x
Freundlich isotherm is also used for equilibrium concentration. = kc1/n where c is concentration
m
of solute in the solution.

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12.6 colloiDAl solUtion

Finely divided particles of any substance with diameter lying within 1 to 100 nm range dispersed in
any medium constitute to form a colloidal solution. Colloidal solutions are intermediate between true
solutions and suspensions.

12.6.1 Comparative Study Between True Sols,


Colloidal solutions and Suspension

Prop True sols Colloidal sols Suspension


Size Less than 1 nm Between 1 nm and 100 nm Greater than100 nm.
Visibility Invisible under Visible only under Visible even to
ultramicroscope ultramicroscope naked eye
Diffusion Diffuse readily through Diffuse slowly through No diffusion
parchment membrane parchment membrane
Filtration Impossible through filter Impossible through filter Possible through filter
paper and parchment paper but possible through paper and parchment
membrane or both parchment membrane membrane or both
Scattering No scattering Scattering takes place and Do not show Tyndall
Tyndall effect is observed effect

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12.126 Chemistry at a Glance

12.6.2 Phases of Colloids


It consists of two phases, namely a dispersed phase and a dispersion medium.

12.6.2.1 Dispersed phase

It is the component present in small proportion and is just like a solute in a true solution. For example, in
the colloidal state of sulphur in water, the sulphur is a dispersed phase.

12.6.2.2 Dispersion medium

It is normally the component present in excess and is just like a solvent in a solution. The particles of the
dispersed phase are scattered in the dispersion medium in a colloidal system.

12.6.3 Types of Colloidal system


Depending upon whether the dispersed phase and the dispersion medium are solids, liquids or gases,
eight types of colloidal system are possible. A gas mixed with another gas forms a homogeneous mixture
and not a colloidal system. Typical examples of various types alongwith their characteristic names are
given in the table hereunder.

Dispersed Dispersion Colloidal System Examples


Phase Medium
Gas Liquid Foam or froth Soap sols, lemonade froth
Gas Solid Solid foam Pumice stone, styrene, foam
Liquid Gas Aerosols of liquid Fog, clouds, fine insecticide sprays
Liquid Liquid Emulsions Milk
Liquid Solid Gels Cheese, butter, boot polish, table jelly
Solid Gas Aerosols of solid Smoke, dust
Solid Liquid Sols Starch dispersed in water, gold sol
Solid Solid Solid sols Ruby glass, some gem stones

12.7 clAssificAtion of colloiDs

Colloids can be classified in a number of ways based upon some of their important characteristics.

12.7.1 Based Upon Appearance


(i) A colloidal system in which the dispersion medium is a liquid or gas is called a solution. They are called
hydrosols or aqua sols, if the dispersion medium is water. When the dispersion medium is alcohol or
benzene, they are accordingly called alcosols or benzosolution They have a fluid-like appearance.
(ii) Colloidal systems in which the dispersion medium is a gas are called aerosols.

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Surface Chemistry 12.127

(iii) Colloids in which the dispersion medium is a solid are called gels, e.g., cheese, etc. They have a more
rigid structure. Some colloids, such as gelatin, can behave both as a sol and a gel. At high tempera-
ture and low concentration of gelatin, the colloid is a hydrosolution But at low temperature and high
gelatin concentration, the hydrosol can change into a gel. The phenomenon of sol–gel transforma-
tion is called thixotropy.

12.7.2 Based Upon Charge


The colloids can be classified into positive or negative colloids according to the charge present on the
dispersed phase particles. Metal hydroxides are generally positively charged while metal sulphides carry a
negative charge.

12.7.2.1 Positive and negative charged sol

Positively Charged Sols Negatively Charged Sols


Ferric hydroxide, aluminium hydroxide Metals such as Pt, Au, Ag,
Basic dyes such as methylene blue Metals sulphides, e.g., As2S3
Haemoglobin Starch, clay, silicic acid, acid dyes, such as eosin.

12.7.3 Based on Interaction or Affinity of Phases


On the basis of the affinity or interaction between the dispersed phase and the dispersion medium, the
colloids may be classified into two types:

12.7.3.1 Lyophilic colloids


The colloidal system in which the particles of dispersed phase have great affinity for the dispersion me-
dium are called lyophilic (solvent-loving) colloids. In such colloids, the dispersed phase does not get
easily precipitated and the solutions are more stable. Such colloidal systems, even if precipitated, may be
reconverted to the colloidal state by simply agitating them with the dispersion medium. Hence, lyophilic
colloids are reversible.

12.7.3.2 Lyophobic colloids


The colloidal system in which the dispersed phase has no affinity for the dispersion medium is called
lyophobic (solvent-hating) colloids. They are easily precipitated (or coagulated) on the addition of small
amounts of the electrolyte or by heating or by shaking. They are less stable and irreversible.

S. No. Property Lyophilic Sols Lyophobic Sols


1. Nature Reversible Irreversible
2. Preparation They are prepared very easily by They are difficult to prepare,
shaking or warming the substance special methods are used.
with dispersion medium. They do Addition of stabilizer is essential
not required any electrolyte for for their stability.
stabilization.
C
( ontinued)

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12.128 Chemistry at a Glance

S. No. Property Lyophilic Sols Lyophobic Sols


3. Stability They are very stable and are not They are generally unstable and
easily coagulated by electrolytes. get easily coagulated on addition
of electrolytes.
4. Charge Particles carry no or very little Colligative particles have
charge depending upon the pH of characteristic charge
the medium. (positive or negative).
5. Viscosity Viscosity is much higher than that Viscosity is nearly the same as
of the medium. that of the medium.
6. Surface Surface tension is usually higher Surface tension is nearly the same
Tension than that of the medium. as that of the medium.
7. Solvation Particles are heavily solvated. Particles are not solvated.
8. Visibility The particles cannot be seen under The particles though invisible, can
an ultramicroscope. be seen under an ultra microscope.
9. Tyndall effect Less distinct. More distinct.
10. Colligative They have relatively higher They have low osmotic pressure,
property osmotic pressure , high depression small depression of freezing point,
of freezing point and high less elevation of boiling point and
lowering of vapour pressure. less lowering of vapour pressure.
11. Action of Large amount of electrolyte is Small amount of electrolyte is
electrolyte required to cause coagulation. sufficient to cause coagulation.
12. Conductivity They show high conductivity Due to their sensitivity in
which can be measured. electrolyte, conductivity can rarely
be measured over a considerable
range of concentration.
13. Examples Mostly organic substances, Generally inorganic substances
e.g., starch, gums, proteins, e.g., metal sols, sulphide and
gelatin, etc. oxides sols.

12.7.4 Based on Molecular Size


Depending upon the molecular size, the colloidal system has been classified into three classes:

12.7.4.1 Multimolecular colloids


The multimolecular colloidal particles consists of an aggregate of atoms of small molecules with diameters
less than 10–9 m or 1 nm. E.g., a solution of gold contains particles of various sizes having several atoms. A
solution of sulphur consists of particles containing a thousand or so S2 molecules. These particles are held
together by Van der Waal’s forces. They are usually lyophobic sols.

12.7.4.2 Macromolecular colloids


The macromolecular colloidal particles themselves are large molecules. They have very high molecular
weights varying from thousands to millions. These substances are generally polymers. Naturally occurring

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Surface Chemistry 12.129

macromolecules are such as starch, cellulose and proteins. Artificial macromolecules are such as polyeth-
ylene, nylon, polystyrene, dacron, synthetic rubber, plastics, etc. The size of these molecules is comparable
to those of colloidal particles and therefore, their dispersion known as macromolecular colloids. Their
dispersion also resemble true solutions in some respects.

12.7.4.3 The associated colloids or micelles &22±

Colloids which behave as normal electrolytes at low concentration, but exhibit col-
loidal properties at higher concentration due to the formation of aggregated parti-
cles called micelles are referred to as associated colloids. The micelles are formed
by the association of dispersed particles above a certain concentration and certain
minimum concentration is required for the process of aggregation to take place.
The minimum concentration required for micelle formation is called critical micellisation
concentration (CMC) and its value depends upon the nature of the dispersed phase. For soaps, CMC is
10–3 mole L–1. Micelles may contain 100 molecules or more.
The formation of a micelle takes place above a particular temperature called kraft temperature (Tk)
and above a particular concentration called critical micellisation concentration (CMC).

12.8 PRoPeRties of colloiDAl solUtions

12.8.1 Physical Properties


12.8.1.1 Heterogeneity

Colloidal solutions are heterogeneous in nature consisting of two phases, viz. the dispersed phase and
the dispersion medium. Experiment like dialysis and ultrafiltration clearly indicate the heterogeneous
character of a colloidal system. Recent investigations, however, have shown that colloidal solutions are
neither obviously homogeneous nor obviously heterogeneous.

12.8.1.2 Filterability
Colloidal particles readily pass through ordinary filter papers. It is because the size of the pores of the filter
paper is larger than that of the colloidal particles.

12.8.1.3 Non-settling nature

Colloidal solutions are quite stable as the colloidal particles remain suspended in the dispersion medium
indefinitely. Thus, there is no effect of gravity on the colloidal particles.

12.8.1.4 Colour

The colour of the colloidal solution is not always the same as the colour of the substances in the bulk. The
colour of the colloidal solution depends upon the following factors:
(a) Size and shape of colloidal particles
(b) Wavelength of the source of light
(c) Method of preparation of the colloidal solution

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12.130 Chemistry at a Glance

(d) Nature of the colloidal solution


(e) The way an observer receives light, i.e., whether by reflection or by transmission.
e.g., (i) Finest gold is red in colour. As the size of particles increases, it becomes purple. Due to this
fact, gold sol is also called purple of cassius.
(ii) Dilute milk gives a bluish tinge in reflected light, whereas reddish tinge in transmitted light.

12.8.2 Mechanical Properties


12.8.2.1 Brownian movement

Robert Brown first observed this motion with pollen grains suspended in water. Colloidal particles ex-
hibit a ceaseless random and swarming motion. This kinetic activity of particles suspended in the liquid is
called Brownian movement.
Cause of movement: Brownian movement is due to bombardment of the dispersed phase particles by
the molecules of the dispersion medium. Brownian movement depends upon the size of sol particles. With
the increase in the size of the particle, the chance of unequal bombardment
increases, and Brownian movement disappears. Due to this fact, suspension
fails to exhibit this phenomenon. It should be noted that Brownian movement
does not change with time but changes with temperatures.

12.8.3 Optical Properties (Tyndall Effect)


When a strong and converging beam of light is passed through a colloidal solution, its path becomes visible
(bluish light) when viewed at right angles to the beam of light. This effect is called Tyndall effect. The light
is observed as a bluish cone which is called Tyndall cone.
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Tyndall effect is due to scattering of light by the colloidal particles. The scattering of light cannot be due
to simple reflection, because the size of the particles is smaller than the wavelength of the visible light and
they are unable to reflect light waves. In fact, colloidal particles first absorb light and then a part of the
absorbed light is scattered from the surface of the colloidal particles as a light of shorter wavelength. Since
maximum scattering of light takes place at right angles to the plane of incident light, it becomes visible
when seen from that direction.

12.8.3.1 Condition for tyndall effect


(i) The diameter of the dispersed particles must not be much smaller than the wavelength of light
employed.

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Surface Chemistry 12.131

(ii) The refractive indices of the dispersed phase and the dispersion medium must differ widely. This
condition is fulfilled by lyophobic colloids. It is important to note that Tyndall effect is not shown
by true solutions as their particles are too small to cause scattering. Tyndall effect has been used in
devising ultramicroscope and in determining the number of a colloidal solution.

12.8.4 Electrical Properties


Electrophoresis or cataphoresis: In a colloidal solution, the colloidal particles are electrically charged
and the dispersion medium has equal but opposite charge. Thus, colloidal solution as a whole is electri-
cally neutral. When an electric current is passed through a colloidal solution, the charged particles move
towards the oppositely charged eletrode where they coagulate due to loss of charge.
The phenomenon involving the migration of colloidal particles under the influence of an electric field
towards the oppositely charged electrode is called electrophoresis or cataphoresis.

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This phenomenon is used to determine the charge on the colloidal particles. For example, when a solution of
ferric hydroxide is taken in a U-tube and subjected to an electric field, the ferric hydroxide (solution) particles
get accumulated near the cathode. This shows that ferric hydroxide solution particles are positively charged.
The solution particles of metals and their sulphides are found to be negatively charged while those of
metal hydroxides are positively charged. Basic dyes such as methylene blue, haemoglobin are positively
charged while acid dyes like eosin are negatively charged.

12.8.4.1 Electrical double layer )L[HGOD\HU

The surface of a colloidal particle acquires a positive or a negative charge by ± 'LIIXVHG
± OD\HU
selective adsorption of ions carrying +ve and –ve charges, respectively. The
±
charged layer attracts counter ions from the medium which forms a second ±
layer. Thus, an electrical double layer is formed on the surface of the parti- ±
cles, i.e., one due to adsorbed ions and the other due to oppositely charged ±
ions forming a diffused layer. This layer consists of ion of both the signs, but ±
its net charge is equal and opposite to those absorbed by the colloidal parti- ±
cles. The existence of charges of opposite signs on the fixed and diffused parts ±
of the double layer creates a potential between these layers. This potential dif- ±
ference between the fixed charge layer and diffused layer of opposite charge ±
is called electrokinetic potential or zeta potential (Z). ±

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12.132 Chemistry at a Glance

4 πην
Z= ; where h is coefficient of viscosity, D is dielectric constant and n is velocity of colloidal
D
particles when an electric field is applied.

12.9 coAgUlAtion

The colloidal solutions are stable due to the presence of electric charges on the colloidal particles. Because
of the electrical repulsion, the particles do not come close to one another to form precipitates. The re-
moval of charge by any means will lead to the aggregation of particles and hence precipitation will occur
immediately.
The coagulation process by means of which the particles instead of settling at the bottom of the con-
tainer, float on the surface of the dispersion medium is called flocculation. Most of the solutions are co-
agulated by adding an electrolyte of opposite sign.

Note:
The minimum amount of an electrolyte required to cause precipitation of one litre of a colloidal solution is called coagu-
lation value or flocculation value of the electrolyte for the solution The reciprocal of coagulation value is regarded as the
coagulating power, e.g., the coagulation values of NaCl; BaCl2 and AlCl3 for arsenic sulphide solution are 51, 0.69 and
1 1 1
0.093 millimoles/litre, respectively. Thus, their coagulating powers are , and , i.e., 0.0196, 1.449 and
51 0.69 0.093
10.75, respectively.

12.9.1 Hardy-Schulze Rules


H. Schulze (1882) and W B Hardy (1900) suggested the following rules to discuss the effect of electrolytes
on the coagulation of the solution
1. Only the ions carrying charge opposite to the one present on the solution particles are effective to
cause coagulation, e.g., the negative charged solution is best coagulated by cation and a positive
solution is coagulated by anion.
2. The charge on coagulating ion influences the coagulation of solution.
‘’Higher is the valency of the active ion, greater will be its power to precipitate the solution’’
Thus, coagulating power of cation is in the order of Al3+ > Ba2+ or Mg2+ > Na+ or K+.
Similarly, to coagulate the positively charged solution the coagulating power of anion is in the order
of [Fe (CN)6]4- > PO43– > SO42– > Cl–.

12.10 PRotective colloiDs


Lyophilic solutions are more stable than the lyophobic sols. This is because, lyophilic colloids are
extensively hydrated and these hydrated particles do not combine to form large aggregates.
Lyophobic solutions are more easily coagulated by the addition of a suitable electrolyte. To avoid
the precipitation of lyophobic solution by the addition of electrolyte, some lyophilic colloid is added to it.
Such a lyophilic colloid is called protective colloid. The substances commonly used as protective colloids
are gelatin, albumin, gum arabic, casein, starch glue, etc. A gold solution containing a little gelatin as
protective colloid needs a very large amount of sodium chloride to coagulate the solution.

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Surface Chemistry 12.133

12.10.1 Gold Number


The protective power of the lyophilic colloids is expressed in terms of gold number, a term introduced by
Zsigmondy. Gold number is the number of milligram of the protective colloid which prevent the coagula-
tion of 10 ml of red gold solution when 1 ml of a 10 per cent solution of sodium chloride is added to it.

Note:
Thus, smaller the gold number of lyophilic colloid, the greater is its protective power.

Congo rubin number: The amount of protective colloid in milligram which prevents colour change in
100 ml of 0.01 per cent congo rubin solution to which 0.15 gram equivalent of KCl is added when observed
after 10–16 minutes.

12.11 emUlsion
An emulsion is a colloidal solution of a liquid. It may be defined as a heterogeneous system consisting of
more than one immiscible liquid dispersed in one another in the form of droplets whose diameter, in gen-
eral, exceeds 0.1 g. The emulsions are classified as:

12.11.1 Classification of Emulsion


12.11.1.1 Oil in water type

In this emulsion, an oil is the dispersed phase and water is the dispersion medium. It is denoted by O/W
or O in W. For example, milk, vanishing cream, etc. fall under this category.

12.11.1.2 Water in oil type


In this emulsion, water is the dispersed phase and oil is the dispersion medium. It is denoted by W/O or
W in O. For example, butter, cod liver oil, cold cream, etc. The type of emulsion obtained by agitating
two immiscible liquids depends upon the relative amounts of two compounds liquids. The liquid that is
in excess forms the dispersion medium. Thus, the two types of emulsion can be interconverted into each
other by changing the concentration of one of the liquids.

12.11.2 Distinction Between two Types of Emulsion


The two types of emulsions may be distinguished from each other in a number of ways.

12.11.2.1 Dye test


It involves the addition of an oil soluble dye to the emulsion under experiment. If the emulsion acquires
the colour of the dye readily , it is water-in-oil type emulsion.

12.11.2.2 Conductivity test


It involves the addition of an electrolyte to the emulsion under experiment. If the conductivity of the
emulsion increases appreciably with the addition of the electrolyte, it is oil-in-water type emulsion and if
conductivity is very small, it is water-in-oil type emulsion.

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12.134 Chemistry at a Glance

12.11.2.3 Dilution test


As a general rule, an emulsion can be diluted with the dispersion medium while the addition of the
dispersed phase forms a separate layer. Thus, if an emulsion can be diluted with oil, it is water-in-oil type.

12.11.3 Preparation of Emulsion (Emulsification)


An emulsion is prepared by subjecting a mixture of the immiscible liquid to a distinct layer upon standing.
The oil globules rise to form an upper layer while aqueous medium forms lower layers.
To prevent the separation of layers and to get the stable emulsion, a small quantity of the third sub-
stance is added. This substance which stabilizes the emulsion is called emulsifier or emulsifying agent.
The commonly used emulsifying agents are soaps, detergents and lyophilic colloids. Casein, a lyophilic
colloid present in milk, acts as an emulsifier as it forms a protective layer around fat molecules dispersed
in water. Hence, milk is a fairly stable emulsion.
Function of emulsifier: The main function of emulsifier or emulsifying agents is to lower the interfacial
tension between oil and water and thus help in the intermixing of two liquids.

12.11.4 Uses of Emulsion


1. Many pharmaceutical preparations such as medicines, ointments, creams and various lotions are
emulsions. It is believed that medicines are more effective and easily assimilated by the body tissues
when they are in colloidal form, i.e., emulsion.
2. The digestion of fat in the intestines is facilitated by emulsification.
3. Soaps and detergents remove dust and dirt from the dirty piece of cloth by making an oil-in-water
type emulsion.
4. In the process of metallurgy, one of the important steps is the concentration of ore which is usually
done by froth floatation process in which an oil is added to the finely-divided ore taken in water.
The particles of ore move to the surface due to formation of foams while the other impurities are left
at the bottom of the vessel.

12.12 gels
Colloidal system in which liquids are the dispersed phase and solid act as the dispersion medium
is called a gel. The common examples are boot polishes, gum arabic, agar agar, processed cheese and
silicic acid .
Gels are divided into two categories, i.e., elastic and non-elastic gels.
Comparative Study Between Elastic and Non-Elastic Gels

Elastic Gels Non-Elastic Gels


1. They change to solid mass on dehydration 1. They change to solid mass on
which can be changed back to original form dehydration which cannot be changed
with water. back to original form with water.
2. They absorb water when placed in with simultane- 2. They do not exhibit imbibitions.
ous swelling. This phenomenon is called imbibition.

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Surface Chemistry 12.135

Note:
When the gels are allowed to stand for a long time, they give out small quantities of trapped liquids which accumu-
late on its surface. This action of gels is known as syneresis or weeping. Some gels such as silica , gelatin and ferric
hydroxide liquefy on shaking and reset on following to stand. This phenomenon of sol–gel transformation is called
thixotropy.

12.13 APPlicAtions of colloiDAl solUtion


12.13.1 Medicine
The medicines containing gold, silver or calcium, etc. in colloidal form are more effective and easily
assimilated by the human systems.

12.13.2 Smoke Screens


Smoke screens which consist of titanium dioxide dispersed in air are used in warfare for the purpose of
concealment and camouflage.

12.13.3 Formation of Delta


The river water carries with it charged clay particles and many other substances in the form of colloidal
solution. When the sea water comes in contact with these particles, the colloidal particles in river water are
coagulated by the electrolytes present in sea water to form deltas.

12.13.4 Purification of Water


The turbidity in water is due to the presence of negatively charged clay particles. The addition
of potash alum, i.e., Al3+ ions neutralizes the negative charge on the colloidal particles
and thus causes their coagulation. The coagulated matter settles down and thus water
becomes clear.

12.13.5 Artificial Rain


Artificial rain can be caused by throwing electrified sand on clouds which are colloidal solution or charged
particles of water in air.

12.13.6 Sewage Disposal


Sewage water consists of particle of dirt , rubbish, mud, etc. which are of colloidal dimensions and carry
an electric charge and thus do not settle down easily. These particles can be removed by cataphoresis.
A system of two tanks fitted with metallic electrodes is used for this purpose. When an electric field is
created, then the dust particles are coagulated on the oppositely charged electrodes. The deposit may be
utilized as a manure.

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12.136 Chemistry at a Glance

12.13.7 Blue Colour of the Sky


Colloidal particles scatter only blue light and the rest of it is absorbed. In sky there are number of dust and
water particles. They scatter blue light and, therefore, sky looks bluish. If there were no scattering, the sky
would have appeared totally dark.

12.14 PRePARAtion of colloiDAl solUtions

12.14.1 Preparation of Lyophilic Sols


The colloidal solutions of lyophilic colloids like starch, glue, gelatin, etc. can be readily prepared by
dissolving these substances in water either in cold or on warming.

12.14.2 Preparation of Lyophobic Solutions


To get a solution in colloidal form either the substance in bulk is broken down into fine parti-
cles of colloidal dimension or increasing the size of molecular particles as to form larger aggre-
gates. A third substance is usually added to increase the stability of the solution These substances are
called stabilizers.
There are two ways by which lyophobic solutions can be prepared.
(a) Dispersion method: By splitting coarse aggregates of a substance into colloidal size. Dispersion
can be done by any one of the following methods.
1. Mechanical disperation: Solid material is first finely ground by usual methods. It is then
mixed with dispersion medium, e.g., water (hydrosols); alcohol (alcosols); benzene (benzosols)
and air (aerosols) which gives a coarse suspension. The suspension is now introduced into a
colloid mill. A machine in which two metal discs are held at a small distance and revolving with
very high speed (700 rev/sec ) in opposite direction. The particles are ground down to colloidal
size and are then dispersed into the liquid. A stabilizer is added to stabilize the colloidal sols.
Colloidal graphite (a lubricant) and printing ink are made by this method. Tannin is used as a
stabilizer for preparation of colloidal graphite and gum arabic in printer ink.
2. Electrodispersion: i.e., Bredig’s arc method: This method is suitable for the preparation of
colloidal solutions of metal like gold, silver, platinum, etc. An arc is struck between the metal
electrodes under the surface of water containing some stabilizing agent such as a trace of KOH.
The water is cooled by immersing the container in an ice bath. The intense heat of the arc va-
pourizes some of the metal which condenses under cold water. This method is not suitable
when the dispersion medium is an organic liquid as considerable charring occurs. This method
involves both dispersion and condensation.
3. Ultrasonic dispersion: The sound waves of high frequency are usually called ultrasonic
waves. These waves can be used for preparation of colloidal solution. e.g., oils, mercury, sul-
phur, sulphides and oxides of metals can be dispersed into colloidal state very easily by
this method.
4. Peptization: The dispersion of a freshly precipitated material into colloidal solutions by the
action of an electrolyte in solution is termed as peptization. Electrolyte used for this purpose is
known as peptizing agent. Some examples of salts obtained by peptization are

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Surface Chemistry 12.137

(i) Freshly prepared Fe(OH)3 + FeCl3 → Reddish brown solutions.


(Small amount) (Peptizing agent)
(ii) SnO2 + HCl → colloidal solution of SnO2
(iii) AgCl + HCl → Colloidal solution of AgCl
(b) Condensation method: By aggregating very small particles (atoms, ions or molecules) into
colloidal size. Condensation can be done by any one of the following methods.
1. By exchange of solvent: Substance whose colloidal solution can be prepared by taking a solu-
tion of the substance in one solvent and pouring it into another solvent in which the substance
is relatively less soluble. e.g., solution of S or P prepared in alcohol and poured in water in which
it is less soluble.
2. By change of physical state: Colloidal solutions of certain elements such as Hg and S are
obtained by passing their vapour through cold water containing a stabilizer as an ammonium
salt of a citrate.
3. Chemical methods: The chemical methods involve chemical reactions in a medium in which
the dispersed phase is sparingly soluble. A condition of super saturation is produced but the
actual precipitation is avoided.
(i) As2 S3 colloidal solution is obtained on passing H2S gas into cold As2O3 solution.
As 2O3 + 3H2S 
→ As 2S3 + 3H2O
(Yellow solution)

(ii) Sb2S3 colloidal solutions is obtained on passing H2S gas into 0.5 per cent solutions of potas-
sium antimonyl tartrate solution.
HO−CH−COOK HO−CH−COOK
| + 3H3S → | + Sb2S3 + 2H2O
HO−CH−COO(SbO) HO−CH−COOH (Orange solution)
(iii) A colloidal solution of S is obtained by passing H2S into a solution of SO2.
2H2S + SO2 → 2H2O + 3S
(iv) Colloidal solutions of metals like gold, silver, platinum, etc. can be obtained when these
salts are acted upon by a reducing agent. 2 AuCl3 + 3SnCl2 → 2SnCl4 + 2Au
Organic reducing agent such as formaldehyde, phenylhydrazine, tannic acid, etc. can also
be used.
AgNO3 + Tannic acid → Silver solution
AuCl3 + Tannic acid → Gold solution
(v) Colloidal solution of Fe(OH)3 can be obtained by boiling a dilute solution of FeCl3.
FeCl 3 + 3H2O 
→ Fe(OH)3 + 3HCl
Red sol.

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Chapter 13 periodiC
ClassifiCation

13.1 Long Form oF Periodic TabLe


Long form of periodic table is also called Modern periodic table (MPT). In 1913, Moseley showed that
the position of an element in the periodic table depends on its atomic number and not on its atomic mass
and gave the following periodic law. ‘The physical and chemical properties of the elements vary in relation
to their atomic numbers’.

13.1.1 Characteristics of Modern Periodic Table


On the basis of electronic configuration of element.
(i) The MPT is divided into 4 blocks namely s, p, d and f. All elements have their last electron in the s,
p, d and f subshell and are placed in s, p, d and f block, respectively.
(ii) The MPT is divided into 7 horizontal rows called the periods. The period number tells us the PQN
of the outermost occupied orbit of the element.
e.g., x15 [Ne]3s2 3p3 y35 4s24p5
Thus, element x and y will be present in the third and fourth periods, respectively.
(iii) The MPT is also divided into a number of vertical columns called groups. The group number tells
us the total number of electrons present in the outermost orbit of an element.
e.g., the elements in above example, x and y will be kept in 5th and 7th group, respectively.
(iv) Groups I to VII are further divided into subgroups A and B. All elements having their last electron
in ‘s or p’ orbital are kept in the subgroup A, whereas the subgroup B contains the elements having
their last electron in the ‘d’ or ‘f ’ orbitals.
(v) In the modern periodic table, the VIII group is divided into three vertical columns, so that all nine
elements are given different positions. Hence, MPT contains ‘18’ vertical columns.

13.1.2 Advantages of MPT over Mendeleef’s Periodic Table


(i) Subgroups A and B are given separate positions.
(ii) In the eighth group, all elements were given separate position.
(iii) The lanthanides and actinides are given a definite position in the form of f block below the main
body of MPT.
35
(iv) All isotopes of an element are given same position as they have same atomic number, e.g., 17 Cl
37
and 17 Cl.

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(v) The highly electropositive and electronegative nature of I A and VII A group may be explained on
13.140

Chemistry at a Glance Final.pdf 146


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4/1/2014 12:26:10 PM
Chemistry at a Glance
ChemiCal
Chapter 14
Bonding

14.1 introduction
YH
Whenever two or more than two atoms combines, then a 3(
smallest stable species called molecule is produced. The binding U

forces holding together the atoms inside a molecule is called
chemical bond. During the formation of chemical bond PE of ,QWHUQXFOHDU
the system decreases and therefore energy is released. Formation GLVWDQFH U
±YH
of chemical bond occurs at that stage where PE of the system is %RQGOHQJWK
minimum.
The nature of a compound depends upon the type of bond present inside it which in turn is governed
by the nature of combining atom.

14.2 tHEorY oF cHEMicAL BondinG


The bond formation takes place to make the system more stable. Stability is in two forms either lowering
of energy of a system or a well defined arrangement of its constituents. For this, two factors are there to
explain atomic interaction.
1. Tendency to acquire noble gas configuration.
2. Tendency to acquire minimum energy.

14.3 ELEctrovALEnt or ionic Bond


Electrovalent bonding requires two atoms of different nature. One atom should have the tendency to lose
electron, i.e., electropositive in nature and the other atom should have the tendency to accept electron,
i.e., electronegative in nature. Ionic bonds are formed by loss and gain of e– between two atoms. The
electrostatic force of attraction developed between the cation and anion is known as ionic bond. It is also
called electrovalent bond due to involvement of electrostatic forces of attraction.
e.g., 1D  &O 1D  &O 1D&O± 1D&O
   

Condition for formation of ionic bond: The following conditions favour the formation of an
electrovalent bond.

Chemistry at a Glance Final.pdf 147 4/1/2014 12:26:10 PM


14.142 Chemistry at a Glance

(i) In general atoms having 1, 2 or 3 valence electrons in outermost shell changes into cation and
atoms having 5, 6 or 7e– in valency shell changes into anion.
(ii) Electronegativity difference: With a great difference in electronegativity of two atoms, it is easier
to form an ionic bond.
(iii) Overall lowering of energy: Energy must be released during ionic bond formation.
(iv) Lattice energy: Higher the lattice energy greater, will be the ease of formation of the ionic
compound.
Factors influencing magnitude of lattice energy are as follows:
(a) Size of ions: Smaller the size of the ions, lesser is the internuclear distance. Consequently, the
interionic attraction will be high and lattice energy will also be large.
(b) Charge on ions: Larger the magnitude of charge on the ions, greater will be the attractive forces
between the ions. Consequently, the lattice energy will be high.

Note:
Lower the value of IE and higher the value of EA there is more ease of formation of the cation and anion from it
respectively and consequently more chances of electrovalent bond formation.

14.3.1 Characteristic of Ionic Compounds


General properties of ionic compounds are as follows:
(i) They are not true bond because they are neither rigid nor directional.
(ii) In the solid state each cation surrounds itself with anions and each anion with cations. These large
number of ions are arranged in an orderly manner called ionic crystal.
(iii) They are hard and brittle.
(iv) They are good conductors of electricity in fused state and in aqueous solution.
(v) They are soluble in polar solvents and insoluble in non-polar solvents.
(vi) They have high mp and bp

14.4 covALEnt Bond


A covalent bond may be defined as the bond formed by mutual sharing of electrons between the
combining atoms (which are short of electrons) of comparable electronegativity. The combining atoms
thus achieve inert gas configuration. The shared electron contribute towards the stability of both atoms.

14.4.1 Covalency
It is defined as the number of electrons contributed by an atom of the element for sharing with other.

14.4.2 Lewis Dot Structure


Six steps are involved in writing Lewis dot structure.
(i) Arrange the atoms in space as per their actual configuration. Least electronegative atom should be
the central atom except hydrogen.
H
e.g., methylnitrite (CH3 NO2 )H C O N O
H

Chemistry at a Glance Final.pdf 148 4/1/2014 12:26:10 PM


Chemical Bonding 14.143

(ii) Count all the valence electrons including the charge and divide this number by 2 to obtain number
of electron pairs.
e.g., in CH3NO2, number of valence electron = 4 + 1 × 3 + 5 + 6 × 2 = 24
⇒ Number of electron pair = 24 / 2 = 12.
(iii) Place one electron pair each between the atoms actually connected by bond.
+
e.g., + & 2 1 2
+
(iv) Place the remaining electron pairs on terminal atoms till their octet is completed. If electron pairs
still remain put them on central atom.
+
e.g., + & 2 1 2
+
(v) Check whether the octet of central atom is complete a not. If not, then convert one or more lone pair
on terminal atoms in double or triple bonds.
Example:
+ +

(a) + & 2 1 2 + & 2 1 2
+ +
(b) CO3–2 number of valence electron= 2 + 4 + 6 × 3 = 24 e–
Number of electron pair = 24 / 2 = 12
± ± ±
2 2 2
& & &
2 2 2 2 2 2

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(vi) Formal charge of central atom should be kept as low as possible. Normally it is equal to zero.
Formal charge = number of valence electrons – number of bond pair –2 × number of lone pair.

14.4.3 Characteristics of Covalent Compounds


(i) Physical state: Under the normal conditions of temperature and pressure, they exist as gases
or liquids of low boiling points. Because of weak forces of attraction, Van der Wall’s forces exist
between discrete molecules.
(ii) Melting and boiling points: With the exception of few which have giant three-dimensional
structures such as diamond, carborundum (SiC), Silica (SiO2), others have relatively low melting
and boiling points.
This is due to the presence of weak attractive forces between the molecules.
(iii) Electrical conductivity:
(a) In general, covalent substances are bad conductors of electricity.
(b) Substances which have polar character like HCl in solution, can conduct electricity.
(c) Covalent solids having giant molecules, are bad conductors since they do not contain charged
particles or free electrons.
(d) The graphite can conduct electricity since electrons can pass from one layer to
the other.

Chemistry at a Glance Final.pdf 149 4/1/2014 12:26:10 PM


14.144 Chemistry at a Glance

(v) Solubility:
(a) Polar compounds are soluble in a polar solvent (i.e., DEN from 0.9 to 1.8), polar solvents
are H2O, CHCl3, alcohol, etc.
(b) Non-polar compounds are soluble in a non-polar solvent. Non-polar solvents are CCl4, benzene,
CS2 etc.

14.4.4 Coordinate Covalent Bond


A covalent bond in which both the electrons in the shared pair come from one atom is called a coordinate
covalent bond. Such type of bond is formed between atoms (or ions), one of which is deficient in at
least two electrons while the other atom has already acquired a stable noble gas configuration. The atom
which contributes both the electrons is called the donor while the other which only shares the electron
pair is known as acceptor. This bond is usually represented by an arrow (→) pointing from donor to the
acceptor atom.

14.5 tHE vALEncE Bond tHEorY

14.5.1 Heitler and London Concept


(i) For a covalent bond to form, two atoms must come closer to each other so that their orbitals overlaps
with each other.
(ii) Overlapping orbitals must have half-filled nature, i.e., they must have unpaired electron and
anti-spin electrons.
(iii) As a result of overlapping, a new localized bond orbital is formed, in which probability of finding an
electron pair is maximum.
(iv) Covalent bond arises due to electrostatic attraction between nuclei and the accumulated electron
cloud.
(v) Greater is the overlapping, lesser will be the bond length, more will be attraction and more will be
bond energy, and the stability of bond.

14.5.2 Pauling and Slater Extension


(i) According to this theory the extent of overlapping of orbitals depends upon nature of orbitals in-
volved in overlapping and nature of overlapping.
(ii) More closer the valence shell of orbital to the nucleus, more will be the overlapping, and the bond
energy will also be high. Bond energy of 1 – 1 > 1 – 2 > 2 – 2 > 2 – 3 > 3 – 3.
(iii) Between two subshells of same energy level, the subshell which is more directionally concentrated
shows more overlapping. Bond energy: 2s – 2s < 2s – 2p < 2p – 2p.
(iv) s-orbitals are spherically symmetrical and thus show only head on overlapping. On the other
hand, p-orbitals are directionally concentrated and thus show either head on overlapping or lateral
overlapping.

14.5.3 Types of Overlapping and Nature of Covalent Bonds


Depending upon the type of overlapping, the covalent bonds may be divided into two types.
(A) sigma (s) bond (B) Pi (p) bond

Chemistry at a Glance Final.pdf 150 4/1/2014 12:26:10 PM


Chemical Bonding 14.145

(i) Sigma (s) bond :


(a) Sigma bond is formed by the end-to-end overlapping of bonding orbitals along the internuclear axis.

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(b) The overlap is known as head on overlap or axial overlap.


(c) The sigma bond is formed by any one of the following type of combinations of atomic orbitals
(d) Free rotation about s bond is possible.
(e) Geometry of a covalent molecule entirely depends upon s bond pair.
(ii) Pi (p) bond:
(a) This type of covalent bond is formed by sidewise overlapping of half-filled atomic orbitals of
bonding atoms.
(b) The orbitals involved in overlap must be parallel to each other and perpendicular to the
internuclear axis.
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(c) It is always accompanied by a s bond and consists of two charge clouds, i.e., above and below the
plane of sigma bond.
(d) Since overlapping takes place on both sides of the internuclear axis, free rotation of atoms around a
p bond is not possible.
(e) Furthermore, formation of a p bond shortens the bond distance between the two atoms involved,
e.g., C – C, C = C, C ≡ C, bond lengths are 1.54Å, 1.3Å and 1.20Å, respectively.

14.6 HYBridizAtion
The concept of hybridization was introduced by Pauling. Hybridization is defined as the intermixing of
dissimilar orbitals of the same atom but having slightly different energies to form same number of new
orbitals of equal energies and identical shapes.
The new orbitals so formed are known as hybrid orbitals whose shape is similar to p-orbital except
that the two lobes are unequal in size.

14.6.1 Characteristics of Hybridization


1. Only orbitals of almost similar energies and belonging to the same atom or ion undergo
hybridization.

Chemistry at a Glance Final.pdf 151 4/1/2014 12:26:10 PM


14.146 Chemistry at a Glance

2. The number of hybrid orbitals produced is equal to the number of pure orbitals mixed during hy-
bridization, e.g., four hybrid orbitals are produced by mixing one s and three p(px, py and pz) pure
orbitals.
3. Half-filled orbitals, fully filled vacant orbitals of equivalent energy can involve in hybridization.
4. Hybrid orbitals are identical in terms shape, size and energy.
5. Orbitals involved in p bond formation do not participate in hybridization.
6. Hybridization never takes place in an isolated atom but it occurs only at the time of bond formation.
7. The hybrid orbitals are distributed in space as far apart as possible resulting in a definite geometry of
molecule.
8. Hybridized orbitals provide efficient overlapping than overlapping by pure s, p and d-orbitals.
9. The number of ‘p’ orbitals that take place in hybridization is called hybridization index (m) and for
organic molecules cos a = –1/m, where a is the bond angle between two hybrid orbitals.
e.g., for sp hybridization, m =1, hence, cos a = –1 or a =180°
1
for sp2 hybridization m = 2, hence, cos α = − or a = 120°
2

14.6.2 Type of Hybridization


(a) sp hybridization: (linear geometry), e.g., BeF2

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) )
%H
V V
SVS VSS

(b) sp2 hybridization: (trigonal planar geometry), e.g., BF3

)
VSS

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% VSS

) )
VSS

(c) sp3 hybridization: (tetrahedral geometry), e.g., CH4

Ħ

&
+ +
+

(d) sp3d hybridization: (trigonal bipyramidal geometry), e.g., PCl5

Chemistry at a Glance Final.pdf 152 4/1/2014 12:26:10 PM


Chemical Bonding 14.147

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)

14.7 vALEncE SHELL ELEctron PAir rEPuLSion tHEorY

The basic concept of this theory as suggested by Sidgwick and Powell (1940) has provided a highly
useful idea for predicting geometries of molecules. According to this model, the arrangement of
bonds around the central atom depends upon the repulsions operating between pairs of electrons
(bonded or non-bonded) around the central atom.
The main postulates of VSEPR theory are
(i) For polyatomic molecules containing 3 or more atoms, one of the atoms is called the central atom
to which other atoms are linked.
(ii) The geometry of a molecule depends upon the total number of valence shell electron pair (bonded
or non-bonded) present around the central atom and their repulsion due to relative sizes and
shapes.
(iii) The lone pair of electrons in a molecule occupy more space as compared to the bond pair of
electrons. This results in greater repulsion between lone pair of electrons as compared to bond pair.
(iv) If the central atom is linked to similar atoms, the repulsion between them are also similar. It gives
the symmetrical shape to the molecule.
(v) If the central atom is linked to atoms of different sizes or is surrounded by lone pairs as well as bond
pairs of e– then the molecule has a distorted geometry. The relative order of repulsion between
electron pairs is as: Lp –Lp > Lp –Bp > BP – BP

Chemistry at a Glance Final.pdf 153 4/1/2014 12:26:10 PM


Types of orbitals Type of Number of Arrangement Shapes of Bond Examples
involved Hybridization Electron Pairs of Pairs Molecules Angle
14.148
s p d LP BP Total
1 1 – sp – 2 2 180°

Chemistry at a Glance Final.pdf 154


Linear (Ax2) BeCl2, BeF2, Co2, CS2,
HgCl2, C2H2, MgCl
1 2 – sp2 – 3 3 Trigonal (AX3) 120° BCl3, BF3, CO3–2, SO3, NO3–,
planar C2H4, graphite, BH3, AlCl3
SO2, NO2–, O3, SnCl2

Distorted 1 2 3 Angular (AX2E) 119°

1 3 – sp3 – 4 4 Tetrahedral (AX4) 190°28′ CCl4, CH4, Diamond, SO42–,


S2O32, PO42, SiCl4, SnCl4+,
ClO4–, BF4–, BH4–, AlH4–,
NH4–, PCl4+, NH3, PH3,
Distorted 1 3 4 Trigonal (AX3E) 107°48′ AsH3, SO3–2
Distorted 1 3 4 Pyramidal 102°30′ NF3

Distorted 2 2 4 Pyramidal (AX3E) 104°27′ H2O, F2O (102°), H2S(90°),


V or bent shape l3, Cl2O, NH2
(AX2E2)

1 3 1 sp3 – 5 5 Triangular 120° and PCl5, PF5, SbCl5


Bipyramidal 90°
(AX5)

Distorted 1 4 5 Seesaw of 101°36′, SF4, TeCl4


distorted 86°33′

4/1/2014 12:26:10 PM
tetrahedron
(AX4E)
Chemistry at a Glance
Types of orbitals Type of Number of Arrangement Shapes of Bond Examples
involved Hybridization Electron Pairs of Pairs Molecules Angle
s p d LP BP Total

Chemistry at a Glance Final.pdf 155


Distorted 2 3 5 T-shape (AX3E2) 37°40′ lCl3, ClF3, BrF3
Chemical Bonding

Distorted 3 2 5 Linear (AX2E3) 180° XeF2, l3

1 3 2 sp3d2 – 6 6 Ocatahedral 90° SF6, SnCl62–, PF62–, SeF6UF6,


(AX6) FeF6

Distorted 1 5 6 Square (AX5E) 34°30′ IF5, XeOF4, BrF5


pyramidal

Distorted 2 4 6 Square planar 90° XeF4


(AX4E2)
1 3 3 sp3d3 – 7 7 Pentagonal (AX7) 72°, 90° IF7
bipyramidal

Distorted 1 6 7 Pentagonal 72°, 90° XeF6


(AX6E) pyramidal

[Ni(CN)4]2–, [Pt(NH3)4]2–,
1 2 1 dsp2 – 4 4 Square planar 90° [Cu(NH3)4]2+, [PtCl4]2–

4/1/2014 12:26:10 PM
14.149
14.150 Chemistry at a Glance

14.8 MoLEcuLAr orBitAL tHEorY

(a) There is another approach to chemical bonding known as molecular orbital theory (MOT)
developed by Mulliken and Hund, which explains the bonding characteristics in a better way.
(b) The MOT considers the entire molecule as a unit with all the electrons moving under the influence
of all the nuclei present in the molecule.
(c) This approach recognizes that each electron belongs to the molecule as a whole and may move
within the entire molecule.

14.8.1 Important Features of MOT

(a) Like an atomic orbital, which is around the nucleus of an atom there are molecular orbitals which are
around the nuclei of a molecule.
(b) The molecular orbitals are entirely different from the atomic orbitals from which they are formed.
(c) The valence electrons of the constituent atoms are considered to be moving under the influence of
nuclei of participating atoms in the molecular orbital.
(d) The molecular orbitals possess different energy levels like atomic orbitals in an isolated atom.
(e) The shape of molecular orbitals are dependent upon the shapes of atomic orbitals from which they
are formed.
(f) Molecular orbitals are arranged in order of increasing energy just like atomic orbitals.
(g) The number of molecular orbitals formed is equal to the number of atomic orbitals combining in
bond formation.
(h) Like atomic orbitals, the filling of electrons in molecular orbitals is governed by the three principles
such as Aufbau principle, Hund’s rule and Pauli’s exclusion principle.

14.8.2 Conditions for Atomic Orbitals to Form Molecular Orbitals


(a) The combining atomic orbitals should be of a comparable energy.
(b) The combining atomic orbitals must overlap to a large extent. Greater the overlap, stable is the
molecule formed.
(c) They should be properly oriented.

14.8.3 Relative Energies of Molecular Orbitals and Filling of e-


(a) Two general criteria, which determine the energy of the molecular orbitals are
(i) Initial energy of the atomic orbitals
(ii) The extent of the overlap of the atomic orbitals.
(b) It is obvious that molecular orbitals formed from lower energy atomic orbitals have lower energy
than the molecular orbitals formed from higher energy atomic orbitals.
(c) The relative energies of the molecular orbitals are obtained experimentally from spectroscopic data.
(d) For diatomic species having less than or equal to 14e–.
s1s, s*1s, s2s, s*2s, p2px = p2py, s2pz, p*2px = p*2py, s*2pz

Chemistry at a Glance Final.pdf 156 4/1/2014 12:26:10 PM


Chemical Bonding 14.151

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(e) For diatomic species having greater than 14e–.


s1s, s*1s, s2s, s*2s,s2pz, p2px = p2py, p*2px = p*2py, s*2pz

(QHUJ\LQFUHDVHV

14.8.3.1 Stability of molecules in terms of bond order


(a) The relative stability of a molecule is further evaluated by a parameter known as bond order.
1
(b) Bond order = [Number of electrons in bonding orbitals – Number of electrons in anti-bonding
2
orbitals].
(c) The bond order of 1, 2 and 3 corresponds to single, double and triple bonds, respectively. It may be
mentioned that according to the MO theory, even a fractional bond order is possible. Thus
(d) Stability of molecule µ bond order
(e) Dissociation energy µ bond order
1
(f) Bond length ∝
Bond order
(g) If all the electrons in a molecule are paired, the substance is diamagnetic. On the other hand, if there
are unpaired electrons in the molecule, the substance is paramagnetic. More the number of unpaired
electrons in the molecule, greater is the paramagnetism of the substance.

14.9 covALEnt cHArActEr in ionic coMPoundS: FAzAn’S ruLE


Although in an ionic compound like M+X– the bond is considered to be 100 per cent ionic, but it has some
covalent character. Likewise, a covalent bond has some ionic character. The partial covalent character of an
ionic bond has been explained by Fazan as follows:
(a) When a cation approaches an anion, the electron cloud of the anion is attracted towards the cation
and hence anion gets distorted. This effect is called polarization of the anion.
(b) The power of the cation to polarize the anion is called its polarizing power.
(c) The tendency of the anion to get polarized is called its polarizability.
(d) The greater is the polarization produced, more is the neutralization of the charges (i.e., charge of the
cation by the electron cloud of the anion) and hence the ionic character decreases or the covalent
character increases.
The formation of covalent bond is favoured by the following factors:
1
Covalent character ∝
Cationic size
(a) µ anionic size (b) µ cationic charge and (c) µ anionic charge.
(d) Electronic configuration of the cation: For the two ions of the same size and charge, one with a
pseudonoble gas configuration (i.e., 18 electrons in the outermost shell ) will be more polarizing than
a cation with noble gas configuration (i.e., 8 electron in outer most shell).

Chemistry at a Glance Final.pdf 157 4/1/2014 12:26:10 PM


14.152 Chemistry at a Glance

14.9.1 Applications of Fazan’s Rule (Ionic Potential f)


The polarizing power of a cation can be expressed in terms of ionic potential, f.
Charge on cation
(i) Ionic potential, φ =
size of cation
(ii) f µ is polarizing power and µ is covalent character.
(iii) In a period f increases and in a group f decreases on moving from top to bottom.
(iv) There is a correlation between nature of oxide and value of f as follows:
√f < 2.2 → Basic
√f = 2.2 to 3.3 → Amphoteric
√f = 3.3 → Acidic in nature
(v) Tendency to form complex compounds increases as the value of f increases.
(vi) Thermal stability of a compound involving polyatomic anion is inversely proportional to polar-
izing power of cation and vice versa for monoatomic anion.

14.10 diPoLE MoMEnt

(a) In a polar molecule, one end of the molecule is negative and the other is positive. In other words, there
are two poles present in the molecule and hence the molecule is said to possess an electric dipole.
(b) The product of magnitude of negative or positive charge (q) and the distance (d) between the centres
of positive and negative charges is called dipole moment. It is usually denoted by µ. µ = q × d
(c) The most commonly used unit of dipole moment is debye (D). 1D = 1 × 10–18 esu cm.

14.10.1 Characteristic of Dipole Moment


(i) Dipole moment is a vector quantity, i.e., it has magnitude as well as direction. It is often represented
by an arrow with its tail at the positive centre and head pointing towards the negative end (+ → –).
(ii) As a polar diatomic molecule possess only one polar bond, the dipole moment of that molecule is
equal to the dipole moment of the polar bond.
(iii) As a polyatomic molecule has more than one polar bond, the dipole moment is equal to the resultant
dipole moment of all the individual bonds.
(iv) Again in case of symmetrical molecules such as BF3, CH4 and CCl4 the molecular dipole moment
is found to be zero. This is again because of the fact that individual dipole moments cancels out on
account of the symmetry of the molecule.

14.10.2 Application of Dipole Moment


14.10.2.1 In determination of polarity of bonds
Greater is the magnitude of dipole moment, higher will be the polarity of the bond. But in the strict sense,
this concept is applicable to molecules containing only one polar bond.

14.10.2.2 In determination of per cent ionic character


The percentage of ionic character of a bond can be calculated from the ratio of the observed dipole
moment to the calculate dipole moment (considering 100 per cent ionic character).

Chemistry at a Glance Final.pdf 158 4/1/2014 12:26:10 PM


Chemical Bonding 14.153

Observed dipole moment


i.e., per cent ionic character = × 100
dipole moment considering 100 per cent ionic character
Dipole moment for 100 per cent ionic character can be calculated as follows µ(ionic) = e × d esu cm
In case of organic compounds µcis > µtrans > µpara
If groups present on benzene ring are of same nature.
µortho > µmeta > µpara;

14.11 HYdroGEn BondinG


(i) When a hydrogen atom linked to a highly electronegative atom (like FO or N) comes under the
influence of another strongly electronegative atom, then a weak bond is developed between them
which is called as hydrogen bond or proton bond.
(ii) Hydrogen bond never involves more than three atoms and atoms must be collinear.
(iii) It is represented by dotted line as follows:
G G± G G± G G±
+±;±±±±+±;±±±±+±;

(iv) As a result of hydrogen bonding, a H–atom links the two electronegative atoms simultaneously, one
by a covalent bond and the other by a hydrogen bond. Hence, it is said to form a hydrogen bridge.
(v) It is merely a strong electrostatic attractive forces and not a normal chemical bond. It is very weak
(strength about 2–10 K cal/mol).

14.11.1 Condition For Hydrogen Bonding


The molecule must contain a highly electronegative atom linked to H-atom. The higher the electronegativ-
ity, more is the polarization of the molecule.

14.11.2 Types of Hydrogen Bonding


14.11.2.1 Intermolecular hydrogen bonding

When hydrogen bonding takes place between different molecules of the same or different compounds, it
is called intermolecular hydrogen bonding, e.g., HF, H2O, ROH (same compound) water-alcohol, water
ammonia (different compound, etc.).

14.11.2.2 Intramolecular hydrogen bonding


The hydrogen bonding which takes place within a molecule itself is
2 2+
called intramolecular H-bonding or chelation.
1 &
Conditions of intramolecular hydrogen bonding: 2 2
1. The molecules should contain two groups such that one group + +
contains H-atom linked to a highly electronegative atom and 2 2
21LWURSKHQRO 6DOLF\OLFDFLG
the other group should also contain a highly electronegative
atom linked to a lesser electronegative atom.

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14.154 Chemistry at a Glance

2. The molecule should be planar.


3. The hydrogen bonding should lead to the formation of a figure of six a membered ring including
the H-atom.

14.11.3 Examples of Hydrogen Bonding )G± )G±

1. HF– due to highest value of electronegativity, fluorine forms the +G +G +G +G
strongest hydrogen bonds.
)G± )G±
2. Water (H2O): The bond between
oxygen and hydrogen is polar due to G± c G c G± G G±
electronegativity difference between oxygen 2 + 2 + 2 +
and hydrogen. Electrostatic attraction ƒ
between the negative end of one molecule G
+ G
+ G
+
and the positive end of the other molecule
results in the formation of hydrogen bond.
4. Ammonia: An ammonia molecule has an electronegative +
G
+
G
+
G

nitrogen atom covalently linked to three hydrogen atoms.


G G± G G± G G±
Due to their electronegativity difference, each hydrogen + 1 + 1 + 1
acquires positive charge and nitrogen becomes negatively
changed. Hence, electrostatic attraction between ammonia + + +
molecules takes place resulting in the formation of an G G G

associated molecule as shown below.


Chlorine has the same electronegativity value (3.0) as that of nitrogen (3.0) but does not form
hydrogen bonded due to its large atomic size.

14.11.4 Effect of Hydrogen Bonding


Hydrogen bond helps in explaining the abnormal physical properties in several cases as described below.
1. Association: Due to hydrogen bonding carboxylic acid exist as dimers due to intermolecular
hydrogen bonding as shown below. The molecular masses of these acids are found to be double than
that calculated from their simple formula.
2. Dissociation: In aqueous solution, hydrogen fluoride dissociates and gives the difluoride ion (HF2–)
instead of fluoride ion (F–). This is due to H-bonding in HF. This explains the existence of KHF2.
3. High melting and boiling points: The compound having hydrogen bonding shows abnormally
high melting and boiling points, e.g., HF has higher BP than
HCl and boiling point of alcohols is larger than ethers. + +
4. Solubility in water: Compounds which can form hydrogen 2 +
+ +
bonding with water will dissolve in water. For example, lower 2
alcohols are soluble in water because their molecules can + + +
2 2
form H-bonds with water. Similarly, ammonia and amines +
2 +
are soluble in water due to H-bonding with water + + +
2
5. Viscosity: The substances which can give more 2 +
extensive hydrogen bonding will have higher viscosity. +
2
E.g., ethanol < glycol < glycerol. +

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Chemical Bonding 14.155

6. Density of Water: In case of solid ice, the hydrogen bonding gives rise to a cage like structure of
water molecules due to which volume of the system increases which results in decrease in density.

14.12 vAn dEr WAAL’S ForcES

(a) This type of attractive forces occur in case of non-polar molecules such as H2, O2, Cl2, CH4, CO2, etc.
(b) The existence of weak attractive forces among the non-polar molecule was first proposed by the
dutch scientist J D Van der Waal.
(c) Van der Waal force µ molecular weight
µ Atomic weight
µ Boiling point

14.12.1 Ion–dipole Attraction


 ± 
This force is between an ion such as Na+ and a polar molecule such
as HCl. 1D +&O

14.12.2 Dipole–Dipole Attraction


 ±  ±
It is again in between two polar molecules such as HF
and HCl. +) +&O J

14.12.3 Ion-induced Dipole Attraction


   
In this case a neutral molecule is induced by an ion as a dipole as
shown in the figure.

14.12.4 Dipole-Induced Dipole Attraction


±   ±  
In this case a neutral molecule is induced as a dipole by another
+&O &O
dipole as shown in the figure.

14.12.5 Induced Dipole-Induced Dipole Attraction


Induced dipole attraction or London dispersion force: It occurs between two  
non-polar molecules as in Cl2, He, etc.
&O &O
Note:
The relative strength of various bonds is as follows:
Ionic bond > Covalent bond > Metallic bond > H-bond > Van der Waal forces.

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Chapter 15 S-BloCk
elementS

15.1 AlkAli metAls


s-block elements are those in which the differentiating electron enters into n–s orbital. Since n–s orbital
can accommodate two electrons so s-block consists of two vertical rows numbered as group I and group II.
Group I members are called alkali metals and have ns1 configuration.
These are called alkali metals because their oxides and hydroxides form strong alkali like NaOH,
KOH, etc. Members are Li, Na; K, Rb, Cs and Fr (Francium is radioactive).

15.2 trends in properties


Density: It increases down the group because increase in atomic mass compensates more than the
increase in atomic size. K is lighter than Na due to the abnormal increase in atomic size.
Melting and boiling point: For alkali metals, there are low and decrease down the group. Francium is a
liquid at room temperature. Alkali metals are soft, malleable, ductile and have metallic luster which is due
to the oscillation of electrons.
Ionization enthalpy: For alkali metals, it is minimum in their respective period and decreases down the
group. Due to the low ionization enthalpy alkali metals are the most electropositive elements and form
unipositive cations.
All alkali metals have body centred cubic structure with coordination number.
Flame colouration: Alkali metals impart characteristic colour to the flame because when heated
in Bunsen flame the electrons gets excited to the higher energy level due to tow ionization enthalpy.
Excited electron when drops back to the ground state emit radiations in the visible range and impart
characteristic colour.
Li Na K Rb Cs
Crimson red Golden yellow Paleviolet Purple Sky blue

Photoelectric effect: Due t o the low ionization enthalpy alkali metals (except Li and Na) show
photoelectric effect. K and Cs are used in photoelectric cells.
Electrical conductivity: Alkali metals are good conductors due to the presence of loosely held valence
electrons. Electrical conductivity increases down the group due to the decrease in ionization enthalpy.

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S-Block Elements 15.157

Reducing power: Alkali metals are the strongest reducing agents in their respective period due to their
lowest ionization enthalpy.
Reducing power is in the order Li > Cs > Rb > K > Na.
During reducing property following changes occur:
M(s) → M(g), sublimation energy
M(g) → M+(g) + e–, ionization enthalpy
M+(g) + H2O → M+(aq), hydration energy
Hydration energy outweighs ionization enthalpy in lithium. So, lithium is the strongest reducing agent.
Ionic mobility: Smaller the size, greater the extent of hydration and hence lesser the ionic mobility.
Lithium ion has the lowest ionic mobility due to its high hydration energy.
Chemical properties: Alkali metals have a tendency to form ionic compounds. Alkali metals do not oc-
cur free in nature due to their low ionization enthalpy. When exposed to air these form oxides, hydroxides,
carbonates and bicarbonates.
Reaction with water: Alkali metals react with water to give hydrogen: 2M + 2H2O → 2MOH + H2
Their reactivity increases down the group.
Alkali metal hydroxides are strong bases.
Thermal stability, solubility and basicity increases down the group.
All alkali metal hydroxides are thermally stable except LiOH.
heat
2LiOH → Li 2O + H2O
Reaction with oxygen: Lithium forms Li2O; Na forms peroxide (Na2O3) and K forms superoxide (KO2).
Superoxides are coloured and paramagnetic due to the presence of unpaired electrons. All oxides, perox-
ides and superoxides are basic in nature.
Reaction with hydrogen: Stability of hydrides of alkali metals decreases down the group. Hydrides of
alkali metals are strong reducing agents.
Reaction with halogen: Alkali metals react with halogens to form ionic halides which are soluble in
water. Melting point of alkali metal halides is in the order: MF > MCl > MBr > MI.
Solubility in liquid ammonia: All alkali metals are soluble in liquid ammonia and give deep blue col-
our. This blue colour is observed due to ammoniated electron, solution is a good conductor of electricity,
paramagnetic and a strong reducing agent. Paramagnetism decreases with increasing concentration of
metal due to the association of ammoniated electrons. Colour also changes to copper bronze due to the
formation of metal ion clusters.
2e − (NH3 )y → [(e − (NH3 )y ]2
Nature of carbonates and bicarbonate: Except Li2O3 all other alkali metal carbonates are stable.
heat
Li 2CO3 → Li 2O + CO2
LiHCO3 does not exist in the solid state, whereas other bicarbonates exist in solid state.
Bicarbonates of alkali metals decompose easily on heating as follows:
2 MHCO3(s) → M2CO3(s) + CO2(g) + H2O(l).
Solubility of carbonates and bicarbonates increases down the group.
Nature of Nitrates: Except LiNO3, alkali metal nitrates decompose to give nitrite and oxygen.
heat heat
2MNO3 → 2MNO2 + O2 ; 4LiNO3 → 2Li 2O + O2 + 4NO2
Nature of sulphate: Except Li2SO4, all alkali metal sulphates are soluble in water.

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15.158 Chemistry at a Glance

Diagnol relationship between Li and Mg: Due to the same charge-to-size ratio and hence same polar-
izing power lithium resembles magnesium. These both decompose water only on heating. Both react with
oxygen to give monoxide. Hydroxides and carbonates of both decompose on heating. Both react with
nitrogen to form nitrides.
Carbonates, oxalates, phosphates and fluorides of lithium and magnesium are sparingly soluble in
water. Nitrates of both on heating give NO2 and O2.
Anomalous behaviour of lithium: Lithium forms only Li2O.
Lithium combines with nitrogen to form nitride.
Lithium hydride is stable.
LiOH and Li2CO3 are thermally unstable.
LiNO3 decomposes to give NO2 and O2.
Li cannot be stored in kerosene oil as it floats in oil due to its low density.
Li2SO4 does not form alum because it is too small to have coordination number six.

Key Points
• Fire caused due to alkali metals is extinguished by CCl4.
• 28 per cent solution of NaCl is known as brine.
• Mixture of Na2O2 and dil. HCl is called oxane.
• Sodium sesqui carbonate is Na2CO3, NaHCO3, 2H2O.
• Common salt fused with little Na2CO3, 5 to 10 per cent Na2SO4 and a little sugar is called kala namak.
• Na2SO4 . 10H2O – Glauber’s salt
• NaNO3 – Chile salt petre
• KNO3 – Indian salt petre

15.3 prepArAtion of naoH


It is prepared by the electrolysis of brine by 1. Nelson cell and 2. Castner-Kellner cell

15.3.1 Nelson Process



 + −
 Na + Cl
NaCl(solution) 
At cathode, Na+ + e– → Na
Na + 2H2O → NaOH + H2
At anode, 2Cl– → Cl2 + 2e–

15.3.2 Castener- Kellner Process



In outer compartment, NaCl  +
 Na + Cl

At cathode, Na– + e– → Na; Na + Hg → Na – Hg


At anode, 2Cl– →Cl2 + 2e–
In middle compartment
At anode, Na – Hg → Na+ + Hg + e–
At cathode, Na+ + e– → Na; Na + 2H2O → NaOH + H2
Properties of NaOH

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S-Block Elements 15.159

3
3+1D+32 =Q
6Q2 1D=Q2+
+21D6Q2 $O2
6Q2 1D$O2+2
+21D6Q2 =Q2
)H62 1D=Q2+2
1D62)H 2+  Ļ 1D2+ &OFROG
+J&O 1D&O1D&O2+2
+J2ĸ+J 2+  &OKRW
$O&O 1D&O1D&O2+2
1D$O2ĸ$O 2+  &2XQGHU3
6Q&O +&221D
1D2ĸ6Q 2+ 

Properties of sodium peroxide


+62
1D62+22
$O2
1D&2
=Q2
1D2 1D&22
&OFROG
$A21D2
&UKR
0Q2±

15.3.3 Preparation of Sodium Carbonate


Preparation by Solvay’s process:
&D>2+@
NH3 + H2O + CO2 → NH3HCO3 1D2+&D&2
NaCl + NH4HCO3 → NaHCO3 + NH4Cl +2&2
1D+&2
heat
2NaHCO3 → Na 2CO3 + H3O + CO2 1D&2 &D&O
&D&21D&A
+
Properties of Na2CO3 &2
Na2 CO3 + K2 CO3 is a fusion mixture.
NaHCO3 is used as an antacid (Eno), in baking powder, in fire extinguishers and in effervescent drinks.
Preparation of potassium carbonate, K2CO3 (potash or pearl ash)
It is not not prepared by Solvay process as KHCO3 is more soluble in water than NaHCO3, therefore
it is prepared by Le Blanc process.
K2CO3 is a colourless and deliquescent powder used in making soft soap.

15.3.4 Preparation of Alkali Metals


Since alkali metals are the strongest reducing agents, they cannot be prepared by chemical reduction of
their oxides.
These cannot be extracted by the electrolysis of their aqueous solution because the metal extrated at
once reacts with water. So, alkali metals are prepared by the electrolysis of the fused halides and impurities
are added to lower the melting point. During of the manufacture of lithium, electrolyte used is 55 per cent
LiCl and 45 per cent KCl. During the manufacture of sodium, electrolyte used is 40 per cent NaCl and
60 per cent CaCl2. Potassium is obtained by the electrolysis of fused KOH.

15.4 AlkAline eArtH metAls


They are Be, Mg, Ca, Sr, Ba and Ra (Ra is radioactive). Their electronic configuration is ns2.
lonization enthalpy: For alkaline earth metals, it is more than group IB and group 1 elements be-
cause the electron is being removed from fully filled ns orbital: Second ionization energy of group

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15.160 Chemistry at a Glance

II elements is less than group I elements because in alkali metals second electron is being removed
from the fully filled inner energy level. They are less electropositive than alkali metals due to higher
ionization energy.
Reducing property: These are weaker reducing agents than alkali metals due to higher ionization
enthalpy.
Flame colouration: Be and Mg do not impart colour to flame due to higher ionization enthalpy.

Ca Sr Ba Ra
Brick red Crimson red Grassy green Crimson red

15.4.1 Chemical Properties


Reaction with water: They react with water to produce hydrogen gas. Their reactivity with water follows
the following trend:
Ba >Sr > Ca > Mg
Reaction with oxygen: Be, Mg and Ca have a tendency to form Ba and Sr forms peroxide.
Reaction with hydrogen: Hydrides of alkaline earth metal: BeCl2 + LiAlH4 → 2BeH2 + LiCl + AlCl3
BeH2 and MgH2 are colvalent and polymeric hydrides are good reducing agents. Stability and solubil-
ity of hydrides increase down the group.
Reaction with halogen: M + X2 → MX2
1070K
BeO + C + Cl 2 
→ BeCl 2 + CO
BeCl2 exists as a polymer in solid state. BeF2 is soluble in water, whereas fluorides of other alkaline
earth metals are insoluble, Chlorides, bromides and iodides of Mg, Ca, Sr and Ba are ionic, and have lower
melting point than the fluorides.
Solubility decreases in the order of MgX, CaX2 > SrX2 > BaX2.
All the halides are hygroscopic in nature.
MgCl 2 + 2NaHCO3 → MgHCO3 + 2NaCl
(Soluble)

Heat
MgHCO3 
→ MgCO3 ↓ + H2O + CO2

15.4.2 Nature of Hydroxides


Be(OH)2 is amphoteric. Basic character of hydroxides increases from Be to Ba.
Solubility of alkaline earth metal compounds: For hydroxides of these compounds it increases down
the group because the decrease in lattice energy is more than the decrease in hydration energy.
Be(OH)2 < Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2
Solubility of sulphates and carbonates decreases down the group.
BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4
BeCO3 > MgCO3 > CaCO3 > SrCO3 > BaCO3
Thermal stability: Stability of carbonates and sulphates increases down the group.
BaCO3 > SrCO3 > CaCO3 > MgCO3 > BeCO3
SrSO4 > CaSO4 > MgSO4 > BeSO4

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S-Block Elements 15.161

15.4.3 Diagonal Relationship Between Be and Al


1. Both become passive on treatment with concentrated nitric acid due to the formation of protective
oxide film.
2. Both dissolve in conc. NaOH to form beryllate and aluminate.
Be + 2NaOH → Na2BeO2 + H2; 2Al + 2NaOH + 2H2O → 2NaAlO3 + 3H2
3. Oxides of both are amphoteric.
4. Carbides of both react with water to give methane.
Be2C + 4H2O → 2Be(OH)2 + CH4; Al4C3 + 2H2O → 4Al(OH)3 + 3CH4
5. Anhydrous halide of both are Lewis acids.
6. Both form complexes, e.g., BeF42–, AlF62–.

15.4.4 Anomalous Behaviour of Be


1. Be is hard but other alkaline earth metals are soft.
2. Be forms covalent compounds; however, others generally form ionic compound.
3. BeO is amphoteric while other oxides are basic in nature.
4. The m.pt., b.pt and ionization energy of Be is maximum amongst alkaline earth metals.
5. Be has bridged polymeric structure.
6. Be does not liberate hydrogen gas from acids while other metals liberate.

Key Points
• MgSO47H2O (Epsom salt) is used as purgative.
• K2SO4.MgSO.6H2O is sold as potash magnesia, a fertilizer.
• CaSO4.2H2O is called gypsum.
• CaSO.1/2H2O is plaster of paris.
• CaSO4.H2O, called alabaster, is used to make ornaments
• Anhydrous CaCl2 is used as a desiccating agent.
• Fire caused due to alkali and alkaline earth metals is extinguished by asbestos.
• MgCl2.5MgO, XH2O is called Sorell’s cement which is used in dentistry.
• Hardening of plaster of paris is due to the transition of orthorhombic form of gypsum to monoclinic
form.
• Mg has the lowest melting point and calcium has the lowest density amongst alkaline earth metals.
• Most of the kidney stones are made up of calcium oxalate, CaC2O4.H2O.
• Aqueous solution of Ba(OH)2 is known as baryata water.

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Chapter 16 p-BloCk
elements

16.1 Group 13 (Boron family)


General electronic configuration of this group is ns2 np1 and except B all are metals; B exist in crystalline
and amorphous forms with icosahedral geometry with B at all 12 corners. Properties of Al are different
form Ga, In and Tl due to intervening transition metals.
Ionization energy: Decreases down the group but ionization energy of Ga is more than Tl due to
intervening (n – l)d orbitals and that of Tl is more than In, due to poor shielding effect of (n – 2) f orbital.
First ionization energy is in the order:
B > Tl > Ga > Al > In
Oxidation state: All the element exhibit +3 oxidation state. On moving down the group, +1 oxidation
state becomes dominant due to inert pair effect. Inert pair effect increases after In. Tl (III) is a strong
oxidizing agent > 4 and increases with the increasing value of n. Reducing character of the elements
increases as we move down the group.
Method of preparation of boron
Acid ∆ Mg
(a) Na 2 [B 4O5 (OH)4 ]8H2O  → H3BO3  → B2O3  → 2B + 3MgO
Borax

Red hot
(b) 2BCl 3 + 3H2 
W fillament
→ 2B + 3l 2
Red Hot
(c) 2Bl 3 
vanArkel
→ 2B + 3l 2

Chemical properties of boron


0J 2
0J% %2
+62 6
+%262 %6
' ' 1
+12 %RURQ
+%212 %1
&2 ;
%2& %;
1D2+
6L2 1D%2+
%26L
1+
%1+

Hydroxide: Al and Ga hydroxides are amphoteric, hydroxide of In is more basic than Ga. Tl reacts with
steam and form TlOH.

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P-Block Elements 16.163

Halides: Boron halides are monomeric and make up the deficiency either by back bonding (in halides)
or by dimerization (in hydrides). The shortening of B–X bond, and also their lewis acidic character is be-
cause of back bonding. Inability of heavier elements to form multiple bond is due to large size of the central
atom, less effective overlapping of more diffused np orbitals and repulsion of inner filled orbitals. Lewis
acidic character of boron halides is in the order Bl3 > BBr3 > BCl3 > BF3.
Hydrides: Hydrides of boron are known as boranes (B-sp3 hybridized) which are electron deficient,
catch fire in air and get hydrolyzed by water.
Method of preparation of B2H6
(a) 4BCl3 + 3LiAlH4 → 2B2H6 + 3LiCl + 3AlCl3
Slient electric
(b) 2BCl 3 + 6H2 →
discharge
B2H6 + 6HCl
(c) 8BF3 + 6LiH → B2H6 + 3LiBF4
Chemical properties of B2H6
UHGKRW
%+
&2 2'
%+&2 %2+2
0H1 +2
0H1++ %+ +%2+
' +&O
%+1+ %+&O+
1+ &O
%&O+&O
%1++ /L+
/L%+

Maximum covalency of boron is four but for other elements is six. Boron shows diagonal relationship with
silicon. Boron halides undergo hydrolysis and give orthoboric acid.
Important compounds of boron: Borazole also called inorganic benzene is isosteric with benzene. Bo-
razole on heating at 3000°C and 10,000 atm pressure produces BN also called inorganic graphite and is as
hard as diamond. It is chemically inert and do not react with mineral acids.

+
%
+²1 1²+

+²% %²+
1
+
,QRUJDQLFEHQ]HQH

Borazole reacts with HCl to produce an addition product as follows:

+ &O
+ % +
1 +
%1++&O + 1
+ % % +
&O 1 &O
+ +

Aluminium: Al, the third most abundant element in earth’s crust, occurs as complex aluminosilicates
(clay, feldspar).

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16.164 Chemistry at a Glance

Ores of aluminium are bauxite and cryolite. If bauxite contains silica as the major impurity it is known
as white bauxite and if it contains red oxide as an impurity it is known as red bauxite. Aluminium is soft,
light and weak when pure but become hard, strong and resistant to corrosion.
Extraction of aluminium: Bayer’s process [Alumina + caustic alkali] and Hall’s process [Alumina +
Na2CO3] are used for the purification of red bauxite and Serpeck’s process [Alumina + N2 + C] is used
for the purification of white bauxite. Pure bauxite is mixed with cryolite (to increase conductivity) and
fluorspar (to lower the melting point) and subjected to electrolysis by Hall and Heroult process to obtain
aluminium. Aluminium is purified by Hoop’s process.
Chemical properties of aluminium
UHGKRW
%+
&2 2'
%+&2 %2+2
0H1 +2
0H1++ %+ +%2+
' +&O
%+1+ %+&O+
1+ &O
%&O+&O
%1++ /L+
/L%+

Key Points
• Alloy duralumin [Al, Cu, Mg, Mn] is used in the construction of aeroplanes, cable rivets, etc.
• Aluminium bronze [Al, Sn, Cu] is used in making utensile, coins, statues, etc.
• Alnico [Al, Ni, Co, Fe] is used in making permanent magnets.
• Magnalium [Al, Mg] is used for making balances and machine parts.
• Nickeloy: Al + Cu + Ni.
• Alcald [duralumin coated with pure Al] is used in making sea planes.
• Y alloy contains Al + Cu + Ni + Mg.
• Due to the corrosion resistant and non-toxic nature aluminium foil is used for wrapping in food
industry. Mixed with linseed oil, aluminium powder is used in silver paints and lacquers.
• Due to its low SRP (–1.66 V) it should reduce water but due to the presence of a protec-
tive layer of Al3O3 on its surface it cannot. Aqueous salts of aluminium are acidic due to
cationic hydrolysis.
Alums: Double salt of aluminium and monovalent metals like sodium and potassium with 24H3O
are known as alums [M2ISO4MIII
2
(SO4)3 . 24H2O]. Alums acts as coagulants, germicides, antiseptic
and mordants.

16.2 Group 14 (CarBon family}


C, Si, Ge, Sn and Pb have electronic configuration as ns2 np3 and show +2 and +4 oxidation states.
Tendency to show +2 oxidation state increases down the group due to inert pair effect. Except lead, all
other element of this group show allotropy.
All elements, except carbon, can expand their octet due to the presence of vacant d-orbitals,
Silicon, due to its large size, is inable to form pp–pp bond and therefore does not exhibit graphite
like structure.

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P-Block Elements 16.165

Hydrides: Stability of hydrides decreases down the group and reducing power of hydrides increase down
the group.
CH4 > SiH4 > GeH4 > SnH4 > PbH4

16.2.1 Oxides

1. Carbon monoxide: Neutral, colourless, odourless and poisonous gas.


Method of preparation:
Conc. H SO
(a) HCOOH 
2 4
→ CO + H2O
Conc. H SO
(b) H2C 2O4 
2 4
→ CO + CO2 + H2O

(c) ZnO + C  → Zn + CO
Properties:
CO forms carboxy heamoglobin with blood which is fatal. CO due to the presence of a lone pair of
electrons on carbon as well as oxygen form metal carbonyls with transition elements in which carbon
is directly attached to the metal. It is a good reducing agent.
ZnO + CO → Zn + CO2
Fe2O3 + 3CO → 2Fe + 3CO2
PbO + CO → Pb + CO2
I2O5 + CO → I2 + 5CO2
2. Carbon dioxide: It is an acidic oxide, colourless and odourless gas. Acidic nature of dioxides CO2
> SiO2 > GeO2 > SnO2 > PbO2
Method of preparation:
(a) Na2CO3 + 2HCl → 2NaCl + H2O + CO2

(b) CaCO3  → CaO + CO2

(c) 2NaHCO3  → Na 2CO3 + H2O + CO2
It turns lime water milky.
CO2
Ca(OH)2 + CO2 → CaCO3 + H2O  → Ca(HCO3 )2
Milky Soluble

3. Silica: It is an acidic oxide. It is widely found as sand and quartz. The main forms of SiO2
are quartz, tridymite and crystobalite. Coloured quartz are used as gems. Amethyst (violet),
rose quartz (pink), etc.
Application of silica:
1. Flint, opal, agate, onyx and jasper are amorphous silica.
2. Kieselguhr is a siliceous rock composed of remains of minute sea organisms.
3. 2HF
SiO2 is soluble in HFSiO2 + 4HF → SiF4  → H2SiF6
4. Silica gel is a granular, vitreous, highly porous form of silica made synthetically from sodium
silicate and is used as a drying agent.
5. mongst dioxides, only CO2 a is gas, and PbO2 is a strong oxidizing agent due to the greater
A
stability of +2 oxidation state.

4. Carborundum (SiC): Carborundum or artificial diamond SiO2 + 3C  → SiC + 2CO
Very hard (Diamond > B4C > SiC). Chemically inert.

Chemistry at a Glance Final.pdf 171 4/1/2014 12:26:11 PM


16.166 Chemistry at a Glance

Soluble in alkali in presence of oxygen SiC + O2 + 4NaOH → Na2SiO3 + Na2CO3 + H2O.


It is used as an abrasive.
5. Halides: Form tetrahalities, except carbon, others form dihalide also. PbBr4 and Pbl4 does not exit
due to strong oxidizing power of Fb4+ and strong reducing power of Br– and I–.
Stability of dihalides increases down the group. Thermal stability of halides is in the order
(CX4 > SiX4 > GeX4 > SnX4 > PbX4).
For the common central atom the thermal stability and volatility of tetrahalides is in the order
MF4 > MCl4 > MBr4 > MI4.
Except carbon halides the other tetrahalides act as strong Lewis acids.
Silicones are Si–O–Si compounds, formed by the hydrolysis ofalkyl substituted chlorosilanes.
Cu; 573K
2RCl + Si 
−2HCl
→ R 2SiCl 2
R2SiCl3 + 2H3O → R2Si(OH)2 (dialkylsilandiol| which polymerizes to give linear
thermoplastic silicon.
5 5 5 5
+ 2
+²2²6L²2²++²2²6L²2²+ +²2²6L²2²6L²2²+
5 5 5 5
5 5
Q56L 2+ 
±Q+2
+²2²6L²2²6L²2²+
5 5 Q

RMgCl RMgCl RMgCl RMgCl


SiCl 4 →
− MgCl 2
RSiCl 3 →
− MgCl 2
R 2SiCl 2 →
− MgCl 2
R 3SiCl →
− MgCl 2
R 4Si

6. Tin and lead: Tin occurs as cassiterite (SnO2) from which tin is obtained by carbon reduction and
tin is purified by zone refining.
Lead occurs as galena (PbS), which is concentrated by froath floatation process, roasted and then the
oxide is reduced by coke to give lead.
Pewter [Pb = 80 per cent, Sn = 20 per cent] Solder [Pb 50 per cent; Sn 50 per cent]; Type metal [Pb, Sb, Sn]
Stannous chloride which is prepared by boiling tin with conc, HC1 in a mild reducing agent and
reducing Fe (III) to Fe (II); Hg(II) to Hg(I) and finally to Hg, Mn (VI) to Mn(VI) ; Cr(VI) to Cr(II).
Lead oxide (PbO, litharge) is yellow when cold and orange when hot.
Pb3O4, red lead, decomposes to PbO and PbO2 on heating.
Except nitrate and acetate Pb2+ salts are insoluble in water.
Lead is used in making vessels for radioactive materials and for making cathode (PbO2) in lead
storage batteries. Since Pb3O4 is a strong oxidizing agent, it is used to give a coating on steel
before painting.
Tetraethyllead is used as antiknock in petrol but its use has been restricted due to its toxicity as it
inhibits the action of certain enzymes.
PbSO4 is soluble in acetic acid due to the formation of stable acetate complexion.

16.3 allotropes of CarBon


Carbon exhibits many allotropic forms; both crystalline as well as amorphous. Diamond and graphite are two
well-known crystalline forms of carbon. In 1985, third form of carbon known as fullerenes was discovered by
H W Kroto, E Smalley and R F Curl.

Chemistry at a Glance Final.pdf 172 4/1/2014 12:26:11 PM


P-Block Elements 16.167

16.4 DiamonD
It has a crystalline lattice. In diamond each carbon atom undergoes sp3
hybridization and linked to four other carbon atoms by using hybridized
orbitals in tetrahedral fashion. The C – C bond length is 154 pm. The 3P
structure extends in space and produces a rigid 3D network of carbon
atoms. In this structure, directional covalent bonds are present throughout
the lattice.
It is very difficult to break extended covalent bonding and, therefore,
diamond is a hardest substance on the earth. It is used as an abrasive for
sharpening hard tools, in making dyes and in the manufacture of tungsten
filaments for electric light bulbs. 7KH6WUXFWXUHRI'LDPRQG

16.5 Graphite SP

Graphite has a layered structure. Layers are held by van der waals forces
and distance between two layers is 340 pm. Each layer is composed of

3P
planar hexagonal rings of carbon atoms. C — C bond length within the
layer is 141.5 pm. Each carbon atom in hexagonal ring undergoes sp2
hybridization and makes three sigma bonds with three neighbouring carbon
atoms. Fourth electron forms a p-bond. The electrons are delocalized over
the whole sheet. Electrons are mobile and, therefore, graphite conducts
electricity along the sheet. Graphite cleaves easily between the layers and,
therefore, it is very soft and slippery. For this reason graphite is used as a
dry lubricant in machines running at high temperature, where oil cannot be
used as a lubricant.
7KHVWUXFWXUHRIJUDSKLWH

16.5.1 Fullerenes
Fullerenes are made by the heating of graphite in an electric arc in the
presence of inert gases such as helium or argon. The sooty material formed
by condensation of vapourized Cn small molecules consists of mainly C60
with smaller quantity of C70 and traces of fullerenes consisting of even
number of carbon atoms up to 350 or above. Fullerences are the only pure
form of carbon because they have smooth structure without having ‘dan-
gling bonds. Fullerenes are cage-like molecules. C60 molecule has a shape
like a soccer ball and is called Buckminsterfullerene.
It contains twenty six-membered rings and twelve five-membered
rings. A six-membered ring is fused with six or five-membered rings but
a five-membered ring can only fuse with six-membered rings. All the carbon atoms are equal and they
undergo sp2 hybridization. Each carbon atom forms three sigma bonds with other three carbon atoms.
The remaining electrons at each carbon is delocalized in molecular orbitals, which in turn give aromatic
character to molecule. This ball-shaped molecule has 60 vertices and each one is occupied by one carbon
atom and it also contains both single and double bonds with C — C distance of 143.5 pm and 138.3 pm
respectively. Spherical fullerenes are also called bucky balls in short.
The structure of C60. Bukminster fullerene: Note that the molecule has the shape of a soccer
ball (football).

Chemistry at a Glance Final.pdf 173 4/1/2014 12:26:11 PM


16.168 Chemistry at a Glance

It is very important to know that graphite is thermodynamically most stable allotrope of carbon and,
therefore, DfH⊖ of graphite is taken as zero. DfH⊖ values of diamond and fullerene, C60 are 1.90 and 38.1
kJ mol—1, respectively.

16.6 Zeolites
If aluminium atoms replace few silicon atoms in 3D network of silicon dioxide, overall structure
known as aluminosilicate, acquires a negative charge. Cations such as Na+, K+ or Ca2+ balance the nega-
tive charge. Examples are feldspar and zeolites. Zeolites, are widely used as catalysts in petrochemi-
cal industries for cracking of hydrocarbons and isomerization, e.g., ZSM-5 (a type of zeolite) used
to convert alcohols directly into gasoline. Hydrated zeolites are used as ion exchangers in softening
of ‘hard’ water.

16.7 siliCates
Silicate minerals together with silica and aluminosilicate clay make 95 per cent of the Earth’s crust. They
contain different modes of combination of (SiO4)4– tetrahedral units. The Si–O bond is 50 per cent ionic
and 50 per cent covalent.
The radius of Si4– (0.4 A°) and O2– (1.4 A°) makes the radius ratio 0.29 with coordination
number 4 around Si.
The (SO4)4– tetrahedral units may be single or share 1, 2, 3 or 4 O-atoms through corners only giving
rise to various types

16.7.1 Type of Silicates


1. Orthosilicates: (Neso–silivates). No O–atoms are shared 6LOLFRQ
R[\JHQ
Contain discrete SiO44− units with the general formula, M||2SiO4 .
e.g., Zircon = ZSiO4
Olivine = (Mg. Fe)2 .[SiO4]
Fenacite = Be2SiO4
Forsterite = Mg2SiO4
Williemite = Zn2 SiO4
2. Pyrosilicates (Soro–silicates)
One O-atom is shared at one corner.
Contains discrete (Si2O7)6– unit.
e.g., Thortveitite: Sc2 Si2O7
Hemimorphite: Zn4 Si2O7 (OH)2 . H2O
Pyrosilicates are rare.
3. Ring (cyclic) silicates:
Two O-atoms are shared per tetrahedron
and contain ( SiO3 )n
2n−
units
e.g., Benitoite: BaTiSi3O9
Beryl: Be3 Al2 (SiO3)6

Chemistry at a Glance Final.pdf 174 4/1/2014 12:26:11 PM


P-Block Elements 16.169

4. Chain silicates:
(a) Single chain (pyroxenes)
Two O-atoms are shared per tetrahedron
and contain (SiO3 )2n− units.
E.g., Spodumene: LiAl(SiO3)2
Diopsite: CaMg(SiO3)2
Enstatite: Mg2(SiO3)2
Wollastonite: Ca3(SiO3)3
(b) Double chains (amphiboles)

Contain (Si 4O11 )6n
n units, asbestos minerals. Some tetrahedrons share two and some share
 1 
three corners  2 0 − atoms  .
 2 
E.g., Tremolite: Ca2 Mg5(Si4O11)2(OH)2
Crocidolite: Na 2Fe3ii Fe2iii (Si 4O11 )2 (OH)2
5. Sheet silicates (phyllo-silicates)
Three O-atoms are shared at three corners of the tetrahedron. Contains (Si2O5)n2n–.
e.g., Muscovite: KAl2(OH)2 AlSi3O10 Mica
Talc: Mg3 (OH)2 Si4O10
Kaolin: Al2 (OH)4 Si2O5 Clay
6. 3D silicates
Four O-atoms are shared from all corners of SiO4 tetrahedron resulting in 3D lattice of formula SiO2
e.g., Quartz: (SiO2)n
Due to replacement of Si atoms it forms
(a) Orthoclase feldspar: KalSi3O8
(b) Zeolite: Na2Al2Si2O8. × H2O
(c) Ultramarine: Na8 [(AlSiO4)6]S2

16.8 Group 15 elements (nitroGen family)


• The group 15 elements are collectively called as pnictogens.
• General outer electronic configuration: ns2 np3 (where, n = 2 to 6)

Element Electronic configuration Oxidation number


Nitrogen (N) [He]2s22p3 –3, –2, –1, +1, +2, +3, +4, +5
Phosphorus (P) [Ne]3s2 3p3 –3, +3, +4, +5
Arsenic (As) [Ar]3d10 4s24p3 –3, +3, +5
Antimony (Sb) [Kr]4d10 5s25p3 –3, +3, +5
Bismuth (Bi) [Xe]4f145d10 6s26p3 +3, +5

• Non-metals: N, P Metalloids: As, Sb Metal Bi


• Allotropy: All elements of group 15 (except N and Bi) show allotropy.
• Atomic radii and density order N < P < As < Sb < Bi.

Chemistry at a Glance Final.pdf 175 4/1/2014 12:26:11 PM


16.170 Chemistry at a Glance

• I E and E N order N > P > As > Sb > Bi


• N2(N≡N) is diatomic, white P, As, Sb are tetraatomic (P4, As4, Sb4) and tetrahedral with a bond
angle of 60°.

3 3 3
±ƒ&
3 3 ,QHUW 3 3² 3 3
DWPRSKHUH
3 3 3
:KLWHSKRVSKRUXV 5HGSKRVSKRXUV

White phosphorus Red phosphorus Black phosphorus


Soft, whitish yellow, waxy solid Red powdery, microcrystalline solid Black solid
Spontaneously inflames in air Only ignites at temperature greater Does not ignite even
above 50°C to give P4O10 and P4O6 than 260°C above 400°C
in limited supply of O2
Combines violently with all Combines slowly with halogens Kinetically inert/stable
halogens
Volatile, highly reactive Non-volatile, less reactive Non-volatile, chemically
inert
Structure consists of discrete P4 Structure consist of chain/sheets Structure is sheet-like
tetrahedra similar to graphite
Poisonous, insoluble in H2O Non-poisonous, insoluble in H2O but Non-poisonous, insolu-
soluble in CS2 ble in both H2O and CS2

• Black phosphorus is of two types: α-block and b-block. α-block prosphorus do not conduct
electricity, where, as b-block phosphorus can conduct electricity.
Preperation of N2: NH4Cl + NaNO3 → N2 + 2H2O + NaCl

( NH4 )2 Cr2O7 
∆ ∆
→ N 2 + C1H2O + Cr2O3 ; 2NH3 + Cuo  → 2Cu + 3H2O + N 2

2NH3 + CaOCl 2 → 3CaCl 2 + 3H2O + N 2

• Oxides: All these elements form oxides of the type X2O3, X2O4 and X2O5.
N2O3 P2O3 As2O3 Sb2O3 BiO3
N2O4 P2O4 As2O4 Sb2O4 BiO4 ↓ Acidic nature increase
N2O5 P2O5 As2O5 Sb2O5 Bi2O5 → Acidic nature decreases
As the electronegativity increases, acidic character of the oxide also increases. Among the oxides of
the same element, higher the oxidation state, greater the acidic character.
• Nitrogen does not form pentahalide due to inability to expand octet and Bi does not form
pentahalide due to inert pair effect.
• Holme’s signals: The spontaneous combustion of phosphine is used in Holme’s signals. Containers
containing CaC2 and Ca3P2 are pierced and thrown into the sea where on reaction with H2O, PH3
and C2H2 is produced along with traces of P2H4 which are highly inflammable. This ignites acetylene
which burns with a luminous flame.

Chemistry at a Glance Final.pdf 176 4/1/2014 12:26:11 PM


P-Block Elements 16.171

• Oxo acids of phosphorus:

Oxoacid Structure Basicity Preparation


Phosphinic acid 2 1 White P4 + alkali
(hypo phosphorus 3
acid), H3PO2 +2 +
+

Phosphonic acid 2 2 P2O3 + 3H2O → 2H3PO3


(ortho phosphorus 3 PCl3 + 3H2O → H3PO3 + 3HCl
acid or phosphorous +2 +
acid), H3PO3 2+

Orthophosphoric 2 3 P4O10 + 6H2O → 4H3PO4


acid H3PO4 3
+2 2+
2+

Meta phosphoric 2 1 ∆
3H3PO3 + 3Br2  → (HPO3)3 + 6HBr
acid (glacial 3
Soalid tube

phosphoric acid), 2 2
(HPO3)n 2+ Q

Pyrophosphorous 2 2 2 PCl3 + 5H3PO3 → 3H4 P2O5 + 3HCl


acid (diphosphorus +²3²2²3²+
acid), H4P2O5
2+ 2+

Pyrophosphoric acid 2 2 4 250° C


(diphosphoric acid), 2H3PO4  → H4P2O7 + H2O
3 3
H4P2O7 2
2+ 2+ 2+
+2

Hypophosphoric 2 2 4 2P(red) + 4NaOCl + 2H2O → H4P2O6 + 4NaCl


acid, H4P2O6 +2²3²3²2+
2+ 2+

States decrease gradually with decrease in electronegativity of the central atom.


HNO2 H3PO3 H3AsO3 H3SbO3
HNO3 H3PO4 H3AsO4 H3SbO4

• Oxoacids of nitrogen

2
2+ + + 2
1 1 2 1 2 1 +2 2 1 2
+2 2 2
+\SRQLWURXVDFLG 1LWURXVDFLG +\SRQLWURXVDFLG 3HUQLWULFDFLG
+12 +12 +12 +12

Chemistry at a Glance Final.pdf 177 4/1/2014 12:26:12 PM


16.172 Chemistry at a Glance

• Hydrides: MH3 type hydrides

1+ 3+ $V+ 6E+ %L+


$PPRQLD 3KRVSKLQH $UVLQH 6WLELQH %LVPXWKLQH
%DVLFFKDUDFWHUGHFUHDVHV
7KHUPDOVWDELOLW\GHFUHDVHV

• As the size increases, the electron density gets diffused over a larger region (due to bigger size) and
hence the ability to donate the electron pair (basic nature) decreases.

16.8.1 Important compounds of nitrogen family

Structure Preparation Properties Uses


1+ N2(g) + 3H2(g) ⇌ 2NH3(g); $J&O 2 Used in refrigera-
>$J 1+ @ 1+ + 1
DHf° = –92.4 kJ/mol +J
, 2 tors manufacturing
1

. +

&O 


W
of rayon, HNO3,
3
(Haber’s process) .2
+1+J2+J,

+ + + 2 +12
%URZQSSW 12 1+&O1 NaHCO3, nitrog-
,I1+LVLQH[FHVV enous fertilizers
3+ Ca3P2 + 6H2O → 1+3+±
1+
3+
'
3+
Used as
3Ca(OH)2 + 2PH3 O
ƒ&
&X  dehydrating
3 +& 
agent
$J


3+&O
2

&X3+62


+ + +
+32 $J+ 32
 

+12 2KNO3 + H2SO4 → 62


+12
&+2 Used as fertilizers
+6212
+ 2 2HNO3 + K2SO4 ±+2 explosives,
2 1 perfumes and
+&

&22+ 
6Q

2
O

+6Q2 + 212&O>&O@ dyes




3&O P4 + 10Cl2 → 4PCl5 3&O


32 Used as
32&O
&O (White or red) chlorinating and
&O
62 

dehydrating
VV

36
2

FH

&O 2
+

agent
H[

62&O32&O

LQ

&O &O
+32+&O 36&O

Properties of HNO3: HNO3 is a powerful oxidizing agent; it oxidizes almost all metals, non-metals and
many compounds.
It gets reduced as
62 &
HNO3 → NO2 → NO → N 2O → N 2 → NH3 +62 +&2
+2 + 6 6
+5 +4 +1 0 −3 +12 +62
6
Greater the change in oxidation state, weaker the oxidizing %U
+%U 3
+32
action of HNO3. Non-metals are oxidized to their higher oxyacids ., ,
, +,2
and HNO3 is reduced to NO2:
Aqua regia (HNO3 + 3HCl);
HNO3 + 3HCl → NOCl + 2H2O + 2Cl
HCl
Au + 3Cl → AuCl3 → HAuCl4

Chemistry at a Glance Final.pdf 178 4/1/2014 12:26:12 PM


P-Block Elements 16.173

16.8.1.1 Action of HNO3 with metal

HNO3 Metal Main Product


Very dilute Mg, Mn → H2 + MNO3
Fe, Zn, Sn → NH4NO3 + MNO3
Dilute Pb, Cu, Ag, Hg → NO + MNO3
Fe, Zn → N2O + MNO3
Sn → NH4NO3 + Sn(NO3)2
Concentrated Zn, Pb, Cu, Ag → NO2 + MNO3
Sn → NO2 + H2SnO3
Fe, Ni, Co, Cr, Al → Passive (inert)

Key Points
• Stability: NH3 > PH3 > AsH3 > SbH3 > BiH3.
• Boiling point: PH3 > AsH3 > NH3 > SbH3 > BiH3.
• Bond angle: NH3(107.8°) > PH3(93.6°) > AsH3(91.8°) ≈ SbH3(91.3°) > BiH3(90°).
• Basicity: NH3 > PH3 > AsH3 > SbH3 > BiH3.
• Reducing power: N2O5 > P2O5 > As2O5 > Sb2O5.
• Reducing power: NH3 < PH3 < AsH3 < SbH3 < BiH3.
• Stability: N2O5 > P2O5 > As2O5 > Sb2O5 > Bi2O5.
• N 2O < NO < N 2O3 < N2O4 < N2O5 (acidity)
 
Neutral Acidic

• Nitrous oxide (N2O): Diamagnetic, produces hysteria (laughing gas), used as an anaesthetic.
• Conc. HNO3 appears yellow due to the presence of dissolved NO2 formed by the photochemical
decomposition of HNO3 .

16.9 Group 16 elements (oXyGen family)

• They are collectively called chalcogens.


• General outer electronic configuration is ns2np4 (where n = 2 to 6).

Element Electronic configuration Oxidation number


Oxygen (O) [He]2s22p4 –2, –1, +1, +2
Sulphur (S) [Ne]3s 3p
2 4
–2, +2, +4, +6
Selenium (Se) [Ar]3d 4s 4p
10 2 4
–2, +2, +4, +6
Tellurium (Te) [Kr]5d10 5s25p4 –2, +2, +4, +6
Polonium (Po) [Xe]4f 5d 6s 6p
14 10 2 4
+2, +4, +6

All element of this group except oxygen are diamagnetic. At room temperature, O2 gas is
paramagnetic.

Chemistry at a Glance Final.pdf 179 4/1/2014 12:26:12 PM


16.174 Chemistry at a Glance

• Atomicity:

O Multiple bonds (pp – pp) Diatomic


S, Se, Te single bonds Octaatomic
Multiple bonds (pp – dp)

Atomic radii and density order: O < S < Se < Te


Ionization energy and electronegativity order: O > S > Se > Te
O2(O=O) is diatomic but others are octaatomic (S8)
• Catenation: Sulphur has highest bond strength of S–S bond. Therefore, S > Se > O > Te.
• Allotropy: This property is shown by all. Sulphur occurs in a number of allotropic forms
such as rhombic (a), monoclinic (b), plastic (g), colloidal (d), l and m-sulphur. These are all
non-metallic in nature.

Sulphur (R)   Sulphur (M)
95.6
• Hydrides: H2M type (where, M is sp3 hybridized)
Melting and boiling points: H2O >H2Te > H2Se > H2S
Acidic nature of hydrides: H2Te > H2Se > H2S > H2O
Stability order: H2O > H2S > H2Se > H2Te
Thermal stability: H2O < H2S < H2Se < H2Te
Volatility: H2O < H2Te < H2Se < H2S
Reducing character: H2S < H2Se < H2Te
Bond angle and dipole moment: H2Te < H2Se < H2S < H2O

16.9.1.1 Halides

Element Fluorine Chlorine Bromine Iodine


Oxygen F2O Cl2O, ClO2, Cl2O7 Br2O I2O5
Sulphur SF6, S2F10, SF4, S2F2 SCl4, SCl2, S2Cl2 S2Br2 –––––––
Selenium SeF6, SeF4, Se2Fe2 SeCl4, SeCl2, Se2Cl2 SeBr4, SeBr2, Se2Br2 –––––––
Tellurium TeF6, Te2F10, TeF4 TeCl2, TeCl4 TeBr4, TeBr2 TeI4
Polonium PoF6 PoCl4, PoCl2 PoBr4, PoBr2 PoI4

• Oxides: The most important oxides are of the MO2 and MO3 type.
SO2 and SeO2 → Acidic
TeO2 and PoO2 → Amphoteric
2
• Acidity: SO < SO2 < SO3 (acidity increases with increase in SP
oxidation number). 6 SP 6
2 ƒ 2 2 ƒ 2
• Thermal stability: SO2 > TeO2 > SeO2 > PoO2 62 62
• Oxoacids of sulphur

Chemistry at a Glance Final.pdf 180 4/1/2014 12:26:12 PM


P-Block Elements 16.175

Oxoacid Oxidation state, Structure Properties


basicity and salt type

Sulphurous acid S = +4, dibasic, and Does not exist in free


(H2SO3) forms two series of salts, 6
form
sulphites (SO32–) and 2 Acts as reducing as well
+2
bisulphites (HSO3–) +2 as oxidizing agents

Sulphuric acid S = +6 monobasic and 2 Stable, acts as oxidizing


(H2SO4) or oil vitriol forms two series of salts, 6
and dehydrating agents
sulphates (SO42–) and 2
+2
bisulphates (HSO 4)

2+

Peroxomonosulphuric S = +6 monobasic and 2 Stable crystalline and


acid (H2SO5) or Caro’s forms single type of salt, 6
hygroscopic solid.
acid peroxy disulphates 2 2 2+ Powerful oxidizing agent
2+

Peroxodisulphuric S = +6 and forms 2 2 Stable crystalline and


acid (H2S2O8) or single type of salt, 6 6
hygroscopic solid.
Marshall’s acid peroxydisulphates 2 2 2 2 Strong oxidizing
(S2O82–) 2+ 2+ agent

Pyrosulphuric acid, S = +6, dibasic 2 2 Acts as a strong


disulphuric acid 6 2 6
dehydrating agent
(H2S2O7) or Oleum 2 2
2+ 2+

H2S2O5 S(+5), S(+3) dibasic O O Corrosive oily,


Di or pyrosulphirous || || hygroscopic
acid HO − S − S − OH
||
O

H2S2O4 Dithionous S(+3), 5(+3) dibasic O O Unstable in pure form


acid || ||
HO − S − S − OH

H2S2O4 Dithionic acid S(+5) dibasic O O Water soluble mild


|| || oxidizing and reducing
HO − S − S − OH agents
|| ||
O O

H2SnO6 Polythionic S(+5), S(0) dibasic O O Stable in aqueous


acid n < 80 || || solutions, interact with
HO − S − (S)n − S − OH strong reducing
|| ||
O O agents

Chemistry at a Glance Final.pdf 181 4/1/2014 12:26:12 PM


16.176 Chemistry at a Glance

16.9.1.2 Dioxygen (O2)

3UHSDUDWLRQ 3URSHUWLHV
1D
1D2
N'
+J2 )H
±+J VWURQJ' )H2
0Q2. +.
.&O2 + 2
±.&O 2
3 KRW
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.0Q20Q2 32
.
&6 KRW
. &262
.&U2
&+
&2+2NM

16.9.1.3 Ozone
3UHSDUDWLRQ 3URSHUWLHV
2 +2,
6LOHQW +,2
HOHFWULF + 6
GLVFKDUJH
+262
3E6
2 3E62
.2+
.2
&+ &+
+2=Q
+&+2
+&O6Q&O
6Q&O

Oxygen is soluble in alkaline pyrogallol, whereas ozone is soluble in turpentine oil also called oil
of cinnamon.

Compound Oxidation state of O Compound Oxidation state of O


In oxides –2 In dioxygen 0
In peroxides –1 In oxygen difluoride +2
In superoxides –1/2 In oxygen monoflouride +1

16.10 Group 17 elements (haloGen family)


• General outer electronic configuration is ns2np5 (where n = 2 to 6)

Element Electronic configuration Oxidation number


Fluorine (F) [He]2s 2p
2 5
–1
Chlorine (Cl) [Ne]3s 3p
2 5
–1, +1, +3, +5, +7
Bromine (Br) [Ar]3d10 4s24p5 –1, +1, +3, +5, +7
Iodine (I) [Kr]4d 5s 5p
10 2 5
–1, +1, +3, +5, +7
Astatine (At) [Xe]4f 5d 6s 6p
14 10 2 5
–––––

Chemistry at a Glance Final.pdf 182 4/1/2014 12:26:12 PM


P-Block Elements 16.177

• Atomic radii, ionic radii and density increase from F to I.


• Electro negativity: F > Cl > Br > I
F is the most electronegative element in the periodic table.
• Electron gain enthalpy: Cl > F > Br > I
• Bond energy: Cl2 > Br2 > F2 > I2.
• Solubility and oxidizing power: F2 > Cl2 > Br2 > I2.
• Oxidizing nature order is F > Cl > Br > I.
• Reducing nature order is Cl– > Br– > I–.
• The solution of iodine (I2) in water increases with addition of KI or NaI due to the formation of
polyamide (triiodide, I3–) ion. KI(aq) + I2(s) ⇌ KI3(aq) ⇌ K+(aq) + I3(aq)–
• Bond length, melting and boiling point: F2 > Cl2 > Br2 > I2.
• Heat of hydration: F– > Cl– > Br– > I–.

16.10.1 Comparison of Halogens

Property Fluorine Chlorine Bromine Iodine


Physical state Gas Gas Liquid Solid
Colour Pale yellow Greenish yellow Reddish brown Voilet
Oxidizing Very strong Strong oxidizing agent Good oxidizing Mild oxidizing
nature oxidizing agent agent agent
Bleaching Destroys the Bleaches vegetable Mild bleaching ––––––––
action reducible coloured colours easily agent
substance
Chemical Highly reactive Quite reactive Less reactive than Least reactive
reactivity chlorine
Reaction with Combines Explosive in light, slow Only on heating On heating and
(i) Hydrogen explosively even in dark in presence of a
in the dark catalyst
(ii) Water Decomposes Forms chlorine hydrate Decomposes No action
forming HF, O2 with ice cold water. slowly in presence
and O3 Decomposes slowly of light, forming
forming HCl and HBr and HBrO or
HClO or HCl and O2. HBr and O2
(iii) Metals Reacts with all Reacts with almost Many metals are Reacts only
metals to form all metals forming acted upon and with few metals
fluorides chlorides. bromides are to form iodides
formed
(iv) Starch No reaction on No action on starch Yellow colour with Blue colour
starch starch with starch

Chemistry at a Glance Final.pdf 183 4/1/2014 12:26:12 PM


16.178 Chemistry at a Glance

• Halides: Halogens combine with all elements except He, Ne and Ar forming a large number of
binary halides.
Ionic character of M–X bond and melting point and boiling point
M – F > M – Cl < M – Br > M – I
Melting and boiling point of metal halides
M – I > M – Br > M – Cl > M – F
Reducing character
I– > Br– > Cl– > F–
Hydrogen halide: Percentage of ionic character, thermal stability and dipole moments
HF > HCl > HBr > HI
Acidity and bond length
HI > HBr > HCl > HF
Stability order HF > HCl > HBr > HI
Boiling point order HCl > HBr > HI > HF
• Here, HF is not stored in glass vessels since it reacts with SiO2 of glasses. It is stored in copper, wax
polythene or gutta-percha.
• Here, HF reacts with glass to form sodium and calcium fluorosilicates Na2SiF6 and CaSiF6. So, it is
used for etching of glass (mixture of sodium and calcium silicates).
Na2SiO3 + 6HF → Na2SiF6 + 3H2O
CaSiO3 + 6HF → CaSiF6 + 3H2O
or SiO2 + 4HF → SiF4 + 2H2O
SiF4 + 3HF → H2SiF6
Reaction of Cl2 : 2HgO + H2O + 2Cl2 → Hgo.HgCl2 + 2HOCl
Cl2 + 2OH–(cold) →OCl– + Cl– + H2O
3Cl2 + 6OH– (hot and conc) → Cl– + ClO3– + 3H2O
2ClO2 + 2NaOH → NaClO2 + NaClO3 + O2
2ClO2 + Na2O2 → NaClO2 + NaClO3 + H2O
Ca(OH)2 + Cl2 → CaOCl2 + O2

2CaCl 2  → 2CaCl 2 + O2
CaOCl2 + 2HCl → CaCl2 + H2O + Cl2 (available chlorine)
• Oxides: OF2, O2F2
Cl2O, ClO2, Cl2O6 and Cl2O7
Br2O, BrO2, BrO3
I2O4, I2O5, I4O9
All are covalent and powerful oxidizing agents
• Oxidizing power: Cl2O > ClO2 > Cl2O6 > Cl2O7
• Stability: Cl2O < ClO2 < Cl2O6 < Cl2O7.
• Solid Cl2O6 is ionic and exists as ClO2+ and ClO4– ions.

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P-Block Elements 16.179

• Oxoacids: Hypohalous acid: HXO, Halous acid: HXO2, Halic acid:HXO3, Perhalic
acid:HXO4.
• Acidity of hypohalous acids: HOCl > HOBr > HOI
Oxygen is more electronegative than halogens. As the electronegativity decreases from Cl to I,
electrons density on the oxygen atom increases from Cl to I, therefore tendency to attract electrons
of O–H bond decreases from Cl to I, hence acidity decreases.
• Oxidizing power of hypohalous acids: HOCl ≈ HOBr > HOI
Oxidising power decreases as the thermal stability of O–H bond increases with increase in the size
of X from Cl to I.
• Acidity of perhalic acids: HOClO3 > HOBrO3 > HOIO3
As the electronegativity decreases from Cl to I, tendency to withdraw electrons of O–H bond by XO3
group decreases and hence the acidity decreases from Cl to I.
• Oxidizing power of perhalates: BrO4– > IO4– > ClO4–
• Acidity of oxoacids with same halogen in different oxidation states: Acidic strength increases
with increase in oxidation state of the halogen atom. HClO < HClO2 < HClO3 < HClO4
This is based on the stability of their conjugate bases. Greater the number of oxygen atoms, greater
will be the dispersal of the negative charge through pp–dp back bonding.
ClO– < ClO2– < ClO3– < ClO4–
• Oxidizing power of oxoacids with same halogen in different oxidation states:
HClO > HClO2 > HClO3 > HClO4
Oxidizing power decreases, as the stability of their conjugate bases increases.

16.11 interhaloGen CompounDs

Molecules Hybridization Shape Examples


XY Sp3 Linear ClF, BrF, BrCl, ICl, IBr, IF (very unstable)
XY3 Sp3d T-shaped ClF3, BrF3, ICl3, IF3
XY5 Sp d
3 2
Square pyramidal ClF5, BrF5, IF5
XY7 Sp3d3 Pentagonal bipyramidal IF7

• Pseudohalogens and pseudohalides:


• Molecules like cyanogens (CN)2, thiocyanogen (SCN)2 and selecocyanogen (SeCN)2 have properties
similar to those of the halogens. Therefore, these are called pseudohalogens.
• They form anions such as CN–, OCN–, etc. which are called as pseudohalides. CN– resembles
Cl–, Br– and I–.
• Polyhalides: Halide ions often react with molecules of halogens or interhalogen and
form polyhalide ions. Iodine is only slightly soluble in water. Its solubility is greatly
increased if some iodide ions are present in the solution due to formation of polyhalide ion,
I3–. I– + I2 → I3–
Polyhalides are formed from interhalogens and metal halides: K[ICl2], K[ICl4], Cs[IBrF]
and K[IBrCl].

Chemistry at a Glance Final.pdf 185 4/1/2014 12:26:12 PM


16.180 Chemistry at a Glance

Key Points
• Because of the tendency to form hydrogen bond, metal fluorides are solvated by HF giving species of
the type HF2–, etc.
KHF2 (KF . HF), KH2F3(KF.2HF) and KH3F4 (KF.3HF) are known examples.
• Concentrated H2SO4 (a strong oxidizing agent) cannot be used since it would oxidize HBr to Br2 and
HI to I2, etc.
• Magnesium perchlorate, Mg(ClO4)2 is used in dry batteries and is also an effective desiccant called
anhydrone. KClO4 is used in fireworks and flares.

16.12 Group 18 elements (noBle Gases)

• General outer electronic configuration is ns2np6 (where n = 2 to 6)

Known as Reason
Rare gases Occur in very minute quantities
Noble gases Obtained under specific conditions
Intert gases Do not react at ordinary temperature
Zero valent element Show zero valency

Element Electronic configuration


Helium (He) 1s2
Neon (Ne) 1s2 2s2 2p6
Argon (Ar) 1s2 2s2 2p6 3s2 3p6
Krypton (Kr) 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6
Xenon (Xe) 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6
Radon (Rn) 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5f14 5s6 5p6 5d10 6s2 6p6

Properties:
• Because of fully filled electronic configuration, they have very high ionization energies.
• They can be liquefied with great difficulty. It is because of the existence of weak Van der Waal’s forces
in these gases.
• Most abundant noble gas: Argon
• Melting point, boiling point, polarizability, ease of liquefication and solubility in water:
He < Ne < Ar < Kr < Xe < Rn
• Ionization enthalpy: He > Ne > Ar < Kr > Xe > Rn
• Electron gain enthalpy: Ne > Ar = Kr > Xe > Rn > He
• Noble gases form clathrate compounds except He and Ne. Noble gases compressed with water or
quinol gets entrapped between water molecules; such compounds are called clathorates or enclosures.

Chemistry at a Glance Final.pdf 186 4/1/2014 12:26:12 PM


16.13 CompounDs of Xenon

Compound Structure Preparation Properties


XeF2 ) Ni tube Acts as fluorinating agent
Xe + F2 → XeF2
400° C

Chemistry at a Glance Final.pdf 187


(Xenon (2: 1) XeF2 + H2O → XeOF2 + 2HF
difluoride) ;H Electric
Xe + F2 
discharg e
→ XeF2
(2: 1)
P-Block Elements

)

 Xe + F2 → XeF2
(Hg vapour)
/LQHDUVSG

XeF4 ) ) Ni tube Colourless crystalline solid with melting point = 117.1°C


Xe + F2 
600° C
→ XeF4
(Xenon (1: 5) XeF4 + 2H2 → 4Xe + 4HF
tetrafluoride) Electric
Undergoes disproportionation in water
;H Xe + F2  → XeF4
discharg e −78° C 6XeF4 + 12H2O → 4Xe + 2XeO3 + 24HF + 3O2
(2: 1)
Gives adduct XeF4 + SbF5 → [XeF3]+ [SbF6]–
) ) Acts as oxidizing and fluorinating agent

6TXDUHSODQDUVSG Dissolves in anhydrous HF

XeO3 Complete hydrolysis of XeF4 and XeF6 Colourless, highly explosive and powerful oxidizing agent
(Xenon ;H 6XeF4 + 12H2O → 2XeO3 + 4Xe + 3O2 With water forms xenic acid
trioxide) + 24HF XeO3 + H2O → H2XeO4
2 2
2 XeF6 + 3H2O → XeO3 + 6HF Undergoes disproportionation when dissolved in alkali
 3\UDPLGDOVS
2XeO3 + 4OH– → Xe + O2 + XeO64– + 2H2O
XeOF2 ) Partial hydrolysis of XeF4 Unstable
−80° C
(Xenon oxy- ;H 2 XeF4 + H2O  → XeOF2 + 2HF
difluoride)
)
 7VKDSHGVSG

XeO2F2 ) Partial hydrolysis of XeOF4 or XeF6 Colourless solid


(Xenon dioxy 2 XeOF4 + H2O → XeO2F2 + 2HF Undergoes hydrolysis readily
difluoride) ;H XeF6 + 2H2O → XeO2F2 + 4HF XeO2F2 + H2O → XeO3 + 2HF
2

4/1/2014 12:26:12 PM
Action of SiO2 on XeOF4
)
 2XeOF4 + SiO2 → 2XeO2F2 + SiF4
'LVWRUWHGWULJRQDO
ELS\UDPLGDOVSG
16.181
16.182 Chemistry at a Glance

Structure of some other important compounds


)
) 2
) 2 )
)
;H ;H ;H
2 2
2
) ) ) )
)
;H)VSG ;H2VS ;H2)VSG
'LVWRUWHGRFWDKHGUDO 7HWUDKHGUDO 6TXDUHS\UDPLGDO

16.13.1 Uses of Noble Gases

Uses Reasons
He Filling of observation balloons Non flammable; 93 per cent lifting power as
He–O2 mixture for deep-sea breathing compared to flammable H2
instead of N2–O2 mixture Low solubility in blood; prevents nitrogen
Diluent for gaseous anaesthetics narcosis and ‘bends’
He–O2 mixture for respiratory patients Non flammable, non-reactive
Heat transfer medium for nuclear reactions Low density flows easily through restricted
Liquid He to maintain very low temperature passages
in research (cryogenics) Transfers heat readily, does not become
radioactive, chemically inert
Extremely low boiling point
Ne Neon is used for filling discharge tubes for Even at low pressure, moderate electric current
optical decorations and advertisements. It causes bright orange-red glow, can be modified
is used for filling sodium vapour lamps. It is by coloured glass or mixing with Ar or Hg
also used in beacon light as safety signal for vapour
air navigators
Ar Argon is used for filling incandescent Inert; prevents vapourization of tungsten and
metal filament of electric bulbs. It is used blackening of bulbs
in advertising signs, for filling radio-values,
rectifiers and fluorescent tubes
Kr Ariport runway and approach lights Gives longer life to incandescent lights than Ar,
but more expensive
Xe Xe and Kr mixture in high-intensity, short Both have fast response to electric current
exposure photographic flash tubes
Rn Rn is used in radiotherapy Its ability to control cell growth

Chemistry at a Glance Final.pdf 188 4/1/2014 12:26:12 PM


D- anD F-BloCk
Chapter 17
elements

17.1 d-BLOCK (TRANSITION ELEMENTS)


• Their general outer electronic configuration is (n – 1) d1–10 ns0–2 (where n is the
outermost shell).

Known as Reason
First transition series (3d-series) Sc (At. No. 21) to Zn (At. No. 30)
Second transition series (4d-series) Y (At. No. 39) to Cd (At. No. 48)
Third transition series (5d-series) La (At. No. 57) to Hf (At. No. 72) to Hg (At. No. 80)
Fourth transition series (6d-series) Ac (At. No. 89) to Rf (At. No. 104) to Cn (At. No. 112)

17.1.1 Electronic Configuration


The d-orbitals of the transition elements project to the periphery of an atom more than the other orbitals
(i.e., s and p), hence they are more influenced by the surroundings as well as affecting the atoms or
molecules surrounding them.
These elements exhibit certain characteristic properties such as display of a variety of oxidation states,
formation of coloured ions and entering into complex formation with a variety of ligands.
In case of transition elements there is greater horizontal similarities in the properties. It is due to the
fact that in a transition series there is no change in the number of electrons of outermost shell and only
change occurs in the (n – 1) d electrons from member to member in a period.

17.1.2 Physical Properties


Presence of unpaired d-electrons favours covalent bond formation, hence greater the number of unpaired
d-electrons, more is the number of covalent bonds resulting in hard metals.
The high melting points of these metals are attributed to the involvement of greater number of elec-
trons from (n – 1)d in addition to the ns electrons in the interatomic metallic bonding. In any row, the
melting points of these metals rise to a maximum at d5. The maxima at about the middle of each series in-
dicate that one unpaired electron per d-orbital is particularly favourable for strong interatomic interaction.

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17.184 Chemistry at a Glance

Cr, Mo and W are very hard metals as they have maximum number of unpaired orbitals while Zn, Cd
and Hg are softer in nature as they do not have any unpaired d-orbitals.
All transition elements have higher melting points as compared to s-block elements due to strong
metallic bonding as well as unpaired d-electron leading to covalence nature.

17.1.3 Variation in Atomic and Ionic Sizes


In general, ions of the same charge in a given series show progressive decrease in radius with increasing
atomic number. This is due to the fact that effective nuclear charge increases gradually with ineffective
shielding created by d-electrons.
When atomic sizes of one series are compared with those of the corresponding elements in the other series,
the curves show an increase from the first (3d) to the second (4d) series of the elements but the radii of
the third (5d) series are virtually the same as those of the corresponding members of the second series.
This phenomenon is associated with the intervention of the 4f orbitals which must be filled before the 5d
series of elements begin. The filling of 4f before 5d orbital results in a regular decrease in atomic radii called
lanthanoid contraction which essentially compensates for the expected increase in atomic size with
increasing atomic number.
The net result of the lanthanoid contraction is that the second and the third d-series exhibit similar
radii (e.g., Zr 160 pm and Hf 159 pm) and have very similar physical and chemical properties much more
than that expected on the basis of usual family relationship. The shielding of one 4f electron by another is
less than that of one d-electron by another, and as nuclear charge increases along the series, there is fairly
regular decrease in the size of the entire 4fn orbitals.

17.1.4 Density
The decrease in metallic radius coupled with increase in atomic mass results in a general increase in
density. In a period on moving from left to right density increases significantly and then, decreases for the
last element. However, while moving from top to bottom in a group of d-block density increases. Highest
density is observed in case of osmium which is equal to 22.57g/cm3.

17.1.5 Ionization Energy


Due to an increase in nuclear charge there is an increase in ionization enthalpy along each series of
the transition elements from left to right. These values show that the successive enthalpies of these
elements do not increase as steeply as in the main group elements. The magnitude of the increase in
the second and third ionization enthalpies for the successive elements, in general is much higher, and
removal of one electron alters the relative energies of 4s and 3d orbitals. So, the unipositive ions have
dn configurations with no 4s electrons. Due to transfer of electron from 4S to 3d oribital, exchange
energy increases which compensate the ionization energy. Smaller the ionization enthalpy of a metal
greater will be the thermodynamic stability of its compound.

IE1 + IE2 (MJ/mol) IE3 + IE4 (MJ/mol)


Ni 2.49 8.8
Pt 2.66 6.7

From these values it is clear that Ni2+ compounds are more stable than Pt2+ compound but
the Pt4+ compounds are more stable than Ni4+ compounds.

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D-and F-Block Elements 17.185

17.1.6 Standard Electrode Potentials


More the negative standard reduction potential of an ion greater will be its '+ƒR[
stability inside the solution. 0 V 0 DT
Standard reduction potential value depends upon following factors: '+ƒD '+ƒK\G
(i) Heat of atomization
(ii) Ionization energy 0 J 0 J
'+ƒL
(iii) Heat of hydration
DH°ox = DH°a + DH°i + DH°hyd
Metals having negative E° values have high enthalpy of atomization, high enthalpy of ionization and
low enthalpy of hydration.

17.1.7 Oxidation State


The stability of a particular oxidation state depends upon the nature of the element with which the
transition metal forms the compound. The highest oxidation states are found in fluorides and oxides.
Since fluorine and oxygen are the most EN elements, their compounds posses highest lattice enthalpy as
well as bond strength. Ruthenium in second transition series and osmium in third transition series has +8
oxidation states.
In case of transition elements their oxidation state differ by unity contrary to main group elements
where oxidation state differ by two units. In case of p-block element while moving from top to bottom in
the group stability of lower oxidation state increases, whereas in case of d-block element on moving from
top to bottom in the group stability of higher oxidation state increases. Mn acquired +7 oxidation state
in the form oxyfluoride MnO3F rather than simple halide and beyond manganese no metal has trihalide
except FeX3 and CoF3. However, fluorides are unstable in the lower oxidation state and similar result is
observed. In case of CuX (X = Cl, Br, and I), on the other hand, all cupric halides are unknown except the
iodide because Cu2+ oxidizes I- to I2 .
2Cu 2+ + 4I− → Cu2I2 + I2
(s)
In aqueous solution, Cu2+ -is more stable when compared to Cu+ because of high hydration
enthalpy of Cu2+.

17.1.8 Complexes
Tendency to form complexes by transition metals is due to
• their smaller size
• higher nuclear charge
• presence of low energy vacant d-orbitals to accept lone pair of electrons donated by ligands
• Complexes where the metal is in +3 oxidation state are generally more stable than those where the
metal is in +2 oxidation state.

17.1.9 Chemical Reactivity and E° values


They differ widely in terms of their chemical reactivity. The metals of first series with the exception of
copper are relatively more reactive and oxidized by 1 M – H+. However, the rate of liberation of H2 is very

Chemistry at a Glance Final.pdf 191 4/1/2014 12:26:13 PM


17.186 Chemistry at a Glance

poor because some of these metals get protected due to the formation of an inert oxide film on their surface
e.g., Cr inspite of having highly –ve standard red potential values is SQ unreactive that it does not liberate
H2 on account of the formation of coating of Cr2O3 on its surface.
This general trend towards less negative E⊖ values is related to the increase in the sum of the first and
second ionization enthalpies. It is interesting to note that the E⊖ values for Mn, Ni and Zn are more negative
than expected from the general trend. However, the stabilities of half-filled d-subshell (d0) in Mn2+ and
completely filled d-subshell (d10) in zinc are related to their Ee values; for nickel , E0 value is related to the highest
negative enthalpy of hydration. Mn3+ and Co3+ ions are the strongest oxidizing agents in aqueous solutions.
The ions Ti2+, V2+ and Cr2+ are strong reducing agents and will liberate hydrogen from a dilute acid.

17.1.10 Oxides/Hydroxides
Covalent character and acidity of oxides and hydroxides directly depend on oxidation state of transition
metal atom present. As the oxidation state increases, their acidity and covalent character also increases.

Element Basic Amphoteric Acidic


V VO, V2O3 VO2 V2O5
Cr CrO, Cr2O3, CrO3
Cr(OH)2 Cr(OH)3 CrO2 (OH)2
H2Cr2O7
Mn MnO Mn3O4 MnO3
Mn2O3 Mn2O7
MnO
Fe FeO, Fe2O3 ––––––––– –––––––––
Fe3O4
Co, Ni, CoO, NiO ––––––––– –––––––––
Cu, Zn CuO, ZnO

17.1.11 Colour
They form coloured compounds.The colour of transition metal ions arises from the excitation of electrons
from the d-orbitals of lower energy to the d-orbitals of higher energy. The energy required for d–d electron
excitations is available in the visible range. It is for this reason that transition metal ions have the property
to absorb certain radiations from the visible region and exhibit the complementary colour. The colour of
light absorbed directly depends upon the nature of ligand present.

17.1.12 Magnetic Properties


Different substances possess mainly two types of magnetic behaviour. Those which are repelled by applied
magnetic field are diamagnetic, whereas those which are attracted by applied field are paramagnetic
substances. Another kind of substances which are attracted very strongly are called ferromagnetic.
Ferromagnetism is the extreme form of paramagnetism. Total magnetism of electrons due to its orbital
and spin motion is given by µ(S=
+L) 4S(S + 1) + L(L + 1)

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D-and F-Block Elements 17.187

S is total spin, i.e., sum of spin quantum number L is the sum of orbital angular momentum quantum
number. In many compounds including those of the first row transition elements the orbital contribution
is compensated by the electric field of the surrounding atoms and as an approximation the observed
magnetic moment may be considered to arise only from unpaired spins. Putting L = O
N N 
µs= 4S(S + 1)= 4× × + 1 = N(N + 2)
2  2 
Q S = N × 1/2

17.1.13 Interstitial Compounds


Interstitial compounds are those which are formed when small atoms like H,C or N are trapped inside the
metallic crystal lattice.
C and N always occupy octahedral holes. Hydrogen is smaller and therefore, always occupy
tetrahedral holes. As only transition metals form such compounds, the d-electrons are presumably involved
in such bonding. The structure of a metal generally changes during the formation of such compounds.

17.1.14 Catalytic Properties


Compounds of transition metals are able to act as catalysts due to:
• utillisation of (n – 1)d and ns-orbitals
• their ability to adopt different oxidation states
• their ability to form complexes

17.1.15 Alloy formation


Alloy is homogeneous mixture of metals. In alloys, the atoms of one metal are distributed randomly
among the atoms of the other. Alloys are formed readily by transition metals because of their similar
atomic size. E.g.
Ferrous alloys: Contains Cr, V, W, Mo and Mn along with Fe
Brass: Cu + Zn
Bronze: Cu + Sn
Potassium permanganate (KMnO4)
Preparation:
2MnO2 + 4KOH + O2 → 2K 2MnO4 + 2H2O
pyrolusite

2MnO2 + 2K 2CO3 + O2 → 2K 2MnO4 + 2CO2

2K 2MnO4 + Cl 2 → 2KMnO4 + 2KCl

2K 2MnO4 + H2O + O3 → 2KMnO4 + 2KOH + O2


Properties:
6± +;
It is a purple coloured crystalline substance. It is well 6 ;
&2±
soluble in water. &2 )H
)H
.0Q2+ 
Colour of MnO4– is due to charge transfer by oxygen 6
+ 6 12±
12±
to Mn, because of which Mn changes from +7 to +6 with 62± ,±
62± ,
one unpaired e- in 3d.

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17.188 Chemistry at a Glance

KMnO4 acts as an OA in acidic, neutral and alkaline media.


Oxidizing nature in acidic medium: MnO−4 + 8H + + 5e − → Mn2+ + 4H2O
Oxidizing nature in neutral medium:
MnO−4 + 2H2O + 3e − → MnO2 + 4OH −
Oxidizing nature in neutral medium or dilute alkaline medium: MnO−4 + 2H2O + 3e − → MnO2 + 4OH −
MnO−4 + e − → MnO24− is a very strong alkaline medium.
While exposed to sunlight or heated: 2KMnO4 → K2MnO4 + MnO2 + O2
2KMnO4 + conc.H2SO4 → Mn2O7 + K 2SO4 + H2O
E xplosiveoil .,
+ 2 .,20Q2.2+
(KMnO4 is excess)
Potassium dischromate (K2Cr2 O7) .0Q2
Preparation: &+ &+
∆ &+²2+
FeCr2O4 + 8Na 2CO3 + 7CO2  → 8Na 2CrO 4 + Fe2O3 + 8CO2
(Chromiteore)
&+²2+
2Na 2CrO4 + H2SO4 → Na 2Cr2O7 + Na 2SO4 + H2O
Na 2Cr2O7 + 2KCl → K 2Cr2O7 + 2NaCl
Properties:
Orange red coloured crystalline substance. Moderately soluble in cold water but freely soluble
in hot water.
In alkaline solutions, orange colour of Cr 2O72− change into yellow colour due to formation of CrO24 .
Again, yellow changes to orange in an acidic medium of pH > 7: Cr2O72− + 2OH − → 2CrO24− + H2O
If pH < 7: 2CrO24− + 2H + → 2Cr2O72− + H2O

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17.2 f-BLOCK (INNER-TRANSITION ELEMENTS)


• The F-block consists of two series of elements known as lanthanides and actinides.
• The general outer electronic configuration of the f-block elements is (n–2)f1–14 (n–1)d0–1 ns2.

Chemistry at a Glance Final.pdf 194 4/1/2014 12:26:13 PM


D-and F-Block Elements 17.189

• Lanthanide ions with less than one electron have similar colour to those with (14 – x)f electrons.
E.g., La3+ and Lu3+ are colourless, Sm3+ and Dy3+ are yellow coloured and Eu3+ and Tb3+ are pink
coloured.
• Lanthanides differ from transition metals in the fact that their magnetic moments do not obey spin
only formula. This is because in case of transition elements the orbital contribution is quenched by
the electric field of the environment but in case of lanthanides 4f orbitals lie too deep to be quenched.
• Silvery white soft metals tarnish rapidly in air, samarium being steel hard, in this regard.
• General outer electronic configuration is 4f1–14 5d0–1 6s2.

Element Atomic Number Electronic Configuration Oxidation Number


La 57 [Xe] 5d1 6s2 +3
Ce 58 [Xe]4f 5d 6s
1 1 2
+3, +4
Pr 59 [Xe]4f3 6s2 +3, (+4)
Nd 60 [Xe]4d4 6s2 (+2), +3, +4
Pm 61 [Xe]4f 6s 5 2
+3
Sm 62 [Xe]4f6 6s2 (+2), +3
Eu 63 [Xe]4f7 6s2 +2, +3
Gd 64 [Xe]4f 5d 6s
7 1 2
+3
Tb 65 [Xe]4f9 6s2 +3, (+4)
Dy 66 [Xe]4f10 6s2 +3, (+4)
Ho 67 [Xe]4f 6s 11 2
+3
Er 68 [Xe]4f12 6s2 +3
Tm 69 [Xe]4f 6s 13 2
(+2), +3
Yb 70 [Xe]4f14 6s2 +2, +3
Lu 71 [Xe]4f 5d 6s
14 1 2
+3

• Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous solutions.
Colour of these ions may be attributed to the presence of f-electrons. Neither La3+ nor Lu3+ ion
shows any colour but the rest do so. However, absorption bands are narrow, probably because of the
excitation within f-level. The lanthanoid ions other than the f0 type (La3+ and Ce4+ ) and the f14 type
(Yb2+ and Lu3+) are all paramagnetic. The paramagnetism rises to maximum in neodymium.
• Their oxides are used in glass industry for polishing glass and for making coloured glasses for
goggles as they gives protection against UV light and as phosphor for television screen and similar
fluorescing surfaces.
• The best single use of the lanthanoids is for the production of alloy steels for plates and pipes.
A (~95 per cent) and iron (~5 per cent) and traces of S, C, Ca and Al. A good deal of mischmetall
is used in Mg-based alloy to produce bullets. Shell and lighter flint, mixed oxides of lanthaniods are
employed as catalysts in petroleum cracking. Some individual Ln oxides are used as phosphors in
television screen and similar fluorescing surfaces.
Lanthanide contraction: It is the decrease in size of atoms and ions with increase in atomic number in
lanthanide series.

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17.190 Chemistry at a Glance

• Consequences of lanthanide contraction


Similar chemical properties
Decrease in basicity with decrease in the size
Similarly of II and III transition series
• Low ionization energies
• Lanthanides have low values of first and second ionization energies (IE1 and IE2) which are closer
to alkaline earth metals specially to calcium. On account of fairly low ionization energy and large
atomic size, lanthanoides are strong electropositive elements

17.2.1 Oxidation States


Lanthanoids show limited number of oxidation states because the energy gap between 4f and sd
subsshell is range
The E0 value of Ce4+/Ce3+ is +1.74 V, which suggest that it can oxidize water. However,
the reaction rate is very slow and hence Ce(IV) is a good analytical reagent.
• Coloured ions: Due to partially filled f-orbitals which allow f–f transitions.
• La3+ (4f0), Gd3+ (4f7), Lu3+ (4f14) → Colourless
/Q2 +
• Ce3+ (4f1) and Yb3+ (4f13) → Colourless despite
GV
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• With halogen: forms MH3 type halides /Q1 /Q 2+ +


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Chlorides → deliquescent and soluble

17.2.2 Actinides
• General outer electronic configuration is 5f1–14 6d0–1 7s2.

Element Atomic Number Electronic Configuration Oxidation Number


Ac 89 [Rn] 6d1, 7s2 +3
Th 90 [Rn]6d , 7s
2 2
+3, +4
Pa 91 [Rn]5f , 6d , 7s
2 1 2
+3, +4, +5
U 92 [Rn]5f3, 6d1, 7s2 +3, +4, +5, +6
Np 93 [Rn]5f4, 6d1, 7s2 +3, +4, +5, +6, +7
Pu 94 [Rn]5f 7s6 2
+3, +4, +5, +6, +7
Am 95 [Rn]5f7, 7s2 +3, +4, +5, +6
Cm 96 [Rn]5f 5d 6s
7 1 2
+3, +4

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D-and F-Block Elements 17.191

Element Atomic Number Electronic Configuration Oxidation Number


Bk 97 [Rn]5f 7s9 2
+3, +4
Cf 98 [Rn]5f , 7s
10 2
+3
Es 99 [Rn]5f11, 7s2 +3
Fm 100 [Rn]5f , 7s
12 2
+3
Md 101 [Rn]5f , 7s
13 2
+3
No 102 [Rn]5f14, 7s2 +3
Lr 103 [Rn]5f , 6d , 7s
14 1 2
+3

• Actinide contraction is similar to lanthanide contraction.


• The ions having 2 to 6 electrons in 5d orbitals are coloured, both in crystalline and in aqueous
solution, due to f–f transition.
• Ions with 5f0, 5f7 and 5f14 configurations are colourless.
Unlike lanthanoids, actinoids show a large number oxidation states. This is because of very small energy
gap between 4f, 6d and 7s subshells; hence, all these electrons can take part in bonding.
The actinoids are highly reactive metals, especially when finely divided. The action of boiling water on
them, for example, gives a mixture of oxide and hydride and combination with most nonmetals takes place
at moderate temperatures. Hydrochloric acid attacks all metals but most are slightly affected by nitric acid
owing to the formation of protective oxide layers, whereas, alkalies have no action in this regard.

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Chapter 18 MetallurgiCal
extraCtion

18.1 INTRODUCTION
The compound of a metal found in nature is called a mineral. The minerals from which metal
can be economically and conveniently extracted are called ores. An ore is usually contaminated
with earthy or undesired materials known as gangue. Hence, all minerals are not ores but all ores
are minerals.
Oxides and hydroxides: Fe, Cu, Zn, Ni, Bi, Cd and Sn; Carbonates: Fe, Cu, Zn, Pb, Ca, Mn and Mg.
Silicates: Cu, Zn Ni, Al, Li, Na, K and Be; Sulphates: Mg, Ba, Ca and Pb
Phosphates: Li, Na, K, Ca, Fe and Mn; Nitrates: Na and K
Nitrate ores are rare because all nitrates are water soluble and at higher temperature they decomposes
into oxides of their metal.

18.1.1 Important Ores of Some Metals


1. Iron: In the combined state iron occurs in the following minerals.
(i) Haematite (Fe2O3): main ore
(ii) Magnetite (Fe3O4)
(iii) Limonite (3Fe2O3.3H2O)
(iv) Siderite (FeCO3).
2. Tin: Cassiterite or tin stone (SnO2): main ore
3. Copper: Occurs in the native state as well as in the compound form. The natural ores of
copper are
(i) Copper pyrites (CuFeS2): main ore
(ii) Malachite (Cu(OH)2.CuCO3) (green colour)
(iii) Cuprite or ruby copper (Cu2O)
(iv) Azurite(CuOH)2.2CuCO3)
(v) Copper glance (Cu2S)
4. Lead
(i) Galena (PbS): main ore (ii) Cerrusite (PbCO3)
(iii) Anglesite (PbSO4) (iv) Wulfenite (PbMnO4)
(v) Stozite (PbWO4)

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Metallurgical Extraction 18.193

5. Magnesium:
(i) Dolomite (MgCO3.CaCO3): main ore (ii) Carnallite (MgCl2.KCl.6H2O)
(iii) Asbestor: (CaSiO3.3MgSiO3) (iii) Magnesite (MgCO3).
(vi) Schonite (MgSO4.K2SO4.6H2O) (vii) Epsom salt (MgSO4.7H2O)
6. Aluminium: Aluminium is the third most abundant element of earth`s crust.
(i) Corundum (Al2O3): main Ore (ii) Diaspore (Al2O3.H2O)
.
(iii) Bauxite (Al2O3 2H2O) (iv) Cryolite (Na3AlF6)
(vi) Alumstone (K2SO4.Al2(SO4)3.2Al(OH)3)
7. Silver: In the native form it is associated with copper and gold. The main ores of silver are
(i) Argentite or silver glance (Ag2S): main ore
(ii) Horn silver (AgCl)
(iii) Proustite or ruby silver (3Ag2S.As2S3)
(iv) Pyrargyrite (3Ag2S.Sb2S3) i.e., Ag3SbS3.
8. Manganese: (i) Pyrolusite, (MnO2) (ii) Braunite (Mn2O3)
9. Zinc: (i) Zinc blende (ZnS) (ii) Calamine (ZnCO3) (iii) Zincite (ZnO)
Oxygen is the most abundant element in the earth’s crust by weight.
Aluminium is the most abundant metal in the earth’s crust.
Most abundant element in the atmosphere is nitrogen.

18.1.2 Other Important Ores


 Fluorspar (CaF2)  Gypsum (CaSO4.2H2O)
 Pitch blende (U3O8)  Borax (Na B O .10H O)
2 4 7 2

 Cinnabar (HgS)  Chile salt peter (NaNO3)


 Indian salt peter (KNO3)  Rutile (TiO2)

18.2 METALLURGICAL OPERATION


Flow sheet for the general metallurgical operation is given below. In the flow sheet, the functions of process
are given on the right side, whereas the methods employed are denoted on the left.
(A) Crushing and grinding: The ore is first crushed by jaw crushers and ground in various size
reduction equipments like ball mill, jaw crusher, etc.
(B) Concentration or dressing of the ore: The process of removal of the unwanted material (gangue)
from the ore is called concentration or dressing or benefaction of the ore. The important methods for
concentration are listed hereunder.
(i) Hydraulic washing or gravity separation or levigation method: The method is based on
the difference in specific gravities of the ore and gangue particles. It is also known as gravity
separation method. The powdered ore is washed with an upward stream of running water,
where the lighter gangue particles are washed away while the heavier ore particles are left
behind, e.g., ores [like tinstone (SnO2), haematite (Fe2O3), chromite (FeO.Cr2O3), etc.] are
concentrated by this method.
Gangue or matrix: The non-metallic impurities such as mica, earth particles, etc. associated
with crude ore are known as gangue or matrix.

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18.194 Chemistry at a Glance

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(ii) Magnetic separation: The method is based on magnetic and non-magnetic prop-
erties of the two components of the ore. This method has limited application. The
ground ore is carried on a travelling band which passes over a magnetic roller. The ore
leaves the band and falls from it. The particles attracted by the magnetic field form a
separate pile. This method is useful for separating tin ore particles from cassiter-
ite (SnO2). The process may also be employed for separating other transition metal
ores such as magnetite (Fe3O4), chromite (FeO.Cr2O3) and pyrolusite (MnO2) from
unwanted gangue.
The method is used for strongly ferromagnetic ores of Fe, Sn, etc. Wolframite (FeWO4) is a
magnetic ore that can be separated from the non-magnetic ore cassiterite (SnO2).

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Metallurgical Extraction 18.195

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(iii) Froth floatation method: This is a very useful technique especially for separating sulphide
ores of zinc, copper and lead from the gangue. A suspension of the finally powdered ore is
made with water. Suspension is mixed with 3.5 per cent by weight of eucalyptus oil (or some
other cheap oil) and the mixture is stirred by compressed air. Froth is generated at surface.
Sulphide particles in ores are preferentially wetted by this froth and rise to the surface. They are
skimmed off by a skimmer. Gangue is preferentially wetted by water and sinks to bottom.
Reagents used in froth floatation process
(a) Froathers: Which create froth, e.g., palm oil.
(b) Collectors: The surface of collectors adsorb small ore particles and these collector
particles come with froth air bubbles. E.g., ethyl xanthate or potassium ethyl xanthate.
(c) Activators: Simple inorganic compounds which enhance the effect of collectors,
e.g., Na2S, CuSO4, etc.

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(d) Depressants: Depressants are used to prevent certain type of particles from forming the
froth with the bubbles. E.g., sodium cyanide can be used as a depressant in the separation
of zinc sulphide ore (ZnS) and lead sulphide ore (PbS). NaCN acts as a depressant for
ZnS but does not prevent PbS from the formation of froth, e.g., NaCN, Na2CO3, KCN,
etc. NaCN forms a layer of zinc complex, Na2Zn(CN)4 on the surface of ZnS and thereby
prevents it from the formation of froth.
(iv) Leaching: This method is useful in cases where ore is soluble in a suitable solvent, but
impurities are insoluble. E.g., in Baeyer’s process pure aluminium oxide is obtained from the
bauxite ore by treating the powdered ore with a concentrated solution of sodium hydroxide
where Al2O3 dissolves leaving behind the impurities.
Al2O3(s) + 2OH–(aq) + 3H2O → 2Al(OH)4–(aq)
The solution of sodium aluminate is filtered and cooled and its pH is adjusted downward by
dilution and/or neutralization with CO2 where aluminium hydroxide is precipitated; seeding
with a little freshly precipitated aluminium hydroxide quickens the process.

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18.196 Chemistry at a Glance

Dilution
Al(OH)4–(aq) →
CO2
Al(OH)3(s) + OH–(aq)
The precipitate of Al(OH)3 is filtered, dried and finally heated to about 1473 K to
obtain pure Al2O3.
2Al(OH)3(s) → Al2O3(s) + 3H2O(g)
In the metallurgy of silver and that of gold, the respective metal/ore leached with a dilute
solution of NaCN or KCN in the presence of air (for O2) from which the metal is obtained later
by replacement.
4M(s) + 8CN–(aq) + 2H2O(aq) + O2(g) → 4[M(CN)2]–(aq) + 4OH–(aq)
2[M(CN)2]–(aq) + Zn(s) → [Zn(CN)4]2–(aq) + 2M(s)
(C) Extraction of the crude metal from the concentrated ore
The concentrated ore must be converted into a form which is suitable for reduction to the metal.
If the ore is a hydroxide (hydrated oxide), carbonate or sulphide it is subjected to calcination or
roasting/melting and thereby converted to the oxide form, for thermodynamic reasons it is easier to
reduce an oxide than the sulphide.
(i) Calcination: When the ore is heated below its melting point in limited supply of air, mainly
decomposition reactions occur. This process is known as calcination. Calcination is highly
endothermic. A reverberatory furnace is usually employed for carrying out calcination.
During calcination:
(a) All the volatile impurities are lost.
(b) Water of crystallizations is lost. E.g., Al2O3.2H2O → Al2O3 + 2H2O(g)

Calcination reactions are: 2Al(OH)3 → Al2O3 + 3H2O
Al2O3.2H2O 

→ Al2O3 + 2H2O

CaCO3 → CaO + CO2
CaCO3.MgCO3 

→ CaO + MgO + 2CO2
(ii) Roasting: Roasting is done at a temperature slightly higher than that of calcination in excess
of air. The ore does not melt during roasting. All the combustible organic matter burns away and
the ore becomes more porous. Exothermic reactions supply much of the heat and much lesser
energy is required in this case. In the roasting process, ore is converted into its oxide or sulphate.
The process of roasting is generally carried out in a reverberatory furnace or blast furnace.
e.g., 2 ZnS + 3O2 → 2 ZnO + 2SO2
2 PbS + 3O2 → 2 PbO + 2SO2
PbS + 2O2 → PbSO4
2Cu2S + 3O2 → 2 Cu2O + 2SO2
In chloridizing roasting, the ore is changed into metal chloride by heating with common salts
in presence of air.
TiC + 4Cl2 → TiCl4 + CCl4 Ag2S + 2NaCl → 2 AgCl + Na2S

Note:
The free energies of formation (DGf°) of most sulphide ore are greater than those for CS2 and H2S. CS2 is, in fact, an
endothermic compound. So neither carbon nor hydrogen is a suitable reducing agent for metal sulphides. Moreover,
the roasting of a sulphide to the oxide is quite advantageous thermodynamically. Hence, the common practice is to
roast sulphide ore to the oxide prior to reduction.

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Metallurgical Extraction 18.197

(iii) Smelting: The process of extraction of metal in fused (molten) state is called smelting.
This process is carried out in blast furnace. During melting, the ore is heated with suitable
reducing agent in order to obtain the metal.
During this process, some infusible impurities are also removed from molten metal by adding
suitable substance known as flux. Even after concentration, ore may contain some infusible
impurities, which may be acidic, i.e., non-metallic oxides like SiO2, P2O5, etc. or basic, i.e., metallic
oxides like CaO, FeO, etc.
Impurity + Flux → Slag (fusible mass, which floats over molten metal)
Slag is a fusible mass and has low m.pt. It is lighter than metal and is immiscible with molten
metal; hence, it floats over the metal. The layer of slag over molten metal prevents the metal
from oxidation.
(a) Acidic flux: They are used to remove basic impurities like CaO, MgO, FeO, etc. They are acidic
in nature, i.e., oxides of non-metals, e.g., SiO2, P2O5, B2O3, etc.
SiO2 + CaO → CaSiO3
Acidic flux Basic impurity Slag

(b) Basic flux: Basic flux removes acidic impurities like SiO2, P2O5, etc. and is basic in nature.
e.g., CaO, (obtained from limestone), MgO (obtained from magnesite MgCO3), etc.
SiO2 + CaCO3 → CaSiO3 + CO2
Acidic flux Basic impurity Slag

Some important reduction process are described below:

18.3 REDUCTION CONVERSION OF ORE TO METAL

The ore, obtained after calcination or roasting, is reduced to metal and choice of reducing agent depends
upon the nature of the ore. Some common reducing agents are listed hereunder:
(a) Reduction by Carbon and Carbon Monoxide
(i) Due to cheapness and high availability, carbon is widely used as a reducing agent. The process
is known as carbon reduction process.
(ii) The metals which are less electropositive and do not form carbides with carbon are reduced by
this method, e.g., oxides of Pb, Fe, Zn, Sn, etc.
(iii) For reduction, the ore is strongly heated with coke or coal in blast furnace, where
metal is obtained in the form of vapours, which are condensed (Zn) or in molten state
(Sn, Fe, etc.) e.g.,
∆ ∆
ZnO + C → Zn + CO; NiO + C → Ni + CO; Cr2O3 + 3C → 2Cr + 3CO
Fe2O3 + 3C → 2Fe + 3CO; (Devil’s process)
(iv) Some disadvantages of carbon reduction process are that some time metallic oxide may form
carbide instead of the metal, e.g., CaO + 3C → CaC2 + CO. In some cases, reversible reaction
may take place and so during the cooling, formation of oxide may take place, e.g., MgO + C ⇌
Mg + CO, thus carbon is not fit for reducing CaO and MgO.
(v) Carbon monoxide also act as a reducing agent. e.g.,
PbO + CO → Pb + CO2; FeO + CO → Fe + CO2;
Fe2O3 + 3CO → 2Fe + 3CO2; Fe3O4 + 4CO → 3Fe + 4CO2

Chemistry at a Glance Final.pdf 203 4/1/2014 12:26:13 PM


18.198 Chemistry at a Glance

Note:
(i) Below 710°C, CO is a better reducing agent than carbon and the reverse is true at temperature higher than 710°C.
It can explained on the basis of Ellingham diagrams given in the thermodynamics of metallurgy.
(ii) Carbon is a good reducing agent for oxides but not for sulphides.

(b) Reduction by Metals:


(i) Highly electropositive metals like Na, K, Li, Al, etc. are used to reduce the less electropositive
metals like Cr, Cu, Mn, etc.
(ii) Reduction by powdered aluminium is known as Gold-Schmidt aluminothermite process. This
process is employed in cases where metals have very high m.pt. and are to be extracted from
their oxides. In this process thermite (mixture of ore and powdered aluminium) is taken in
a steel crucible. The reaction is started by using ignition mixture (Mg powder and barium
peroxide). It is called thermite process because large amount of heat is released during the
reduction, which fuses both ore and metal. E.g., reduction of Cr2O3 by Al powder takes
place as follows:
Mg + BaO2 → BaO + MgO + Heat
Heat
Cr2O3 + 2Al  → 2Cr(l) + Al2O3 + Heat (112 kcal)
Similarly, 3Mn3O4 + 8Al → 9Mn + 4Al2O3
(c) Reduction by H2 or water gas (CO + H2)
(i) The oxides of metals, which are less electropositive than hydrogen (e.g., CuO, FeO, Ag2O, etc.)
may be reduced by this method. E.g.,
CuO + H2 → Cu + H2O MoO3 + 3H2 → Mo + 3H2O
Ag2O + H2 → 2Ag + H2O Cr2O3 + 3H2 → 2Cr + 3H2O
Fe3O4 + 4H2 → 3Fe + 4H2O 2NiO + CO + H2 → 2Ni + CO2 + H2O
(ii) Water formed during the reaction escapes out in the form of vapours.
(d) Self-reduced or auto reduction: Oxides of unreactive metals (like those of Hg, Pb, Cu, etc.) are
reduced by air/anion of ore. Here, no external reducing agent is added. E.g.,
(i) Extraction of Hg from cinnabar: 2HgS + 3O2 → 2HgO + 2SO2; 2HgO + HgS → 3Hg + SO2
(ii) Extraction of Cu from copper glance: 2Cu2S + 3O2 → 3Cu2O + 2SO2; Cu2S + 2Cu2O
→ 6Cu + SO2
(iii) Extraction of Pb from galena: 2PbS + 3O2 → 2PbO + 2SO2; 2PbO + PbS → 3Pb + SO2
(e) Hydrometallurgy or displacement method
(i) This method is based on the fact that a more reactive metal displaces less reactive metal from
its salt solution.
(ii) In this method, ore is converted into soluble form where more reactive metal is added in it. E.g.,
(a) Extraction of copper from malachite: CuCO3.Cu(OH)2 → 2CuO + H2O + CO2
CuO + H2SO4 → CuSO4 + H2O; CuSO4 + Zn → ZnSO4 + Cu ↓
(b) Cyanidation process for Ag and Au: Ag2S + 4NaCN ⇌ 2Na[Ag(CN)2] + Na2S
Na2S + 2O2 → Na2SO4; 2Na[Ag(CN)2] + Zn → Na2[Zn(CN)4] + 2Ag ↓
(f) Amalgamation process: The process is used for extraction of noble metals like Pt, Au, Ag, etc.
Finely powdered ore is treated with Hg to form amalgam. Amalgam, on distillation, is decomposed
to the metal and Hg.
Distillation
Ore + Hg → Amalgam  → Metal + Hg vapours

Chemistry at a Glance Final.pdf 204 4/1/2014 12:26:14 PM


Metallurgical Extraction 18.199

(g) Electrolytic reduction: It is the most commonly used method of reduction. The ores of highly
electropositive metals like alkali metals and alkaline earth metals cannot be reduced by common
reducing agents like H2, C, etc., because of formation of carbides. For electrolytic reduction, oxide,
hydroxide or halide (as suitable) ore is fused. If melting point is quite high, some substances are
added to lower the fusion temperature. The quantitative aspects of electrolytic reduction are based
on Faraday’s laws of electrolysis. The cell used for electrolysis is known as electrolytic cell and its
functioning may be explained as given below.
Let an ore AB (containing An+ cation of metal and Bn– anion) is subjected to electrolytic reduction.
AB(l) → An+ + Bn– An+ + ne– → A(l) (at cathode) Bn– → B + ne– (at anode)
The nature of electrode, EMF applied, etc. depends upon the nature of the metal.

18.4 ELLINGhAM DIAGRAM


During combination reactions, the entropy of system decreases. Therefore DS is negative for combination
reaction. Gibbs free energy change, DG = DH = TDS
1
M + O2 → MO, DH = –ve then DG will be less negative for this type of reaction if temperature is
2
increased as TDS becomes more negative. After a certain temperature, reaction will become
non-spontaneous as the value of DG will become positive.
When activity of all reacting substances is unity, then DG = DG°. For one mole common reactant (like
oxygen, halogen, sulphur, etc.) value of DG° may be plotted against temperature. These DG° vs T curves are
known as Ellingham diagrams.
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18.4.1 Important Features of Ellingham Diagrams


(i) A typical Ellingham diagram follows a straight line unless there is large entropy change due to
melting or vapourization.
(ii) All the plots slope upwards because DG° becomes more positive when temperature increases.
(iii) At a certain temperature DG° = 0 and above this temperature, it is positive. The metal oxide
(or other products like sulphide or halide) formation is spontaneous below this temperature.
Theoretically, all oxide are thermally unstable provided that this temperature can be attained.

Chemistry at a Glance Final.pdf 205 4/1/2014 12:26:14 PM


18.200 Chemistry at a Glance

(iv) A metal can reduce the oxide of metal placed above in the diagram, due to more negative free en-
ergy, e.g., Al can reduce Cr but not Mg or Ca.
(v) Reducing behaviour of carbon : There may be three types of reactions:
C(s) + O2 → CO2 ......(i)
2C(s) + O2 → 2CO .....(ii)
2CO(g) + O2 → 2CO2 .......(iii)

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For reaction (i), the volume of CO2 formed is almost equal to volume of O2 consumed. So, DS does
not change significantly and Ellingham plot is almost horizontal.
For reaction (ii), plot is downward and unlike other reactions in this reaction DG° value becomes
more negative as temperature is increased. It is due to positive value of DS because here two volumes
of CO are produced for one volume of O2 consumed, thus DS is positive.
For reactions (iii), again DS is negative because 3 moles of gases react to form two moles gas and so
DG° becomes more positive with rise in temperature.
The plots for three reactions cross at 710°C and it shows that formation of CO2 from CO is more
favoured below 710°C while at higher temperatures CO is formed preferably. Formation of CO2
from carbon is not much affected by temperature.
Due to downward slope theoretically C will reduce any metal oxide provided that temperature is
sufficiently high. However, it is not attempted due to possibility of formation of carbide at high tem-
peratures and maintenance of such high temperature is not economically profitable. Below 710°C,
CO is a better reducing agent than carbon because of more negative value of DG° of the reaction,
2CO + O2 → 2CO2 upto this temperature.

18.5 REFINING OR PURIFICATION OF METAL


The metals extracted by any of the above operations are in their crude form. The crude form is usually
contaminated with impurities of following nature.
(a) Impurities of other metals obtained by the simultaneous reduction of their respective oxides present
in the ore as impurities.
(b) Impurities of non-metals like silicon or phosphorous formed by reduction in the furnace.
(c) Impurities of unreduced oxides and sulphides of the metals.
(d) Impurities of residual slag, flux, etc. introduced during treatment in the furnace.
To remove these impurities, the crude metal is subjected to the process of purification or refining.
Refining of the crude metals may be done by the following methods depending upon the nature of
the metal and impurities.

Chemistry at a Glance Final.pdf 206 4/1/2014 12:26:14 PM


Metallurgical Extraction 18.201

18.5.1 Electrolytic Refining


In this method, the impure metal is converted into a block which forms the anode while cathode is a rod
or plate of same pure metal. These electrodes are suspended in an electrolyte which is the solution of a
soluble salt of the metal usually a double salt of the metal. When electric current is passed, metal ions from
the electrolyte are deposited at the cathode in the form of pure metal while an equivalent amount of metal
dissolves from the anode and goes into the electrolyte solution as metal ion. The soluble impurities present
in the crude metal anode go into the solution while the insoluble impurities settle down below the anode
as anode mud or anode sludge.

18.5.2 Liquation Process


The refining process for crude metal based on the difference in fusibility of metal and impurities is named
as liquation process. Zn–Pb mixture is separated by heating the crude Zn just above the melting point of
Zn, whereas Pb remains as non fusible mass. The molten mass is allowed to flow on an inclined plane,
whereas non-fusible mass is left behind.

18.5.3 Distillation Method


Volatile metals (Hg, Zn and Cd) are easily purified by distillation. The impure metal is heated in a retort
and vapours of volatile metals are collected and condensed in a receivers leaving behind non-volatile
impurities in a retort.

18.5.4 Heating of Crude form with Ores


Fe and Sb ores are heated with crude form which removes the contaminated reducing agents (S and C) with
it and pure metal is obtained.

18.5.5 Oxidation Process


Impurities in crude form having more affinity for O2 than the metal itself are oxidized in suitable furnaces.
The oxides formed at the surface are skimmed off. The various oxidation processes used for different metals
involve poling, puddling, bessemerization and cupellation.
(a) Poling: The molten impure metal (Cu) containing oxides as impurity is stirred with green poles of
wood which releases hydrocarbon gases. These hydrocarbon gases reduce oxide to metal.
(b) Puddling: It involves the preparation of nearly pure wrought iron from cast iron that contains
a high percentage of carbon. The cast iron is heated with hematite (Fe2O3), the oxygen of which
oxidizes the carbon.
(c) Bessemerization: A process for making steel from cast iron, named after its discoverer H.
Bessemer. The impure molten metal is heated in a Bessemer converter (a large, egg-shaped vessel
with holes below) and air is blown up to oxidize the impurities. Now the required amount of spiegel
is added to introduce correct amount of carbon for the type of steel required.
(d) Cupellation: The separation of silver, gold and other noble metals from impurities that are oxidized
by hot air. The impure metal is placed in a cupel, a flat dish made of porous refractory material and
a blast of hot air is directed upon it in a special furnace. The impurities are oxidized by air and are
partly swept away by the blast and partly absorbed by cupel. This method is also based on different
affinities of metal and impurity towards oxygen, Method is known as cupellation because impure

Chemistry at a Glance Final.pdf 207 4/1/2014 12:26:14 PM


18.202 Chemistry at a Glance

metal is fused in small boat shaped dishes of boneash or cement called cupels. This method is useful
for removal of Pb impurity from Ag and Au.
(e) Mond’s process: Impure nickel is purified by this process. Ni forms Ni(CO)4 on passing steam of
CO over impure Ni at 60°–70°C which on heating in another tower at 180°C decomposes.
60°−70° C 180° C
Impure Ni + 4CO  → Ni (CO)4(g)  → Ni + 4CO(g)
(f) Van-Arkel method: This method is used to obtain ultrapure samples of Ti, Zr, HF, Si, etc. Such
metals on heating with I2 gives vapours of iodides which decomposes on heating more to give
ultrapure metals.
523k 1700k
Ti + 2I2 
→ TiI4(g) 
→ Ti + 2I2(g)

18.6 ExTRACTION OF IRON


Both iron and tin are extracted by the carbon reduction method.

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Chemistry at a Glance Final.pdf 208 4/1/2014 12:26:14 PM


Metallurgical Extraction 18.203

18.6.1 Extraction of Iron


Iron is extracted from its principal ore hematite.
After the preliminary washing, concentration and roasting, the ore is smelted in the presence of coke
and limestone in a blast furnace. Roasted ore (8 parts) with desulphurized coke (4 parts) and limestone
pieces (1 part) is fed into the blast furnace from the top. Preheated air in blown in through water-jacketed
pipes called tuyers fixed in the lower part of the furnace. There is a temperature gradient as we move from
the bottom (temperature about 2000 K) to the top (temperature around 500 K) of the blast furnace. The
blast furnace may be broadly divided into three main parts as described hereunder.
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(i) Zone of fusion: The lower portion where coke burns and produces CO2 and a lot of heat is known
as zone of fusion.
C + O2 → CO2 DH = –406 kJ/mol
Here, the temperature is about 1775 K. A little above this, where temperature is about 1475 K–1575
K, iron is obtained in molten form.
(ii) Zone of heat absorption: in the middle portion (temperature 1075K–275 K), CO2 rising up is
reduced to CO with the absorption of heat: CO2 + C → 2CO DH = 163 kJ/mol.
In this portion, limestone coming from above is decomposed and the resultant lime (CaO), which
acts as a flux, combines with silica (present as impurity, i.e., gangue) to form calcium silicate
(fusible slag).
Ca CO3 → CaO + CO2 CaO + SiO2 → Ca SiO3 (slag).
(iii) Zone of reduction: This is the upper portion (675 K–975 K) where iron oxide is reduced to
spongy iron by carbon monoxide rising up the furnace: Fe2O3 + 3CO → 2 Fe + 3 CO2.

Chemistry at a Glance Final.pdf 209 4/1/2014 12:26:14 PM


18.204 Chemistry at a Glance

The reduction is believed to takes place in stages: 3Fe2O3 + CO → 2Fe3O4 + CO2.


Fe3O4 + CO → 3FeO + CO2 Fe O + CO → Fe + CO2
At the bottom of the furnace the molten iron sinks down while above this floats the fusible slag
which protects the molten iron form oxidation. These two can be removed from different holes.
Waste gases escaping at the top consists of about 30 per cent CO, 10 per cent CO2 and the rest
nitrogen. Iron obtained from the blast furnace is known as pig iron.

18.6.2 Types of Iron


Following are the commercial varieties of iron depending on the percentage of carbon content.
(i) Cast iron: It is the most impure form of iron containing the highest percentage of carbon
(2.5 to 5 per cent) and about 2 per cent of other impurities like Si, P, Mn and S. Cast iron is of
two types as listed hereunder.
1. White cast iron: Carbon is present in the form of cementite, Fe3C.
2. Grey cast iron: Carbon is present in the form of graphite.
Properties of cast iron:
(a) Due to the presence of impurities, cast iron melts at 1250°C, whereas pure iron melts
at 1530°C.
(b) The molten cast iron expands on solidification and thus produces good castings.
(c) It does not rust easily. It is neither tempered nor magnetized easily.
(d) It is hard and brittle due to high carbon content and cannot be welded.
(e) Due to very little ductility, it is not suitable for forging.
(f) It is used for casting, railing, hot water pipe, electric poles, etc. where strain is minimum.
(ii) Wrought iron: It is the purest form of iron containing the lowest percentage of carbon from
0.1 to 0.25 per cent and 0.3 per cent as other impurities. It is manufactured from cast iron by
puddling process in a special type of reverberatory furnace, the hearth of which is lined with
hematite (Fe2O3).
(iii) Properties of wrought iron:
1. Wrought iron is extremely tough, highly malleable and ductile and has high magnetic perme-
ability.
2. It softens at about 1000°C and then it can be forged and welded.
3. Due to the presence of very small percentage of slag, it has fibrous structure and thus can with-
stand high stresses.
4. Wrought iron is resistant towards rusting and corrosion.
(iv) Uses of wrought iron: Wrought iron is used
1. In the manufacture of articles capable to hold sudden stress, e.g., chains, nails, hooks, bolts, etc.
2. In the manufacture of electromagnet and agricultural implements.
3. In making wires and bars.

18.6.3 Steel
The most important commercial variety of iron having percentage of carbon in midway between that of
cost iron and wrought iron, i.e., 0.25 to 2 per cent. The properties of steel depend upon its carbon contents,
since with the increase in carbon content, the hardness of steel increases while its ductility decreases.
The presence of Si gives steel a fibrous structure. Presence of Mn produces elasticity and increases tensile
strength. Cr imparts resistance to chemical action.

Chemistry at a Glance Final.pdf 210 4/1/2014 12:26:14 PM


Metallurgical Extraction 18.205

1. Alloy steel: Steel mixed with small amounts of nickel, cobalt, chromium, tungsten, molybdenum,
manganese, etc., acquires special properties. Such products are called special steels or alloy steels.
Some important alloy steels are given in the table hereunder.
S. Name of Metal Added Properties Uses
No. Alloy Steel
1. Invar 36 per cent Ni Coefficient of expansion Measuring tapes and
is very small pendulums
2. Chrome 1 per cent Cr, High tensile strength Springs, shafts,
vanadium steel 0.15 per cent V axles, etc.
3. Manganese steel 12–15 per cent Mn Hard and tough Rock crushing
machinery safes,
helmets, etc.
4. Stainless steel 11.5 per cent Cr, Resists corrosion Common articles
2 per cent Ni
5. Tungsten steel 14–20 per cent W, Very hard High speed tools
3–8 per cent Cr

18.7 MANUFACTURE OF STEEL


Manufacture of steel is made by either of the following methods.
(a) The Bessemer process: The process is carried out in Bessemer converter made up of steel plates
lined with silica bricks (if impurities in cast iron are of basic nature, i.e., MnO) or lined with CaO or
MgO (if impurities in cast iron are of acidic nature, i.e., P4O10 or SO2 or SiO2). The molten cast iron is
introduced in the converter and a blast of hot air is blown through it from the bottom, keeping the
mouth of the converter vertically upwards. Impurities of MnO or P or S present in cast iron are first
oxidized and then combine to form slag.
Si + O2 → SiO2 2Mn + O2 → 2MnO MnO + SiO2 → MnSiO3
4P + 5O2 → P2O10 P4O10 + 6CaO → 2Ca3(PO4)2 (Thomas slag)
Finally carbon is oxidized to carbon monoxide which burns with blue flame at the mouth of the
converter. Some iron is also oxidized which converts the carbon into carbon monoxide.
4 Fe + 3 O2 → 2 Fe2 O3 Fe2O3 + 3C → 2Fe + 3CO
When whole of the carbon is oxidised (i.e., the blue flame suddenly dies out), the air supply is stopped
for a while and the requisite amount of spiegeleisen (an alloy of Fe, Mn and C) is added. The blast is
continued just for a moment to ensure complete mixing. Mn and C serve as deoxidizer and reduce
FeO (if any) and the rest amount of Mn and C is mixed with molten steel to give manganese steel.
Mn makes steel harder and increases its tensile strength.
(b) Open Hearth process or Siemens-Martin process :
This is the modern process and the furnace used consists of an open hearth lined with silica or
calcined dolomite (CaO.MgO) depending upon the nature of impurities present in pig or cast iron.
Silica lining is used if the impurities are of manganese, silicon, etc. and calcined dolomite lining is
used if phosphorus is present in appreciable amount.
The charge consisting of pig or cast, iron scrap, iron ore (hematite) and lime heated on the hearth of
the furnace at about 1500°C by producer gas. The following reactions occur.
Acidic process: 3Si + 2 Fe2O3 → 4Fe + 3SiO2; 3Mn + Fe2O3 → 2Fe + 3 MnO; MnO + SiO2 →
MnSiO3 (slag)
Basic process: 12P + 10 Fe2O3 → 3P4O10 + 20Fe; 6CaO + P4O10 → 2Ca3(PO4)2 (slag)

Chemistry at a Glance Final.pdf 211 4/1/2014 12:26:14 PM


18.206 Chemistry at a Glance

Finally C and S are oxidized forming volatile gases: CaO + SiO2 → CaSiO3 (slag)
2Fe2O3 + 3S → 3SO2 + 4Fe; Fe2O3 + 3C → 3CO + 2Fe
Samples of steel drawn from time to time and tested for carbon content, finally spiegeleisen (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, i.e., longer time than Bessemer process (20–30 minutes) but it
has the following advantages over the Bessemer’s process.
(i) The temperature can be controlled as the heating is done externally.
(ii) The composition and quality can be well controlled as it is a slow process.
(iii) In this process, scrap iron is reused.
(iv) The loss of iron in this process is only 4 per cent while the loss is about 15 per cent in
Bessemer’s process.
(v) This yields better quality of steel.
(c) Duplex process: This is actually a combination of acid Bessemer process and open hearth pro-
cess. Si, Mn, S and C (partially) are oxidized and removed as slag or volatile oxides.

18.8 hEAT TREATMENT OF STEEL


(a) Annealing: It is a process of heating steel to bright redness and then cooling it very slowly to make
the steel soft and ductile.
(b) Quenching: It is a process of heating steel to bright redness and then cooling it suddenly by plung-
ing in water or oil to have extremely hard and brittle steel. It has very low elasticity.
(c) Tempering: It is a process of heating the quenched steel to a temperature much below redness and
then cooling it slowly. Such a steel is neither hard nor so brittle. During the process of tempering, a
thin film of the oxide is formed on the surface of steel. The colour of the oxide film depends on the
temperature at which the quenched steel is heated.

Temperature range (°C) Colour of the oxide film


200°–230 °C Yellow
225°–270 °C Brown
300 °C Blue

18.9 ExTRACTION OF TIN


Metallic tin is extracted from tin stone or cassiterite (SnO2) which contains about 10 per cent of the metal
as SnO2. The rest being siliceous matter and tungstates of Fe, Cu and As.
After crushing, the ore is concentrated by washing in a current of water (gravity process to remove
lighter gangue particles) and by magnetic separator to remove tungstates of Fe and Mn.
Finally, the ore is smelted in a reverberatory furnace or in a blast furnace at 1475–1575 K. The ore is
mixed with one-fifth of its mass of powdered anthracite (coal) and little of lime or fluorspar which is used
as flux. Tin oxide is reduced to tin.
SnO2 + 2 C → Sn + 2CO

18.9.1 Refining of Tin


(i) Liquation or sweating: When the block of impure tin is heated on the sloping hearth of
reverberatory furnace, tin along with Pb and Bi (all having much lower melting points than other
metals) run off leaving a dross of an alloy of Mn, Fe, Cu, W and As.

Chemistry at a Glance Final.pdf 212 4/1/2014 12:26:14 PM


Metallurgical Extraction 18.207

(ii) Poling: The sweated tin is stirred with logs of green wood where impurities get oxidized and scum
formed is skimmed off, from where 99 per cent pure tin is obtained. Scum and dross are repurified.
Slag contains 10–25 per cent Sn as SnSiO3 because of amphoteric nature of tin. This is recovered by
smelting with carbon and CaO flux at a much higher temperature.
SnSiO3 + CaO + C → Sn + CaSiO3 + CO
(iii) Electrolytic refining:
Cathode: Pure tin
Anode: Impure tin
Electrolyte: SnSO4(aq) with sulphuric acid and hydro fluorosilicic acid.

18.10 ExTRACTION OF COPPER


Both Cu and lead may be extracted by self-reduction method. Cu is mainly extracted from copper pyrites.
After the concentration of its ore by froth floatation process, the ore is roasted by current of air to
remove arsenic, Sb and much of sulphur. The ore is then mixed with a little of coke and sand and smelted
in a water jacketed blast furnace. The minor reactions that occurred during roasting continue here too.
Ferrous oxide combines with sand to form a slag. Cuprous oxide formed combines with ferrous sulphide
to give, ferrous oxide and cuprous sulphide. This is because iron has more affinity for oxygen than Cu.
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Chemistry at a Glance Final.pdf 213 4/1/2014 12:26:14 PM


18.208 Chemistry at a Glance

Molten mass collected from the bottom of furnace contain large cuprous sulphide and a little
ferrous sulphide. This molten mass is known as matte. The molten matte is finally transferred to
Bessemer converter. A blast of sand and air is blown in the converter through tuyeres which are situated
a little above the bottom and this causes removal of sulphur and arsenic oxides and ferrous oxide
as slag. At the same time, Cu2S is oxidised mostly into Cu2O and partly into CuO and CuSO4. All of
these react with Cu2S giving Cu. Finally, copper may be refined electrolytically, using an electrolyte
(copper sulphate).
At anode → Impure Cu
At Cathode → Pure Cu

18.11 ExTRACTION OF LEAD

Pb is mainly extracted from galena. After the concentration of the ore by the froth floatation process, the
ore is roasted in a reverberatory furnace.
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Hot conc. H2SO4 dissolves lead with evolution of SO2 but the reaction becomes lower due to
formation of insoluble PbSO4.
The obtained lead contains impurities such as Cu, Ag, Bi, Sb and Sn. Ag is removed by
Parke’s process, where molten Zn is added to molten impure lead. The former is immiscible with the later.
Ag is more soluble in molten Zn than in molten lead. Zn–Ag alloy solidifies earlier than molten lead and
thus can be separated. After this, crude lead is refined electrolytically.

Chemistry at a Glance Final.pdf 214 4/1/2014 12:26:14 PM


Metallurgical Extraction 18.209

Electrolyte → Lead silica fluoride (PbSiF6) and hydro fluoro silicic acid (H2SiF6) with a little gelatin
At anode → Crude lead At cathode → Pure lead

18.12 ExTRACTION OF MAGNESIUM


It is commonly obtained by the electrolysis of fused magnesium chloride containing a little
(25 per cent) NaCl and NaF at 700°C in an air-tight from pot which itself serves as the cathode.
The anode being a graphite rod which dips into the electrolyte. The anode is surrounded
by a perforated porcelain tube for the exit of chlorine. The electrolysis is carried in the
atmosphere of a cool gas so as to prevent the attack of atmospheric oxygen and nitrogen on
Mg. Molten Mg, being lighter than the electrolyte, floats over the fused electrolyte and is
withdrawn.
In Dow`s process, Mg is recovered from sea water as magnesium chloride which is then electrolyzed
using a cell as described hereunder:
(i) DOW’s sea-water process: Sea water contains about 0.13 per cent Mg2+ ions and the extraction
of Mg depends on the fact that Mg(OH)2 is very much less soluble than Ca(OH)2 [slaked lime].
Ca(OH)2 is added to sea water and calcium ions dissolve and Mg(OH)2 is precipitated. This is fil-
tered off, treated with HCl to produce MgCl2 and electrolyzed.

2\VWHU 'RUHWKLFNQHVV
0J&D 2+  &HOOV
&D0J 2+  GLO+&OSHUFHQW
0J&O+2
6SUD\
GU\LQJ

(OHFWURO\VLV ' 
0J SXUH 0J&O 0J&O +2
'U\+&O 

(ii) DOW’s natural brine process:


∆ Dil. HCl CO2
MgCO3 ⋅ CaCO3  → MgO ⋅ CaO → MgCl 2(aq) + CaCl 2(aq)  → CaCO3
(Dolomite) (Calcine dolomite)

(iii) Electrolysis: Anhydrous carnallite (KCl.MgCl2.6H2O) may also be employed as the starting
material of MgCl2. The cathode may be a layer of molten lead on the floor of the cell and
anode may be the graphite rod which are suspended above the molten lead. Mg liberated at
the cathode dissolves in the molten lead. The alloy of Pb–Mg is subjected to electrolysis to
obtain pure Mg.
Electrolyte used → Fused carnallite
Anode → Pb–Mg alloy
Cathode → Steel rods

18.13 ExTRACTION OF ALUMINIUM


Al is isolated from the electrolysis of bauxite (Al2O3.2H2O). Since it is difficult to purify Al, bauxite ore is
purified either by Baeyer’s process or Hall’s process or Serpeck’s process. Depending upon the impurity
present in the ore, if the bauxite contains iron oxide as the impurity one can use Baeyer’s or Hall’s process
as described hereunder:

Chemistry at a Glance Final.pdf 215 4/1/2014 12:26:14 PM


18.210 Chemistry at a Glance

Aluminium ore, Al 2O3 ⋅ 2H2O(bauxite)



Refining of bauxite
(a) Baeyer's process
(b) Hall's process
(c) Serpeck's process

$O2+2
Calcination
)H2 6L2
1500° C
Al(OH)3  → Al 2O3
Anhydrous alumina
5HG :KLWH

6HUSHFN¶V
Electrolytic reduction
& 1
Electrolyte Al 2O3 dissolved in Na 3 AlF6 and CaF2 %DH\HU¶V +DOO¶V
Cathode - carbon lining Anode-graphiterods $O16L&2
Electrolysis
1D2+ 1D&2 +2
Al 2O3 
→ 950° C
Al + O3
99.8 per cent pure

1D$,2 1$,2 $O 2+ 

+ 2
Electrolytic refining
$O 2+  $O 2+ 
(Hoope's process)
,JQLWLRQ

Pure Al (99.98 per cent pure) $O2 DOXPLQD

Electrolytic reduction of Al2O3: After obtaining pure Al2O3, it is dissolved in fused cryolite (Na3AlF6)
with a little fluorspar (CaF2) and is electrolyzed in an iron tank lined with blocks of carbon which serve
as the cathode. The anode consist of a number of graphite rods suspended vertically inside the tank.
Aluminium gets settled at the bottom of the tank and can be removed.

18.14 ExTRACTION OF SILVER AND GOLD


Silver and gold are extracted by the cyanide process (MacArthur forest process).

18.14.1 Mac Arthur Forest Process


After the preliminary crushing and concentration by froth floatation process the ore (crushed auriferous rocks
in the case of gold) is leached with dilute (0.4 – 7 per cent) solution of NaCN (made alkaline by adding lime and
kept agitated by a current of air). Ag (or Au) pass into the solution as argento-cyanide (or aurocyanide).
Air is blown into remove Na2S as Na2S2O3 and Na2SO4 causes the above reaction to proceed
to completion. The solution obtained is filtered and treated with scrap iron or zinc where Ag (or Au)
gets precipitated. The obtained Ag is purified electrolytically (electrolyte is silver nitrate solution
containing 1 per cent HNO3.
At anode: Impure Ag At cathode: Pure Ag

Chemistry at a Glance Final.pdf 216 4/1/2014 12:26:14 PM


Metallurgical Extraction 18.211

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6LOYHURUH DUJHQWLWH

&RQFHQWUDWLRQE\IURWKIORDWDWLRQSURFHVV
3RZGHUHGRUH:DWHU3LQHRLO$LU
)URWKFDUU\LQJVXOSKLGHSDUWLFOHV
)LOWDWLRQ

&\DQLGDWLRQ
1D62+21D>$J &1 @1D6
%ODFNSSW
)XVH
%ODFNSSWRI$J.12 &RPSDFWPDVV
VLOYHUPHWDO

(OHFWURO\WLFUHILQLQJ
$QRGH,PSXUHVLOYHU
&DWKRGH3XUHVLOYHUSODWH
(OHFWURO\WH$J12VROXWLRQ+12
3XUHVLOYHUGHSRVLWHGRQWKHFDWKRGH

Methods of extraction of metals: A brief review

Electrode Standard Main Main Method Equation for


process Electrode Occurrence of Extraction Extraction
Potential/V
Na, Na+ –2.7 Rock salt NaCl, Chile Electrolysis of fused
saltpeter, NaNO3 NaCl with CaCl2 ↑
added
Mg, Mg2+ –2.37 Carnallite, KCl . MgCl2 Electrolysis of fused Most of these involve
. 6H2O, MgCl2 with KCl electrolytic reduction
Magnesite, MgCO3 added Mn+ + ne– → M
Al, Al3+ –1.66 Bauxite, Al2O3.2H2O Electrolysis of Al2O3

Silicate rocks in molten Na3AlF6
Mn, Mn2+ –1.18 Pyrolusite MnO2 Reduction of oxide 3Mn3O4 + 8Al →
Hausmannite Mn3O4 with Al or C 9Mn + 4Al2O3
Zn, Zn2+ –0.76 Zinc blende ZnS, Reduction of ZnO ZnO + C → Zn +
Calamine ZnCO3 with C or electrolysis CO
of ZnSO4
Fe, Fe2+ –0.44 Magnetite, Fe3O4, Reduction of oxide Fe2O3 + 3CO → 2Fe
Haematite, Fe2O3 with CO + 3CO2
Sn, Sn2+ –0.14 Cassiterte, SnO2 Reduction of SnO3 SnO2 + 2C → Sn +
with C 2CO
Cu, Cu2+ –0.13 Galena PbS, C Reduction of PbO PbO + C → Pb + CO
with C
Continued

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18.212 Chemistry at a Glance

Electrode Standard Main Main Method Equation for


process Electrode Occurrence of Extraction Extraction
Potential/V
Cu, Cu2+ +0.34 Copperpyrite, CuFeS2 Partial oxidation of 2Cu2O + Cu2S →
Cuprite, Cu2O sulphide ore 6Cu + So2
Ag, Ag2+ +0.80 Argentite, Ag2S, occurs Special method Ag2S + 4NaCN →
as metal involving use of 2NAaAg(CN)2 +
sodium cyanide Na2S
2NaAg(CN)2
+ Zn → 2Ag +
Na2Zn(CN)4
Hg, Hg2+ +0.85 Cinnabar, HgS Directional reduction HgS + O2 → Hg +
of HgS by heat alone So2
Au, Au3+ +1.50 Occurs as metal Special methods Similar to that for
involving use of silver
sodium cyanide 2NaAu(CN)2
+ Zn → 2Au +
Na2Zn(CN)4

Metals found in traces in living organisms


From Living Organisms Metals Obtained From Living Organisms Metals Obtained
(i) Haemoglobin Iron (v) Eyes of cats and cows Zn
(ii) Blood Sodium (vi) Prawns Cr
(iii) Chlorophyll Magnesium (vii) Bones Ca
(iv) Chloroplast Mn, Fe and Cu (viii) Cucumbers Vanadium

Chemistry at a Glance Final.pdf 218 4/1/2014 12:26:14 PM


Coordination
Chapter 19
Compounds

19.1 Coordination Compounds

19.1.1 Addition Compound


Addition compounds are formed when stoichiometric amount of two or more stable compounds join
together.

Examples:

1. KCl + MgCl 2 + 6H2O 


→ KCl ⋅ MgCl 2 ⋅ 6H2O
(Carnallite)

2. K 2SO4 + Al 2 (SO4 )3 + 24H2O 


→ K 2SO4 ⋅ Al 2 (SO4 )3 ⋅ 24H2O
(Potassium alum)

3. CuSO4 + 4NH3 + H2O 


→ CuSO4 ⋅ 4NH3H2O
(Tetraammine copper (II) sulphate monohydrate)

4. Fe(CN)2 + 4KCN 
→ Fe(CN)2 ⋅ 4KCN
(Potassium ferrocyanide)

19.1.2 Classification of Addition Compounds


(a) Addition compounds are of two types as listed hereunder:
(i) Double salts: Double salts are those which lose their identity in solution, e.g., carnallite, potash
alum, etc., when crystals of carnallite are dissolved in water, the solution shows the properties of K+,
Mg2+ and Cl– ions.
(ii) Complexes or coordination compound: Complexes are compounds which retain their identity
in solutions.
E.g., [Cu(NH3)4 (H2O)2]SO4, K4[Fe(CN)6], etc. When these two are dissolved in water they do
not form simple ions Cu2+, Fe2+, CN–, etc. but instead their complex ions remain intact. Thus the
cupraammonium ion [Cu(H2O)2(NH3)4]2+ and the ferrocyanide ion [Fe(CN)6]4– exist as distinct
entities both in the solid and in the solution.
A complex or coordination compound is a compound consisting either of complex ions with other
ions of opposite charge.

Chemistry at a Glance Final.pdf 219 4/1/2014 12:26:14 PM


19.214 Chemistry at a Glance

Examples:
1. → 4k + + [Fe(CN)6 ]4−
K 4[Fe(CN)6 ] 
(other ion) (complex anion)

2. → 4Cl − + [Pt(en)3 ]4+


[Pt(en)3 ]Cl 4 
(other ion) (complex cation)

3. [Pt(en)2Cl2] → no ionization (neutral complex)

19.2 Werner’s Coordination theory

In 1823, Werner put forward his famous theory of coordination to explain the formation and structures of
complex compounds.
The important postulates of Werner’s coordination theory are as follows:
1. In coordination compounds, the metal atoms exhibit two types of valency, viz., the primary
valency and the secondary valency. The primary valency is ionizable and is non-directional
whereas the secondary valency is non-ionizable and is directional. In modern terminology, the
primary valency corresponds to oxidation state and the secondary valency corresponds to the
coordination number.
2. Every metal atom has a fixed number of secondary valencies, i.e., it has a fixed coordination number.
3. The metal atom tends to satisfy both its primary as well as secondary valencies. Primary valencies
are satisfied by negative ions, whereas secondary valencies are satisfied either by negative ions or by
neutral molecules.
4. The secondary valencies are always directed towards fixed positions in space and this leads to
definite geometry of the coordination compound. For example, if a metal ion has six secondary
valencies these are arranged octahedrally around the central metal ion. If the metal ions has
four secondary valencies, these are arranged in either tetrahedral or square planar arrangement
around the central metal ion. The secondary valencies, thus, determine the stereochemistry of
the complex. The secondary valencies are represented by thick lines and the primary valencies
by dotted lines.
Structure of CoCl3.6NH3 Complex

1+ &O
+ 1
1+

&O &R

+ 1 1+
1+ &O
1XPEHURI&O±LRQVSUHFLSLWDWHG 
7RWDOQXPEHU 

19.2.1 Ligands
A ligand is a species that is capable of donating an electron pair to a central ion. It is a Lewis base.
In accepting electron pairs, the central ion acts as a lewis acid.

Chemistry at a Glance Final.pdf 220 4/1/2014 12:26:14 PM


Coordination Compounds 19.215

19.2.1.1 Classification of ligands

(i) Neutral molecules such as H2O, NH3, etc.


(ii) Anions such as CN–, C2O42–, Cl–, etc. The name organic ligand ends with –0.
(iii) Cations (but in rare cases since an electron pair of an cation is held firmly by the positive charges
and would not be involved in coordinate bonding) such as NO+, etc. The name of cationic ligand
ends with–ium.
On the basis of denticity, ligands can be classified into two types as listed hereunder.
(a) Unidentate ligands: A ligand is said to be unidentate if it has only one pair of electrons that it can
donate.
Some common unidentate ligands are listed hereunder

Name of Ligand Formula Donor Name of Ligand Formula Donor


(aqua) H2O O Hydroxido OH –
O
ammine NH3 N Cyano CN –
C
Pyridine C5H5N N Nitro NO2 N
Carbonyl CO O Nitrito ONO –
O
Nitrosyl NO N Oxo O–
O
Triphenyl phosphine (C6H5) 3P P Thiocyanato CSN –
S or N
Halido X– X isothiocynato NCS– S or N

(b) Multidentate ligands: If a ligand is capable of donating more than one electron pairs, then it is
called multidentate ligand.
Some common multidentate ligands

Name of Ligand Structure/Formula Donor Atom Abbreviation


&+1+
Ethylene diamine N en
&+1+

&22±
Oxalato O Ox
&22±

1+
Glycinato + & N and O gly
&22±

&+±& 12±
Dimethyl glyoximato N and O DMG
&+±& 12+

2, 2-Dipyridyl N dipy.
1 1

Chemistry at a Glance Final.pdf 221 4/1/2014 12:26:14 PM


19.216 Chemistry at a Glance

Tridentate ligands

&+²1+²&+
Diethylene triamine
&+ &+ N dien
1+ 1+

Hexadentate ligands

±
22&&+ &+&22±
Ethylene diamine tetraacetato 1±&+±&+±1 N and O EDTA
±
22&&+ &+&22±

Ambidentate ligands: Some ligands can be coordinated to the metal through either of the sides.
They are called ‘ambident’ ligands. E.g., CN– and NC–NO2 and ONO, etc.
Chelates: Some ligands are capable of donating more than a single electron pair, from
different atoms in the ligands and to different sites in the geometrical structure of a complex.
These are called multidentate ligands. When the bonding of a multidentate ligand to a metal
ion produces a ring (usually five or six-membered), we refer to the complex as a chelate.
The multidentate ligand is called a chelating agent and the process of chelate formation is
called chelation.

2 + 2

&+±& 1 1 &±&+
1L
&+±& 1 1 &±&+

2 + 2

Nickel (II) dimethyl glyoximate (chelate) [bis–(dimethyl glyoximato nickel (II) ]

19.3 Coordination number of metal ions

The coordination number of a metal atom in a complex is the total number of bonds the metal atom forms
with ligands.

Metal ion Coordination number Metal ion Coordination number


Ag +
2 Co 3+
6
Cu +
2, 4 Ni 2+
4, 6
Cu 2+
4, 6 Zn 2+
4
Fe , Fe
2+ 3+
6 Cr 3+
6
Co2+ 4, 6 Pt2+/ Pt4+ 4

Chemistry at a Glance Final.pdf 222 4/1/2014 12:26:14 PM


Coordination Compounds 19.217

19.3.1 Complexes of various coordination number

Complex Coordination Number Complex Coordination Number


[Ag(NH3)2]+ 2 [CO(NH3)6]3+, [W(CO)6 6
[PtCl4] , [Ni(CO)4]
2–
4 Fe(CO)5, [Co(CN)5] 3–
5

19.4 isomerism in Coordination Compounds

The compounds having same molecular formula but different physical and chemical properties on account
of different structure are called isomers and the phenomenon in known as isomerism. Isomerism in coor-
dination compounds may be divided into two main types:
1. Structural isomerism
2. Stereo isomerism

19.4.1 Structural Isomerism


It is displayed by compounds that have different ligands within their coordination spheres. The different
types of structural isomerism shown by coordination compounds are discussed hereunder.
(i) Ionization isomerism: This type of isomerism arises when the coordination compounds give
different ions in solution. For example, there are two isomers of formula [Co(NH3)5Br]SO4.
[Co(NH3)5 Br]SO4 ⇌ [Co(NH3)5Br]2+ + SO42–
This isomer gives a white precipitate of BaSO4 with BaCl2 solution.
[Co(NH3)5SO4]Br ⇌ [Co(NH3)5SO4]+ + Br–
The above isomer a gives light yellow precipitate with AgNO3 solution.
(ii) Hydrate isomerism: This type of isomerism arises when different number of water molecules are
present inside and outside the coordination sphere. This isomerism is best illustrated by the three
isomers that have the formula CrCl3.6H2O.
(a) [Cr(H2O)6]Cl3: Violet. All the six water molecules are coordinated to Cr. It has three
ionizable chloride ions.
(b) [Cr(H2O)5Cl]Cl2.H2O: Green. Five water molecules are coordinated to Cr. It has two
ionizable Cl– ions.
(iii) Coordination isomerism: This type of isomerism is observed in the coordination compound
having both cationic and anionic complex ions. The ligands are interchanged in both the cationic
and anionic ions to form isomers. Here, complete exhange of liquid is done, e.g., [Pt(NH3)4] [CuCl4]
and [Cu(NH3)4] [PtCl4]
(iv) Linkage isomerism: This type of isomerism occurs in complex compounds which contain
ambidentate ligands like NO2− ,SCN − ,CN − ,S2O23− and NCO–. These ligands have two donor atoms
but at a time only one atom is directly linked to the central metal atom of the complex. These
types of isomerism are distinguished by infra-red (IR) spectroscopy. E.g., [Co(NH3)5 NO2]Cl2 and
[Co(NH3)5ONO]Cl2.
(vi) Coordination position isomerism: This type of isomerism is exhibited by polynuclear
complexes by changing the position of ligands with respect to different metal atoms present in
the complex.

Chemistry at a Glance Final.pdf 223 4/1/2014 12:26:15 PM


19.218 Chemistry at a Glance

For example:
 
1+ 1+
1+ &R &R 1+ &O DQG 1+ &O&R &R 1+ &O
2 2

19.5 stereo isomerism


Compounds are stereo isomers when they contain the same ligands in their coordination spheres but dif-
fer in the way that these ligands are arranged in space. Stereoisomerism is of two types, viz,. geometrical
isomerism and optical isomerism.

19.5.1 Geometrical Isomerism


This isomerism is due to ligands occupying different positions around the central metal atom or ion. The
ligands occupy positions either adjacent or opposite to one another. This type of isomerism is also known
as cis- and trans isomerism. Geometrical isomerism is very much commmon in coordination number 4
and 6 complexes.
Square planar complexes (coordination number four) exhibit geometrical isomerism
D E E D E D D E E D E D

0 0 0 0

D D D D D D D D
D E D E
&LV 7UDQV &LV 7UDQV
>0DE@ >0DE@

(i) Complexes with general formula Ma2b2 (where both a and b are monodentate) can have cis and
trans-isomers.
(ii) Complexes with general formula, Ma2 bc can have cis and trans-isomers.
D E D F + 1 &O +1 12

0 0 3W 0

E F E D &O 1+ &O


&LV 7UDQV &LV 7UDQV 12
>0DEF@ >3W 1+ &O@

(iii) Complexes with general formula, Mabcd can have three isomers.
D E D G D E

0 0 0

G F F E F G
L LL LLL

Chemistry at a Glance Final.pdf 224 4/1/2014 12:26:15 PM


Coordination Compounds 19.219

(iv) Square planar complexes having unsymmetrical bidentate ligands can also show geometrical isom-
erism. For example, platinum glycinato complex, [Pt(Gly)2], exhibits geometrical isomerism.
&+±1+ +1±&+ &2±2 +1±&+
3W 3W
&2±2 2±&2 &+±1+ 2±&2
&LVLVRPHU 7UDQVLVRPHU

[Ma4]n± and [Ma3b]n± type square planar complexes do not show geometrical isomerism.
Tetrahedral and linear complexes: do not show geometrical isomerism.
Octahedral complexes: of the type Ma4b2 and Ma3b3 exhibit geometrical isomerism

D E D E D E D E
E D E E

0 0 0 0

D D D D D D D D
D E D E
&LV 7UDQV &LV 7UDQV

>0DE@ >0DE@

Facial and meridional isomers: A set of three ligands (similar) may be arranged on an octahedron
in all cis-fashion, giving facial or ‘fac’ isomer. In other words, three similar ligands on the same face
of an octahedron give rise to a facial isomer.
1+ D

1+ &O± D E

&2 0

D E
1+ &O±

E
&O±

A set of three similar ligands may be arranged on an octahedron with one pair trans (meridian of
octahedron), giving rise to meridional or ‘mer’ isomer.
1+ D
&O± &O±
D E

&R 0
D E

1+ &O ±

1+ E

Chemistry at a Glance Final.pdf 225 4/1/2014 12:26:15 PM


19.220 Chemistry at a Glance

19.5.2 Optical Isomerism


A coordination compound which can rotate the plane of polarized light is said to be optically active. The
essential requirement for a substance to be optically active is that the substance should not have a plane of
symmetry in its structure. The isomer which rotates the plane of polarized light to right direction is termed
dextro (D-form) while the isomer which rotates the plane of polarized light to left direction is termed
leavo (L-form).
Optical isomerism is expected in tetrahedral complexes of the type Mabcd but no optical isomer has
been isolated untill now.
However, compounds containing two unsymmetrical bidentate ligands have been resolved into
optical isomers.
Optical isomerism rarely occur in square planar complexes on account of the presence of axis of
symmetry. Optical isomerism is very common in octahedral complexes. Octahedral complexes of general
formulae
[Ma2b2c2]n±, [Mabcdef]n±, [M(AA)3]n± and [M(AA)2a2]n± (where AA = symmetrical bidentate ligands)
[M(AA)2 ab]n± and [M(AB)3]n± (where A and B are unsymmetrical ligands), show optical isomerism.
Examples:
 
S\ S\
&O S\ S\ &O

3W 3W

&O +1 &O


1+
1+ 1+
&LV'LVRPHU 0LUURU &LV,LVRPHU

(b) [Mabcdef]; [Pt(py)NH3NO2ClBrI]


%U %U
S\ 12 21 S\

3W 3W

&O 1+ &O


+1
O O
'LVRPHU 0LUURU ,LVRPHU

(c) [MAA)3]; [Co(en)3]3+


 
HQ HQ

HQ
&R &R

HQ
HQ HQ
'IRUP 0LUURU ,IRUP

Chemistry at a Glance Final.pdf 226 4/1/2014 12:26:15 PM


Coordination Compounds 19.221

19.6 nomenClature of Coordination Compounds

1. While writing the IUPAC name of a complex, the name of cation is written first followed by the
name of anion.
2. While writting the IUPAC name of the complex, the ligands are written in alphabetical order, regard-
less of their charge followed by the name of metal.
3. When there are several ligands of the same kind we normally use the prefixes di, tri, tetra, penta and
hexa to show the number of ligands of that type.
Exception occurs when the name of ligand includes a number, e.g., dipyridyl or ethylenediamine. To
avoid confusion in such cases bis, tris and tetrakis are used instead of di, tri, tetra and the name of
the ligand is placed in brackets.
4. The oxidation state of central metal is shown by a roman numeral in brackets immediately following
its name, e.g., titanium (III).
5. Complex positive ions and neutral molecules have no special ending but complex negative ions ends
with -ate.
e.g., [Pt(py)4] [Pt Cl4] can be named as Tetra pyridine platinum (II) tetra chloro
platinate (II).
6. If the complex contains two or more metal atoms, it is termed as polynuclear. The bridging ligands
which link the two metal atoms together are indicated by the prefix m-. If there are two or more
bridging groups of the same kind, this is indicated by di–m–, tri–m–, etc. Bridging groups are listed
alphabetically with the other groups unless the symmetry of the molecules allows a simpler name.
If a bridging group bridges more than two metal atoms it is shown as m3, m4, m5 or m6 to indicate how
many atoms it is bonded to.
e.g., [(NH3) 5Co.NH2Co(NH3)5] (NO3)5.
m–amido bis [pentaammine cobalt (III)] nitrate [(CO)3 Fe(CO)3 Fe(CO)3]
Tri - m - carbonyl - bis [tricarbonyl iron (O)]

[Co(NH3)6]Cl3 Hexa ammine cobalt (III) chloride


[CoCl(NH3)5] 2+
Penta ammine chloro cobalt (III) ion
[CoCl. CN. NO2. (NH3)3] Tri ammine chloro cyano nitro cobalt (III).
Li[Al H4] Lithium tetrahydrido aluminate (III)
K4[Fe(CN)6] Potassium hexa cyano ferrate (II)
K2[Os Cl5N] Potassium penta chloro nitrido osmate (VI)
[Cr(PPH3) (CO)5] Penta carbonyl triphenyl phosphine chromium (O)
[Co(en)2F2]ClO4 Bis (ethylenediamine) difluoro cobalt (III) perchlorate
[Ni(dmg)2] Bis (dimethylglyoximato) nickel (II)
Co(NH3)4Cl2]3 [Cr(CN)6] Tetra ammine dichloro cobalt(III)hexa cyano chromate (III)

19.6.1 Effective Atomic Number


Effective atomic number (EAN) of the metal in a complex is given by
EAN = z – (ON) + 2(CN) where ON is oxidation number, CN is coordination number and z is the
atomic number.

Chemistry at a Glance Final.pdf 227 4/1/2014 12:26:15 PM


19.222 Chemistry at a Glance

Complex Ion Central Atomic Oxidation Number of EAN


Metal No. State of Metal Electron Donated
Atom in Emplexion by Ligands
[Fe(CN)6]–4 Fe 26 +2 6 × 2 = 12 26 – 2 + 12 = 36
[Cu(CN)4]–3 Cu 29 +1 4×2=8 29 – 1 + 8 = 36
[Pt(NH3)6] –4
Pt 78 +4 6 × 2 = 12 78 – 4 + 12 = 86
[Co(en)3]3+ Co 27 +3 3 × 4 = 12 27 – 3 + 12 = 36

19.7 bonding in Complexes

There are three theories of metal to ligand bonding in complexes.

19.7.1 Valence Bond Theory


This theory was proposed by Pauling. The main points of this theory are given as follows:
1. The central metal ion in the complex makes available an adequate number of empty orbitals for the
formation of coordinate bonds with suitable ligands. The number of empty orbitals made available
for the purpose is equal to the coordination number of the central metal ion.
G V S
D 1L ,, LRQ
ҡ
ҡ
ҡ
ҕ
ҕ

E >1L &O @±LRQ


ҡ
ҡ
ҡ
ҕ
ҕ

ҡ
ҡ
ҡ

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2. The appropriate atomic orbitals of the metal hybridize to give an equal number of new orbitals
of equivalent energy called hybrid orbitals. The hybrid orbitals are directed towards the ligand
positions according to the geometry of the complex.
3. The d-orbitals involved in the hybridization may be inner, viz., (n – 1)d orbitals or the outer, viz., nd
orbitals. The complexes thus formed are referred to as low spin and high spin complexes, respectively.
4. Each ligand has at least one orbital containing a lone pair of electrons.
5. The empty hybrid orbitals of metal ion overlap with the fully filled orbitals of the ligand, forming the
ligand–metal coordinate bond. The number of such bonds varies with the number of empty orbitals
made available by the central metal ion.

19.7.2 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.
(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 arranged against the Hund’s
rule while at other times the electronic configuration is not disturbed.

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Coordination Compounds 19.223

(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 other are inert.

19.7.3 Crystal Field Theory


Crystal field theory was proposed by H. Bethe and Van Vleck and was originally applied to ionic crys-
tals to explain their optical properties and is, therefore, called crystal field theory. The main points
of the theory are:
(a) According to crystal field theory, the bonding in complex ions is purely electrostatic. This theory
regards the ligand atoms of ionic ligands such as F–, Cl– or CN– as negative point charges and if the
ligand molecules are neutral, these are regarded as point dipoles or simply dipoles, the negative end
pointing towards central metal ion.
(b) The complex is regarded as a combination of a central metal ion surrounded by ligands which act as
point charges or point dipoles. The arrangement of ligands around the central metal ion or atom is
such that the repulsion between these negative points or dipoles is minimum.
(c) Interactions between positively charged nucleus of the central metal ion or atom and the negatively
charged ligands are of two types:
(i) The attractive forces arise due to the positive metal ion and the negatively charged ligands or the
negative end of polar neutral molecules.
(ii) The repulsive forces arise between the lone pairs on the ligands and electrons in the d-orbitals
of the metal.
(d) In a free transition metal or ion, there are five d-orbitals which are designated as dxy, dyz, d