33 Years NEET Chapterwise & Topicwise Solved Papers CHEMISTRY 2020 PDF

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CONTENTS
1. Some Basic Concepts of Chemistry 1-10 7. Equilibrium 70-89
Topic 1 : Significant Figures, Laws of Chemical Topic 1: Law of Mass Action, Equilibrium
Combinations and Mole Concept Constant (Kc and Kp) and its Application
Topic 2: Percent Composition and Empirical Topic 2: Relation between K, Q and G and
Formula Factors Effecting Equilibrium
Topic 3: Stoichiometric Calculations Topic 3: Theories of Acids and Bases, Ionic
2. Structure of Atom 11-20 Product of Water and pH Scale
Topic 4: Ionisation of Weak Acids and Bases
Topic 1 : Atomic Models and Dual Nature of
and Relation between Ka and Kb
Electromagnetic Radiation
Topic 5: Common Ion Effect, Salt Hydrolysis,
Topic 2 : Bohr's model for Hydrogen Atom
Buffer Solutions and Solubility Product
(Emission and Absorption Spectra)
Topic 3: Dual Behaviour of Matter and 8. Redox Reactions 90-93
Heisenberg Uncertainty Principle Topic 1: Oxidation and Reduction Reactions
Topic 4 : Quantum Mechanical Model of Atom Topic 2: Oxidation Number
Topic 3: Disproportionation and Balancing of
3. Classification of Elements and Redox Reactions
Periodicity in Properties 21-27 Topic 4: Electrode Potential and Oxidising,
Topic 1: Modern Periodic Table Reducing Agents
Topic 2: Periodic Trends in Properties of
9. Hydrogen 94-97
Elements
Topic 1: Preparation and Properties of
4. Chemical Bonding and Molecular Hydrogen
Structure28-48 Topic 2: Preparation and Properties of Water
Topic 1: Electrovalent, Covalent and Topic 3: Preparation and Properties of
Co‑ordinate Bonding Hydrogen Peroxide
Topic 2: Octet rule, Resonance and Hydrogen
10. The s-Block Elements 98-104
Bonding Topic 1: Preparation and Properties of Alkali
Topic 3: Dipole Moment and Bond Polarity Metals and their Compounds
Topic 4: VSEPR Theory and Hybridisation Topic 2: Some Important Compounds of
Topic 5: Valence Bond and Molecular Orbital Sodium
Theory Topic 3: Preparation and Properties of Alkaline
5. States of Matter 49-57 Earth Metals and their Compounds
Topic 1: Gas laws and Ideal gas Equation Topic 4: Some Important Compounds of
Topic 2: Kinetic Theory of Gases and Molecular Calcium
Speeds 11. The p-Block Elements
Topic 3 : van der Waal's Equation and (Group 13 & 14) 105-109
liquefaction of Gases Topic 1: Boron Family
Topic 4: Liquid State Topic 2: Carbon Family
6. Thermodynamics 58-69 12. Organic Chemistry - Some Basic
Topic 1: First Law and Basic Fundamentals of Principles and Techniques 110-122
Thermodynamics Topic 1: Classification and Nomenclature of
Topic 2: Laws of Thermochemistry Organic Compounds
Topic 3: Entropy and Second Law of Topic 2: Isomerism in Organic Compounds
Thermodynamics Topic 3: Concept of Reaction Mechanism in
Topic 4: Spontaneity and Gibb's Free Energy Organic Compounds
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13. Hydrocarbons 123-141 22. The d-and f-Block Elements 210-222
Topic 1: Alkanes Topic 1: Characteristics of d-Block Elements
Topic 2: Alkenes Topic 2: Compounds of Transition Metals
Topic 3: Alkynes Topic 3: Lanthanoids and Actinoids
Topic 4: Aromatic Hydrocarbons 23. Coordination Compounds 223-240
14. Environmental Chemistry 142-144 Topic 1: Coordination Number, Nomenclature
Topic 1: Air Pollution and Isomerism of Coordination Compounds
Topic 2: Water and Soil Pollution Topic 2: Magnetic Moment, Valence Bond
Theory and Crystal Field Theory
15. The Solid State 145-151
Topic 3: Organometallic Compounds
Topic 1: Properties and Types of Solids
Topic 2: Crystal Structure of Solids 24. Haloalkanes and Haloarenes 241-254
Topic 3: Cubic System and Bragg's Equation Topic 1: Preparation and Properties of
Topic 4: Imperfection in Solids Haloalkanes
16. Solutions 152-162
Haloarenes
Topic 1: Solubility and Concentration of
Topic 3: Some Important Polyhalogen
Solutions
Compounds
Topic 2: Vapour Pressure, Laws of Solutions
and Ideal, Non-ideal Solutions 25. Alcohols, Phenols and Ethers 255-268
Topic 3: Colligative Properties and Abnormal Topic 1: Preparation and Properties of Alcohols
Molecular Masses Topic 2: Preparation and Properties of Phenols
Topic 3: Preparation and Properties of Ethers
17. Electrochemistry 163-174
26. Aldehydes, Ketones and
Topic 1: Conductance and Conductivity
Carboxylic Acids 269-290
Topic 2: Electrolysis and Types of Electrolysis
Topic 1: Methods of Preparation of Carbonyl
Topic 3: Cells and Electrode Potential, Nernst
Compounds
Equation
Topic 2: Properties of Carbonyl Compounds
Topic 4: Commercial Cells and Corrosion
18. Chemical Kinetics 175-187 Carboxylic Acids
Topic 1: Rate of Reaction, Rate Laws and Rate
27. Amines 291-304
Constant
Topic 1: Aliphatic and Aromatic+ Amines
Topic 2: Order of Reaction and Half Life Period
Topic 2: Amides, Cyanides and Isocyanides
Topic 3: Theories of Rate of Reaction Topic 3: Nitrocompounds, Alkyl Nitrites and
19. Surface Chemistry 188-192 Diazonium Salts
Topic 1: Adsorption 28. Biomolecules 305-315
Topic 2: Catalysis and Theories of Catalysis Topic 1: Carbohydrates and Lipids
Topic 3: Colloids and Emulsions Topic 2: Amino Acids and Proteins
20. General Principles and Processes Topic 3: Nucleic Acid and Enzymes
of Isolation of Elements 193-195 Topic 4: Vitamins and Hormones
Topic 1: Occurrence of Metals 29. Polymers 316-322
Topic 2: Metallurgical Processes Topic 1: Classification of Polymers
Topic 3: Purification and Uses of Metals
21. The p-Block Elements Polymers
(Group 15, 16, 17 and 18) 196-209 Topic 3: Uses of Polymers
Topic 1: Nitrogen Family
30. Chemistry in Everyday Life 323-324
Topic 2: Oxygen Family
Topic 3: Halogen Family 31. Nuclear Chemistry 325-328
Topic 4: Noble Gases
NEET
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(iv)
Some Basic Concepts of Chemistry 1
1 Some Basic Concepts

of Chemistry
Trend Analysis with Important Topics & Sub-Topics
2020 2019 2018 2017 2016

Topic Name Sub-Topic QNS. LOD QNS. LOD QNS. LOD QNS. LOD QNS. LOD
Significant figures,law mole concept 1 E 1 E 1 E
of chemical
combinations and
mole concept
stoichiometric
Stoichiometric 1 A
calculations
calculations
LOD - Level of Difficulty E - Easy A - Average D - Difficult Qns - No. of Questions
Topic 1 : Significant Figures, Laws of Chemical (a) 4 : 1 (b) 16 : 1

Combinations and Mole Concept (c) 2 : 1 (d) 1 : 4
5. The number of water molecules is maximum in :
1. Which one of the followings has maximum [2015 RS]
number of atoms ? [2020] (a) 18 molecules of water
(a) 1 g of Mg(s) [Atomic mass of Mg = 24] (b) 1.8 gram of water
(b) 1 g of O2(g) [Atomic mass of O = 16] (c) 18 gram of water
(c) 1 g of Li(s) [Atomic mass of Li = 7] (d) 18 moles of water
(d) 1 g of Ag(s) [Atomic mass of Ag = 108] 6. If Avogadro number NA, is changed from
2. The number of moles of hydrogen molecule 6.022 × 1023 mol–1 to 6.022 × 1020 mol–1 this
required to produce 20 moles of ammonia would change : [2015 RS]
through Haber’ s process is: [2019] (a) the definition of mass in units of grams
(a) 10 (b) 20 (b) the mass of one mole of carbon
(c) 30 (d) 40 (c) the ratio of chemical species to each other
3. In which case is number of molecules of water in a balanced equation.
maximum? [2018] (d) the ratio of elements to each other in a
(a) 18 mL of water compound
(b) 0.18 g of water 7. When 22.4 litres of H2(g) is mixed with 11.2 litres
(c) 10–3 mol of water of Cl2(g), each at S.T.P., the moles of HCl(g)
(d) 0.00224 L of water vapours at 1 atm and formed is equal to : [2014]
273 K (a) 1 mole of HCl (g)
4. A mixture of gases contains H2 and O2 gases in (b) 2 moles of HCl (g)
the ratio of 1 : 4 (w/w). What is the molar ratio of (c) 0.5 moles of HCl (g)
the two gases in the mixture ? [2015] (d) 1.5 moles of HCl (g)
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2 CHEMISTRY
8. 1.0 g of magnesium is burnt with 0.56 g O2 in a (c) 0.5 g of H2 gas

closed vessel. Which reactant is left in excess (d) 10 g of O2 gas
and how much ? [2014] 18. Which has maximum number of molecules?
(At. wt. Mg = 24 ; O = 16) (a) 7 g N2 (b) 2 g H2 [2002]
(a) Mg, 0.16 g (b) O2, 0.16 g (c) 16 g NO2 (d) 16 g O2
(c) Mg, 0.44 g (d) O2, 0.28 g 19. Specific volume of cylindrical virus particle is
9. Which has the maximum number of molecules 6.02 × 10–2 cc/g whose radius and length are 7 Å
among the following ? [2011 M] & 10 Å respectively. If NA = 6.02 × 1023, find
(a) 44 g CO2 (b) 48 g O3 molecular weight of virus [2001]
(c) 8 g H2 (d) 64 g SO2 (a) 3.08 × 103 kg/mol (b) 3.08 × 104 kg/mol
10. The number of atoms in 0.1 mol of a triatomic (c) 1.54 × 104 kg/mol (d) 15.4 kg/mol
gas is : [2010] 20. Assuming fully decomposed, the volume of CO2
(NA = 6.02 ×1023 mol–1) released at STP on heating 9.85 g of BaCO3
(a) 6.026 × 1022 (b) 1.806 × 1023 (Atomic mass, Ba = 137) will be [2000]
(c) 3.600 × 1023 (d) 1.800 × 1022 (a) 2.24 L (b) 4.96 L
11. What volume of oxygen gas (O2) measured at (c) 1.12 L (d) 0.84 L
0°C and 1 atm, is needed to burn completely 1L 21. Haemoglobin contains 0.334% of iron by weight.
of propane gas (C3H8) measured under the same The molecular weight of haemoglobin is
conditions ? [2008] approximately 67200. The number of iron atoms
(a) 7 L (b) 6 L (at. wt. of Fe is 56) present in one molecule of
(c) 5 L (d) 10 L haemoglobin are [1998]
12. Number of moles of MnO-4 required to oxidize (a) 1 (b) 6
one mole of ferrous oxalate completely in acidic (c) 4 (d) 2
medium will be : [2008] 22. The number of significant figures for the three
(a) 0.6 moles (b) 0.4 moles numbers 161 cm, 0.161 cm, 0.0161 cm are
(c) 7.5 moles (d) 0.2 moles (a) 3, 4 and 5 respectively [1998]
13. Volume occupied by one molecule of water (b) 3, 4 and 4 respectively
(density = 1 g cm–3) is : [2008] (c) 3, 3 and 4 respectively
–23 3 (d) 3, 3 and 3 respectively
(a) 9.0 × 10 cm (b) 6.023 × 10 23 cm3
–
23. The weight of one molecule of a compound
(c) 3.0 × 10–23 cm3 (d) 5.5 × 10– 23 cm3 C60H122 is [1995]
14. The number of moles of KMnO4 that will be
needed to react with one mole of sulphite ion in (a) 1.2 × 10–20 gram (b) 1.4 × 10–21 gram
acidic solution is [2007] (c) 5.025 × 1023 gram (d) 6.023 × 1023 gram
(a) 4/5 (b) 2/5 24. In the final answer of the expression
(c) 1 (d) 3/5 ( 29.2 - 20.2) (1.79 ´ 10 5 )
15. An element, X has the following isotopic 1.37
composition : [2007] the number of significant figures is : [1994]
200X : 90% 199X : 8.0 % 202X : 2.0%
(a) 1 (b) 2
The weighted average atomic mass of the (c) 3 (d) 4
naturally occuring element X is closest to 25. If NA is Avogadro’s number then number of
(a) 201 amu (b) 202 amu valence electrons in 4.2g of nitride ions (N3–) is
(c) 199 amu (d) 200 amu (a) 2.4 NA (b) 4.2 NA [1994]
16. The number of moles of KMnO4 reduced by one (c) 1.6 NA (d) 3.2 NA
mole of KI in alkaline medium is: [2005] 26. The molecular weight of O2 and SO2 are 32 and
(a) one (b) two 64 respectively. At 15°C and 150 mm Hg pressure,
(c) five (d) one fifth one litre of O2 contains ‘N’ molecules. The
17. The maximum number of molecules is present in number of molecules in two litres of SO2 under
(a) 15 L of H2 gas at STP [2004] the same conditions of temperature and pressure
(b) 5 L of N2 gas at STP will be : [1990]
(a) N/2 (b) N 35. Percentage of Se in peroxidase anhydrase

(c) 2N (d) 4N enzyme is 0.5% by weight (at. wt. = 78.4) then
27. Boron has two stable isotopes, 10B (19%) and minimum molecular weight of peroxidase
11B (81%). Average atomic weight for boron in anhydrase enzyme is [2001]
(a) 1.568 × 103 (b) 15.68
the periodic table is [1990] (c) 2.136 × 104 (d) 1.568 × 104
(a) 10.8 (b) 10.2 36. An organic compound containing C, H and O
(c) 11.2 (d) 10.0 gave on analysis C – 40% and H – 6.66%. Its
28. The number of oxygen atoms in 4.4 g of CO2 is empirical formula would be [1999, 94]
[1990] (a) C3H6O (b) CHO
(a) 1.2 × 1023 (b) 6 × 1022 (c) CH2O (d) CH4O
(c) 6 × 1023 (d) 12 × 1023 37. An organic compound containing C, H and N
gave the following analysis :
29. The number of gram molecules of oxygen in
C = 40% ; H = 13.33% ; N = 46.67%
6.02 × 1024 CO molecules is [1990] Its empirical formula would be [1998]
(a) 10 g molecules (b) 5 g molecules (a) C2H7N2 (b) CH5N
(c) 1 g molecules (d) 0.5 g molecules (c) CH4N (d) C2H7N
30. What is the weight of oxygen required for the 38. The percentage weight of Zn in white vitriol
complete combustion of 2.8 kg of ethylene ? [ZnSO 4.7H2O] is approximately equal to
(a) 2.8 kg (b) 6.4 kg [1989] ( Zn = 65, S = 32, O = 16 and H = 1) [1995]
(c) 9.6 kg (d) 96 kg (a) 33.65 % (b) 32.56 %
31. Ratio of Cp and Cv of a gas ‘X’ is 1.4. The number (c) 23.65 % (d) 22.65 %
of atoms of the gas ‘X’ present in 11.2 litres of it 39. A metal oxide has the formula Z2O3. It can be
at NTP will be [1989] reduced by hydrogen to give free metal and
(a) 6.02 ×10 23 (b) 1.2 × 1023 water. 0.1596 g of the metal oxide requires 6 mg
of hydrogen for complete reduction. The atomic
(c) 3.01 × 1023 (d) 2.01 × 1023 weight of the metal is [1989]
32. 1 c.c. N2O at NTP contains : [1988] (a) 27.9 (b) 159.6
1 . 8 (c) 79.8 (d) 55.8
(a) ´ 10 22 atoms
224 Topic 3: Stoichiometric Calculations
6.02
(b) ´ 10 23 molecules 40. A mixture of 2.3 g formic acid and 4.5 g oxalic
22400 acid is treated with conc. H2SO4. The evolved
1.32 gaseous mixture is passed through KOH pellets.
(c) ´ 10 23 electrons Weight (in g) of the remaining product at STP
224
(d) all the above will be [2018]
(a) 1.4 (b) 3.0
33. At S.T.P. the density of CCl4 vapours in g/L will
(c) 4.4 (d) 2.8
be nearest to : [1988]
41. 20.0 g of a magnesium carbonate sample
(a) 6.87 (b) 3.42 decomposes on heating to give carbon dioxide
(c) 10.26 (d) 4.57 and 8.0 g magnesium oxide. What will be the
Topic 2: Percent Composition and percentage purity of magnesium carbonate in
the sample ? [2015 RS]
Empirical Formula
(a) 75 (b) 96
34. An organic compound contain s carbon, (c) 60 (d) 84
hydrogen and oxygen. Its elemental analysis 42. What is the mass of precipitate formed when 50
gave C, 38.71% and H, 9.67%. The empirical mL of 16.9% solution of AgNO3 is mixed with 50
formula of the compound would be : [2008] mL of 5.8% NaCl solution ? [2015 RS]
(Ag = 107.8, N = 14, O = 16, Na = 23, Cl = 35.5)
(a) CH3O (b) CH2O
(a) 28 g (b) 3.5 g
(c) CHO (d) CH4O (c) 7 g (d) 14 g
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4 CHEMISTRY
43. In an experiment it showed that 10 mL of 0.05 M 50. In Haber process 30 litres of dihydrogen and
solution of chloride required 10 mL of 0.1 M 30 litres of dinitrogen were taken for reaction
solution of AgNO3, which of the following will which yielded only 50% of the expected product.
be the formula of the chloride (X stands for the What will be the composition of gaseous mixture
symbol of the element other than chlorine): under the aforesaid condition in the end? [2003]
[NEET Kar. 2013] (a) 20 litres ammonia, 25 litres nitrogen, 15 litres
(a) X2Cl (b) X2Cl2 hydrogen
(c) XCl2 (d) XCl4 (b) 20 litres ammonia, 20 litres nitrogen, 20 litres
44. 6.02 × 1020 molecules of urea are present in hydrogen
100 mL of its solution. The concentration of (c) 10 litres ammonia, 25 litres nitrogen, 15 litres
solution is : [NEET 2013] hydrogen
(a) 0.01 M (b) 0.001 M (d) 20 litres ammonia, 10 litres nitrogen, 30 litres
(c) 0.1 M (d) 0.02 M hydrogen
51. In the reaction
45. What is the [OH] in the final solution prepared 4 NH3 (g) + 5 O2 (g) ® 4 NO(g) + 6 H2O(l)
by mixing 20.0 mL of 0.050 M HCl with 30.0 mL of When 1 mole of ammonia and 1 mole of O2 are
0.10 M Ba(OH)2? [2009] made to react to completion, [1998]
(a) 0.40 M (b) 0.0050 M (a) 1.0 mole of H2O is produced
(c) 0.12 M (d) 0.10 M (b) 1.0 mole of NO will be produced
46. 10 g of hydrogen and 64 g of oxygen were filled (c) all the oxygen will be consumed
in a steel vessel and exploded. Amount of water (d) all the ammonia will be consumed
produced in this reaction will be: [2009] 52. Liquid benzene (C6H6) burns in oxygen according
(a) 3 mol (b) 4 mol to the equation
(c) 1 mol (d) 2 mol 2C6H6(l) + 15O2(g) ¾® 12CO2(g) + 6H2O(g)
47. How many moles of lead (II) chloride will be
How many litres of O2 at STP are needed to
formed from a reaction between 6.5 g of PbO
complete the combustion of 39 g of liquid
and 3.2 g of HCl ? [2008]
benzene? (Mol. wt. of O2 = 32, C6H6 = 78)
(a) 0.044 (b) 0.333
[1996]
(c) 0.011 (d) 0.029
(a) 74 L (b) 11.2 L
48. Concentrated aqueous sulphuric acid is 98%
(c) 22.4 L (d) 84 L
H2SO4 by mass and has a density of 1.80 g mL– 1.
53. A 5 molar solution of H2SO4 is diluted from
Volume of acid required to make one litre of 0.1M
1 litre to a volume of 10 litres, the normality of
H2SO4 solution is [2007]
the solution will be : [1991]
(a) 16.65 mL (b) 22.20 mL (a) 1 N (b) 0.1 N
(c) 5.55 mL (d) 11.10 mL (c) 5 N (d) 0.5 N
49. The mass of carbon anode consumed (giving 54. One litre hard water contains 12.00 mg Mg2+.
only carbon dioxide) in the production of Mili-equivalents of washing soda required to
270 kg of aluminium metal from bauxite by the remove its hardness is : [1988]
Hall process is (Atomic mass: Al = 27) [2005] (a) 1 (b) 12.16
(a) 270 kg (b) 540 kg (c) 1 × 10–3 (d) 12. 16 × 10–3
(c) 90 kg (d) 180 kg
ANSWER KEY
1 (c) 7 (a) 13 (c) 19 (d) 25 (a) 31 (a) 37 (c) 43 (c) 49 (c)
2 (c) 8 (a) 14 (b) 20 (c) 26 (c) 32 (d) 38 (d) 44 (a) 50 (c)
3 (a) 9 (c) 15 (d) 21 (c) 27 (a) 33 (a) 39 (d) 45 (d) 51 (c)
4 (a) 10 (b) 16 (b) 22 (d) 28 (a) 34 (a) 40 (d) 46 (b) 52 (d)
5 (d) 11 (c) 17 (a) 23 (b) 29 (b) 35 (d) 41 (d) 47 (d) 53 (a)
6 (b) 12 (b) 18 (b) 24 (c) 30 (c) 36 (c) 42 (c) 48 (c) 54 (a)
Hints & Solutions

1. (c) Number of atoms
W
= ´ N A ´ atomicity Number of
M
Molar mass moles
.
ol
u lt m
s m
i pl a s
as y
1
m ly b
yb s
Di
.
(a) Number of Mg atoms = ´ NA ´1
l
tip
v id m a
ym
s o
as m
ul
24
e b ss
m by
ol .
M
ym
e
id
1
iv
o l.
D
(b) Number of O atoms = ´ NA ´ 2 Divide by mol.
32 Mass in mass Number of
1 grams molecules
(c) Number of Li atoms = ´ N A ´ 1 Multiply by mo l.
7 mass
1 6. (b) If 6.022 × 1023 changes to 6.022 × 1020/mol

(d) Number of Ag atoms = ´ N A ´1
108 then this would change mass of one mole of
2. (c) N2 + 3H2 ¾® 2NH3 carbon.
3 Mass of 12C carbon is used to define the atomic
1 Mol NH3 = mol H2 mass unit. In this system, 12C is assigned a mass
2 of exactly 12 a.m.u.
3 Earlier one mole was defined as the amount of
20 mol NH3 = × 20 mol H2 = 30 mol H2
2 substance that contains as many particles as there
\ 30 moles of H2 are required. are atoms in exactly 12 g of the 12C isotope. From
3. (a) November 2018, one mole is defined as exactly
(1) Mass of water = 18 × 1 = 18 g 6.02214076 × 1023 constitutive particles, which
Molecules of water = mole × NA may be atoms, molecules, ions or electrons.
Hence, if we change the value of NA from 6.022 ×
18 1023 mol–1 to 6.022 × 1020 mol–1 then mass of one
= NA = N mole of carbon will also change.
18 A
(2) Molecules of water = mole × NA The definition of mass is independent of Avogadro
number NA.
0.18
= NA = 10–2 N
18 A 7. (a) H2(g) + Cl2(g) ¾® 2HCl(g)
(3) Molecules of water = mole × NA = 10–3 NA 22.4 L 11.2 L 0 initial
= 1 mole = 0.5 mole
0.00224 1 – 0.5 0.5 – 0.5 2 × 0.5 final
(4) Moles of water = = 10–4 Moles of HCl formed = 2 × 0.5 = 1
22.4
Molecules of water = mole × NA = 10–4 NA 1
8. (a) Initially Mg + O 2 ¾® MgO
4. (a) Ratio of weight of gases = wH : wO = 1 : 4 2
2 2 1g
0.56
1 4
Ratio of moles of gases = nH : nO = : or 1
mole
0.56
mole
2 2 2 32 24 32
1 32 0.041 7 mole 0.0175 mole
\ Molar Ratio = ´ = 4 :1 (0.0417 – 2 0 mole
2 4 × 0.0175)
5. (d) No. of moles of water = 0.0067 mole
In 1.8 g of H2O = 0.1 moles \ Mass of Mg = 0.0067 × 24 = 0.16g
In 18 g of H2O = 1 moles 9. (c) No. of molecules
1 mole contains 6.022 × 1023 molecules of water 44
Moles of CO2 = = 1, N
therefore maximum number of molecules is in 18 44 A
moles of water.
EBD_8336
6 CHEMISTRY
48 Thus, volume occupied by 1 molecule of water

Moles of O3 = =1, N 1 ´ 18
48 A
= cm 3 = 3.0×10–23 cm3.
8 6.023 ´ 10 23
Moles of H2 = = 4 , 4N i.e. the correct answer is option (c).
2 A
14. (b) The balance chemical equation is :
64
Moles of SO2 = =1, N 2MnO -4 + 6H + + 5SO32 - ¾¾
®
64 A
10. (b) The number of atoms in 0.1 mol of a triatomic 2Mn 2 + + 5SO4 2 - + 3H 2O
gas = 0.1 × 3 × 6.023 × 1023. From the equation it is clear that
= 1.806 × 1023 Moles of MnO4– require to oxidise 5 moles of
11. (c) Writing the equation of combustion of SO32 – are 2
propane (C3H8), we get Moles of MnO4– require to oxidise 1 mole of
C3 H 8 + 5O 2 ® 3CO 2 + 4H 2 O SO32– are 2/5.
1vol 5vol 15. (d) Average isotopic mass of
IL 5L
From the above equation we find that we need 200 ´ 90 + 199 ´ 8 + 202 ´ 2
5 L of oxygen at N.T.P. to completely burn 1 L of X =
90 + 8 + 2
propane at N.T.P.
If we change the conditions for both the gases 18000 + 1592 + 404
=
from N.T.P. to same conditions of temperature 100
and pressure. The same results are obtained. 19996
i.e. 5 L is the correct answer. = = 199.96 ; 200 amu
100
COO– – +
12. (b) 5 +2 MnO4 + 16 H Average atomic mass
COO– = (Mass of isotope A × % natural abundance) +
oxalate ion (Mass of isotope B × % natural abundance) +
2+
2 Mn +10CO2+8H2O .................
(% Natural abundance of A + % natural abundance
From above equation 2 moles of MnO4 required of B) + ........
to oxidise 5 moles of oxalate.
Thus number of moles of MnO4– required to 16. (b) In weak alkaline medium, the equation is:
– –
oxidise one mole of oxalate = 2 × 2/5 = 0.4 moles 2Mn SO4– + H2O + I ¾® 2MnO2 + IO4– + 2O H
In KMnO 4 the oxidation state of Mn is +7. In Hence, one mole of KI reduce, 2 moles of KMnO4.
acidic medium Mn takes up five electrons and 17. (a) No. of molecules in different cases
making it an oxidizing agent. In strongly alkaline (a) Q 22.4 litre at STP contains
solution it takes up only 1 electrons and making it
= 6.023×1023molecule of H2
much weaker oxidising agent. In neutral medium it
gives up 3 electrons to form MnO2. 15
Acidic medium: \15 litre at STP contains = ´ 6.023 ´ 10 23
– 22.4
MnO4 + 8H+ + 5e– ® Mn2+ + 4H2O
– 2–
(b) Q 22.4 litre at STP contains
Alkaline medium: MnO4 + e– ® MnO4 = 6.023×1023 molecule of N2
Neutral medium: 5
–
MnO4 + 4H+ + 3e– ® MnO2 + 2H2O \ 5 litre at STP contians = ´ 6.023 ´ 10 23
22.4
13. (c) \ Volume occupied by 1 gram water = 1 cm3 (c) Q 2 g of H2= 6.023×1023 molecules of H2
or Volume occupied by 0.5
\ 0.5 g of H2= ´ 6.023 ´ 10 23
6.023 ´ 1023 2
molecules of water = 1 cm3 (d) Similarly 10 g of O2 gas
18
1 10
[\ 1g water = moles of water] = ´ 6.023 ´ 10 23 molecules
18 32
Thus (a) will have maximum number of molecules
18. (b) 2g of H2 means one mole of H2, hence (29.2 – 20.2)(1.79 ´ 105 )
contains 6.023 × 1023 molecules. Others have 24. (c)
less than one mole, so have less no. of molecules. 1.37
As the least precise number contains 3
19. (d) Specific volume (volume of 1 g) of significant figures therefore, answers should also
cylindrical virus particle = 6.02 × 10–2 cc/g contains 3 significant figures.
Radius of virus (r) = 7 Å = 7 × 10–8 cm 25. (a) No of moles of nitride ion
Length of virus = 10 × 10–8 cm
4.2
Volume of virus = = = 0.3 mol = 0.3 ´ N A nitride ions.
22 14
pr 2 l = ´ (7 ´ 10 -8 ) 2 ´10 ´10 -8 Valence electrons = 8 × 0.3 NA = 2.4 NA
7
Nitride ion has seven protons in the nucleus and
= 154 × 10–23 cc ten electrons surrounding the nucleus. Therefore
volume total no. of electrons is 10. Number of valence
Wt. of one virus particle =
specific volume electrons is (5 + 3) = 8.
Mol. wt. of virus = Wt. of NA particle 26. (c) According to Avogadro's law "equal
154 ´ 10 -23 volumes of all gases contain equal numbers of
= ´ 6.02 ´ 10 23 molecules under similar conditions of
-2
6.02 ´ 10 temperature and pressure". Thus if 1 L of one
= 15400 g/mol = 15.4 kg/mol gas contains N molecules, 2 L of any gas under
20. (c) BaCO3 ® BaO + CO2 the same conditions will contain 2N molecules.
197 g 19 ´ 10 + 81 ´ 11
27. (a) Average atomic mass =
As 197 g of BaCO3 will release 100
22.4 litre of CO2 at STP = 10.81
\ 1 g of BaCO3 will release 28. (a) 1 mol of CO2 = 44 g of CO2
22.4 4.4
= litre of CO2 4.4 g CO2 = = 0.1 mol CO2
197 44
And 9.85 g of BaCO3 will release carbon dioxide = 6 × 1022 molecules
22 .4 = 2 × 6 × 1022 atoms or 1.2 × 10 23 atoms of oxygen.
= ´ 9.85 = 1.12 litre of CO
197 2 29. (b) 6.02 × 1023 molecules of CO =1mole of CO
21. (c) Given : Percentage of the iron = 0.334%; 6.02 × 1024 CO molecules = 10 moles of CO
Molecular weight of the haemoglobin = 10 g atoms of O = 5 g molecules of O2
= 67200 and atomic weight of iron = 56. We know
that the number of iron atoms 30. (c) C2H4 + 3 O2 ¾ ¾® 2CO + 2H O
2 2
Molecular wt. of haemoglobin ´ % of iron
28 kg 96 kg
= As 28 kg of C2H4 undergo complete combustion
100 ´ Atomic weight of iron
67200 ´ 0.334 by 96 kg of O2
= =4
100 ´ 56 \ 2.8 kg of C2H4 undergo complete combustion
22. (d) Number 161 cm, 0.161 cm and 0.0161cm have by 9.6 kg of O2.
3, 3 and 3 significant figures respectively. 31. (a) Cp / Cv = 1.4 shows that the gas is diatomic.
All non-zero digits are significant and the zeros at 22.4 litre at NTP º 6.02 × 1023 molecules
the beginning of a number are not significant. 11.2 L at NTP = 3.01 × 1023 molecules
No. of atoms in gas = 3.01 × 1023 × 2 atoms
23. (b) Molecular weight of C60H122 = 6.02 × 1023 atoms
= (12 × 60) + 122 = 842.
Cp 2
Therefore, weight of one molecule r= = 1 + , where F = degree of freedom of
Cv F
Molecular weight of C60 H122
= the gas molecules
Avogadro's number For mono atomic gas, F = 3
842 Cp 2 5
= 23
= 1.36 ´ 10-21 g ; 1.4 ´ 10-21 g \ g= = 1 + = = 1.67
6.023 ´ 10 Cv 3 3
EBD_8336
8 CHEMISTRY
For diatomic gas, F = 5 36. (c) Table for empirical formula :

Cp 2 7 Element % At. Relative Ratio
\ g= = 1 + = = 1.40 wt number
Cv 5 5
For triatomic gas, F = 6 or 7 (depending upon the 40 3.33
nature of the gas) C 40 12 = 3.33 =1
12 3.33
Cp 2
\ g= = 1 + = 1.33
6.66 6.66
Cv 6 =2
H 6.66 1 = 6.66
Cp 2 1 3.33
g= = 1 + = 1.29
Cv 7 53.34 3.33
O 53.34 16 = 3.33 =1
32. (d) At NTP, 22400 cc of N2O 16 3.33
= 6.02 × 1023 molecules (% of O in organic compound
\ 1 cc of N O contain = 100 – ( 40 + 6.66 ) = 53.34 % )
2
6.02 ´ 1023 \ Empirical formula of organic compound = CH2O.
= molecules
22400 37. (c) As the sum of the percentage of C, H & N
3 ´ 6.02 ´ 10 23
1. 8 is 100. Thus, it does not contains O atom.
= = ´ 1022 atoms Table for empirical formula
22400 224
(Q N2O molecule has 3 atoms) Element % At. Relative Ratio
No. of electrons in a molecule of N 2O wt. Number
= 7 + 7 + 8 = 22 40 3.33
C 40.00 1 2 = 3.33 =1
Hence, no. of electrons 12 3.33
6.02 ´ 1023 1.32 ´ 10 23 13.33 13.33
= ´ 22 = electrons H 13.33 1 = 13.33 =4
22400 224 1 3.33
33. (a) 1 mol CCl4 vapour = 12 + 4 × 35.5 46.67 3.33
= 3.33 =1
= 154 g º 22.4 L at STP N 46.67 1 4
14 3.33
Hence, empirical formula = CH4N
\ Density = 154 gL-1 = 6.875 gL-1
22.4 38. (d) Molecular weight of ZnSO 4 .7H 2O
34. (a) = 65 + 32 + (4 × 16) + 7(2 × 1 + 16) = 287.
Element % Atomic Atomic Simple
\ percentage mass of zinc (Zn)
weight ratio ratio
65
= ´ 100 = 22.65%
C 38.71 12 38.71
= 3.23
3.23
=1
287
12 3.23 39. (d) The reaction can be given as
H 9.67 1 9.67 9.67
= 9.67 =3 Z2 O3 + 3H2 ¾ ¾® 2Z + 3H2O
1 3.23
O 100 - 16 51.62
= 3.23
3.23
=1
0.1596 g of Z2O3 react with H2 = 6 mg = 0.006 g
(38.71 + 9.67) 16 3.23
= 51.62 \ 1 g of H2 react with
0.1596
Thus, empirical formula is CH3O. = = 26.6 g of Z2O3
35. (d) Suppose the mol. wt. of enzyme = x 0.006
Given 100 g of enzyme wt of Se = 0.5 g \ Eq. wt. of Z O = 26.6
2 3
0.5 (from the definition of eq. wt.)
\ In x g of enzyme wt. of Se = ´x
100 Eq. wt. of Z + Eq. wt. of O (8) = 26.6
0.5 ´ x Þ Eq. wt. of Z = 26.6 – 8 = 18.6
Hence 78.4 =
100 Valency of metal in Z2O3 = 3
\ x = 15680 = 1.568 × 104
Atomic wt. 2.9g

Eq. wt.of metal = nNaCl = = 0.0495 moles
valency (23 + 35.5) g/ mol
\ At. wt. of Z = 18.6 × 3 = 55.8
AgNO3 + NaCl ® AgCl ¯ + Na+ + NO3–
H2SO4
40. (d) HCOOH ¾¾¾¾®
Dehydrating CO + H2O 1 mole 1 mole 1 mole
agent \ 0.049 mole 0.049 mole 0.049 mole of AgCl
[H 2O absorbed by H 2SO 4] w
2.3 1 n= ® w = (nAgCl) × Molecular Mass
At start = = 0 0 M
46 20
(moles) = (0.049) × (107.8 + 35.5) = 7.02 g
1 1
Final moles 0
20 20
43. (c) Millimoles of solution of chloride
H2SO4 = 0.05 × 10 = 0.5
H2C2O4 ¾¾¾® CO + CO2 + H2O
Millimoles of AgNO3 solution = 10 × 0.1 = 1
[H 2O absorbed by H 2SO 4]
4.5 1 So, the millimoles of AgNO3 are double than the
At start = = 0 0 0
90 20 chloride solution.
(moles)
1 1 1 \ XCl2 + 2AgNO3 ¾® 2AgCl + X (NO3)2
Final moles 0
20 20 20 6.02 ´ 10 20 ´ 1000 6.02 ´ 1021
44. (a) M = 23 =
CO2 is absorbed by KOH. 100 ´ 6.02 ´ 10 6.02 ´ 1023
So, the remaning product is only CO. = 0.01 M
Moles of CO formed from both reactions 45. (d) No. of milli equivalent of HCl
1 1 1 = 20 × 0.05 = 1.0
= + = No. of milli equivalent of Ba (OH)2
20 20 10
Left mass of CO = moles × molar mass = 30 × 0.1 × 2 = 6.0
After neutralization, no. of milli equivalents in
1
= ´ 28 = 2.8 g 50 mL. of solution = (6 – 1) = 5
10 Total volume of the solution = 20 + 30 = 50 mL
41. (d) ® MgO + CO 2
MgCO 3 ¾¾ \ No. of equivalent of OH– in 50 mL is
84 g of MgCO3 form 40 g of MgO 5 ´ 1000
[OH - ] = ´ 10 -3 = 0.1 M
40 ´ 20 50
\ 20g of MgCO3 form g of MgO
84 1
46. (b) H2 + ® H2O
O2 ¾¾
= 9.52 g of MgO 2
Since 8.0 g of MgO is formed 10g 64g
(5 mol) (2 mol)
8 In this reaction oxygen is the limiting agent.
Purity of sample = ´ 100 = 84.0%
9.52 Hence, amount of H2O produced depends on
42. (c) 50 mL of 16.9% solution of AgNO3 the amount of O2 taken.
æ 16.9 ö Q 0.5 mole of O2 gives H2O = 1 mol
ç 100 ´ 50 ÷ = 8.45 g of Ag NO3 \ 2 mole of O2 gives H2O = 4 mol
è ø
8.45g When there is not enough of one reactant in a
nmole = chemical reaction, the reaction stops. To find the
(107.8 + 14 + 16 ´ 3) g / mol
amount of product produced, we must determine
æ 8.45 g ö reactant that will limit the chemical reaction (the
=ç ÷ = 0.0497 moles limiting reagent) we can find the limiting reagent
è 169.8g / mol ø by calculating the amount of product that can be
50 mL of 5.8% solution of NaCl contain formed by each reactant, the one that produces
less product is the limiting reagent.
æ 5.8 ö
NaCl = ç ´ 50 ÷ = 2.9 g
è 100 ø
EBD_8336
10 CHEMISTRY
47. (d) Writing the equation for the reaction, we get Again,
PbO + 2HCl ¾¾ ® PbCl2 + H2O No. of gram equivalent of C
207 + 16 2 × 36.5 207 + 71 mass in gram
=
= 223 g = 73g = 278g gram equivalent weight
From this equation we find 223 g of PbO reacts mass
with 73 g of HCl to form 278 g of PbCl2. Þ 30 × 103 =
3
If we carry out the reaction between 3.2 g HCl Þ mass = 90 × 103 g = 90 kg
and 6.5 g PbO.
50. (c) N 2 + 3H 2 ® 2NH 3
Amount of PbO that reacts with 3.2 g HCl 1 vol. 3 vol. 2 vol.
223 10 litre 30 litre 20 litre
= ´ 3.2 =9.77 g.
73 It is given that only 50% of the expected product
Since amount of PbO present is only 6.5 g so is formed hence, only 10 litre of NH3 is formed.
PbO is the limiting reagent. N2 used = 5 litres, left = 30 – 5 = 25 litres
Amount of PbCl 2 formed by 6.5 g of PbO H2 used = 15 litres, left = 30 – 15 = 15 litres
278 51. (c) According to Stoichiometry, they should
= ´ 6.5g react as follow:
223
Number of moles of PbCl2 formed 4 NH 3 + 5O 2 ¾ ¾® 4 NO + 6H 2 O
4 moles 5 moles 4 moles 6 moles
0.8 moles
278 6.5 0.8 moles 1 mole 1.2 moles
= ´ moles = 0.029 moles.
223 278 Thus, for 1 mole of O2 only 0.8 moles of NH3 is
48. (c) Molarity of H2SO4 solution consumed. Hence O2 is consumed completely.
98 ´ 1000 52. (d) 2C6 H 6 + 15O2 (g) ¾¾
®12CO2 (g) + 6 H 2 O(g)
= ´ 1.80 = 18.0
98 ´ 100 2(78) 15(32)
Suppose V mL of this H2SO4 is used to prepare Q 156 g of benzene, required oxygen
1 lit. of 0.1M H2SO4 = 15 × 22.4 litre
\ V ´ 18.0 = 1000 ´ 0.1 \ 1g of benzene, required oxygen
15´ 22.4
1000 ´ 0.1 = litre
or V = = 5.55 mL. 156
18.0 \ 39 g of benzene, required oxygen
49. (c) 2Al 2O 3 + 3C ¾¾ ® Al + 3CO 2
15 ´ 22.4 ´ 39
Gram equivalent of Al2O3 º g equivalent of C = = 84.0 litre
156
27
Now equivalent weight of Al = =9 53. (a) 5 M H2SO4 = 10 N H2SO4,
3 (Q Basicity of H2SO4 = 2)
Equivalent weight of C N1V1 = N2V2,
12 0 +4 10 × 1 = N2 × 10 or N2 = 1 N
= = 3 ( C ® C O2 )
4 54. (a) Mg2+ + Na 2 CO3 ¾¾ ® MgCO3 + 2Na +
3
270 ´ 10 1 g eq. 1g eq.
No. of gram equivalent of Al = 1 g eq. of Mg2+ = 12 g of Mg2+ = 12000 mg
9
= 30 × 103 = 1000 milli eq. of Na 2CO3
Hence, \ 12 mg Mg2+ = 1 milli eq. Na2CO3
No. of gram equivalent of C = 30 × 103
2 Structure of Atom
2020 2019 2018 2017 2016

Bohr's model for H Absortion/emission
1 E
atom spectra
uncertainity
Dual behaviour of
principle/orbital
matter and Heisenberg 1 A
stability/de-Broglie
uncertainity principle
wavelength
Quantum mechanical Quantum numbers 1 A 1 E
model of atom orbital energy 1 A
Topic 1 : Atomic Models and Dual Nature of 4. The energies E1 and E2 of two radiations are 25
Electromagnetic Radiation eV and 50 eV, respectively. The relation between
their wavelengths i.e., l1 and l2 will be: [2011]
1. Calculate the energy in joule corresponding to (a) l1 = l2 (b) l1 = 2l2
light of wavelength 45 nm :
(Planck’s constant h = 6.63 × 10–34 Js; speed of 1
(c) l1 = 4l2 (d) l1 = l2
light c = 3 × 108 ms–1) [2014] 2
(a) 6.67 × 1015 (b) 6.67 × 1011 5. The energy absorbed by each molecule (A2) of
(c) 4.42 × 10–15 (d) 4.42 × 10–18 a substance is 4.4 × 10–19 J and bond energy
2. According to law of photochemical equivalence per molecule is 4.0 × 10–19 J. The kinetic energy
the energy absorbed (in ergs/mole) is given as of the molecule per atom will be: [2009]
(h = 6.62 × 10–27 ergs, c = 3 × 1010 cm s–1, (a) 2.2 × 10–19 J (b) 2.0 × 10–19 J
NA = 6.02 × 1023 mol–1) [NEET Kar. 2013] (c) 4.0 × 10–20 J (d) 2.0 × 10–20 J
1.196 ´ 1016 1.196 ´ 108 6. The value of Planck's constant is 6.63 × 10–34 Js.
(a) (b) The velocity of light is 3.0 × 108 m s–1. Which value
l l
is closest to the wavelength in nanometers of a
2.859 ´ 105 2.859 ´ 1016
(c) (d) quantum of light with frequency of 8 × 1015 s–1 ?
l l [2003]
3. The value of Planck’s constant is 6.63 × 10–34 Js.
(a) 3 × 107 (b) 2 × 10–25
The speed of light is 3 × 1017 nm s–1.. Which
(c) 5 × 10–18 (d) 4 × 101
value is closest to the wavelength in nanometer
7. If the energy of a photon is given as 3.03 × 10–19 J
of a quantum of light with frequency of
then, the wavelength (l) of the photon is :
6 × 1015 s–1? [NEET 2013]
(a) 6.56 nm (b) 65.6 nm [2000]
(a) 25 (b) 50
(c) 656 nm (d) 0.656 nm
(c) 75 (d) 10
EBD_8336
12 CHEMISTRY
8. In the photo-electron emission, the energy of (a) n = 6 to n = 1 (b) n = 5 to n = 4

the emitted electron is [1994] (c) n = 6 to n = 5 (d) n = 5 to n = 3
(a) greater than the incident photon 14. The energy of second Bohr orbit of the
(b) same as than of the incident photon hydrogen atom is -328 kJ mol -1; hence the
(c) smaller than the incident photon energy of fourth Bohr orbit would be:
(d) proportional to the intensity of incident [2005]
photon. (a) -41 kJ mol-1 (b) -82 kJ mol-1
9. The electron was shown experimentally to have (c) -164 kJ mol-1 (d) -1312 kJ mol-1
wave properties by [1994] 15. The frequency of radiation emitted when the
(a) de Broglie electron falls from n = 4 to n = 1 in a hydrogen
(b) Davisson and Germer atom will be (Given ionization energy of
(c) N. Bohr H=2.18 ×10–18J atom–1and h = 6.625 × 10–34 J s )
(d) Schrodinger. [2004]
10. Which of the following is never true for cathode
rays ? [1994] (a) 1.54 ´1015 s -1 (b) 1.03 ´1015 s -1
(a) They possess kinetic energy (c) 3.08 ´1015 s -1 (d) 2.00 ´1015 s -1
(b) They are electromagnetic waves
(c) They produce heat 16. In hydrogen atom, energy of first excited state
(d) They produce mechanical pressure. is –3.4 eV. Find out KE of the same orbit of
Hydrogen atom [2002]
Topic 2 : Bohr's model for Hydrogen Atom (a) + 3.4 eV (b) + 6.8 eV
(Emission and Absorption Spectra) (c) – 13.6 eV (d) + 13.6 eV
11. Which of the following series of transitions in 17. According to Bohr’s theory the energy required
the spectrum of hydrogen atom falls in visible for an electron in the Li2+ ion to be emitted from
region ? [2019] n = 2 state is (given that the ground state ionization
(a) Lyman series (b) Balmer series energy of hydrogen atom is 13.6 eV) [1999]
(c) Paschen series (d) Brackett series (a) 61.2 eV (b) 13.6 eV
æ Z2 ö (c) 30.6 eV (d) 10.2 eV
12. Based on equation E = – 2.178 × 10-18 çç 2 ÷÷ J, 18. The Bohr orbit radius for the hydrogen atom (n = 1)
èn ø is approximately 0.530 Å. The radius for the first
certain conclusions are written. Which of them excited state (n = 2) orbit is (in Å) [1998]
is not correct ? [NEET 2013] (a) 0.13 (b) 1.06
(a) Larger the value of n, the larger is the orbit (c) 4.77 (d) 2.12
radius. 19. The radius of hydrogen atom in the ground state
(b) Equation can be used to calculate the change is 0.53 Å. The radius of Li2+ ion (atomic number = 3)
in energy when the electron changes orbit. in a similar state is [1995]
(c) For n = 1, the electron has a more negative (a) 0.17 Å (b) 0.265 Å
energy than it does for n = 6 which mean (c) 0.53 Å (d) 1.06 Å
that the electron is more loosely bound in 20. If ionization potential for hydrogen atom is
13.6 eV, then ionization potential for He+ will be
the smallest allowed orbit.
(a) 54.4 eV (b) 6.8 eV [1993]
(d) The negative sign in equation simply
(c) 13.6 eV (d) 24.5 eV
means that the energy or electron bound
21. The energy of an electron in the nth Bohr orbit
to the nucleus is lower than it would be if of hydrogen atom is [1992]
the electrons were at the infinite distance
13.6 13.6
from the nucleus. (a) – 4 eV (b) – 3 eV
13. According to the Bohr Theory, which of the n n
following transitions in the hydrogen atom will give 13.6 13.6
(c) – 2 eV (d) – eV
rise to the least energetic photon? [2011 M] n n
Structure of Atom 13
22. If r is the radius of the first orbit, the radius of 29. Given : The mass of electron is 9.11 × 10–31 kg
nth orbit of H-atom is given by [1988] Planck constant is 6.626 × 10–34 Js,
(a) rn2 (b) rn the uncertainty involved in the measurement of
(c) r/n (d) r2 n2 velocity within a distance of 0.1 Å is [2006]
23. The spectrum of He is expected to be similar to (a) 5.79 × 107 ms–1 (b) 5.79 × 108 ms–1
that [1988] 5
(c) 5.79 × 10 ms –1 (d) 5.79 × 106 ms–1
(a) H (b) Li+
30. The position of both, an electron and a helium
(c) Na (d) He+
atom is known within 1.0 nm. Further the
Topic 3: Dual Behaviour of Matter and momentum of the electron is known within
Heisenberg Uncertainty Principle 5.0 × 10–26 kg ms–1. The minimum uncertainty
in the measurement of the momentum of the
24. In hydrogen atom, the de-Broglie wavelength helium atom is [1998]
of an electron in the second Bohr orbit is (a) 50 kg ms–1 (b) 80 kg ms–1
[Given that Bohr radius, a0 = 52.9 pm]
(c) 8.0 × 10–26 kg ms–1 (d) 5.0 × 10–26 kg ms–1
[NEET Odisha 2019]
(a) 105.8 pm (b) 211.6 pm 31. The momentum of a particle having a de Broglie
(c) 211.6 p pm (d) 52.9 p pm wavelength of 10–17 metres is [1996]
25. Which one is the wrong statement ? [2017] (Given h = 6.625 × 10–34 Js)
(a) The uncertainty principle is (a) 3.3125 × 10–7 kg ms–1
DE ´ Dt ³ h / 4p (b) 26.5 × 10–7 kg ms–1
(b) Half filled and fully filled orbitals have (c) 6.625 × 10–17 kg ms–1
greater stability due to greater exchange (d) 13.25 × 10–17 kg ms–1
energy, greater symmetry and more 32. Uncertainty in position of an electron
balanced arrangement. (mass = 9.1 × 10–28 g) moving with a velocity of
(c) The energy of 2s orbital is less than the energy 3 × 104 cm/s accurate upto 0.001% will be
of 2p orbital in case of Hydrogen like atoms (use h/4(p) in uncertainty expression where
h h = 6.626 ×10–27 erg-second) [1995]
(d) de-Broglie's wavelength is given by l = ,
mn (a) 1.93 cm (b) 3.84 cm
where m = mass of the particle, n = group (c) 5.76 cm (d) 7.68 cm
velocity of the particle 33. When an electron of charge ‘e’ and mass ‘m’
26. A 0.66 kg ball is moving with a speed of 100 m/s. moves with a velocity ‘v’ about the nuclear
The associated wavelength will be charge ‘Ze’ in circular orbit of radius ‘r’, the
( h = 6.6 ´10 -34
)
Js : [2010] potential energy of the electrons is given by
[1994]
(a) 1.0 ´ 10–32m (b) 6.6 ´ 10–32m
(c) 6.6 ´ 10–34m (d) 1.0 ´ 10–35m (a) Ze2 / r (b) - Ze2 / r
27. The measurement of the electron position if 2
associated with an uncertainty in momentum, (c) Ze2 / r (d) mv / r
which is equal to 1 × 10–18 g cm s– 1 . The 34. Which of the following statements do not form
uncertainty in electron velocity is, [2008] a part of Bohr’s model of hydrogen atom ?
(mass of an electron is 9 × 10– 28 g) [1989]
(a) 1 × 109 cm s–1 (b) 1 × 106 cm s–1 (a) Energy of the electrons in the orbits are
5
(c) 1 × 10 cm s –1 (d) 1 × 1011 cm s–1 quantized
28. If uncertainty in position and momentum are (b) The electron in the orbit nearest the nucleus
equal, then uncertainty in velocity is : [2008] has the lowest energy
(c) Electrons revolve in different orbits around
1 h h the nucleus
(a) (b)
2m p 2p (d) The position and velocity of the electrons
1 h h in the orbit cannot be determined
(c) (d) simultaneously.
m p p
EBD_8336
14 CHEMISTRY
Topic 4 : Quantum Mechanical Model of Atom 42. The correct set of four quantum numbers for the
valence electron of rubidium atom (Z = 37) is
35. Orbital having 3 angular nodes and 3 total nodes is
[2012]
[NEET Odisha 2019]
(a) 5, 1, 1 + 1/2 (b) 6, 0, 0, + 1/2
(a) 6 d (b) 5 p
(c) 3 d (d) 4 f (c) 5, 0, 0, + 1/2 (d) 5, 1, 0, + 1/2
36. 4d, 5p, 5f and 6p orbitals are arranged in the 43. Maximum number of electrons in a subshell with :
order of decreasing energy. The correct option l = 3 and n = 4 is : [2012]
is: [2019] (a) 14 (b) 16
(a) 5f > 6p > 5p > 4d (b) 6p > 5f > 5p > 4d (c) 10 (d) 12
(c) 6p > 5f > 4d > 5p (d) 5f > 6p > 4d > 5p 44. If n = 6, the correct sequence for filling of
37. Which one is a wrong statement? [2018] electrons will be : [2011]
(a) Total orbital angular momentum of electron (a) ns ® (n – 2) f ® (n – 1) d ® np
in 's' orbital is equal to zero (b) ns ® (n – 1) d ® (n – 2) f ® np
(b) An orbital is designated by three quantum (c) ns ® (n – 2) f ® np ® (n – 1) d
numbers while an electron in an atom is (d) ns ® np (n – 1) d ® (n – 2) f
designated by four quantum numbers 45. The total number of atomic orbitals in fourth
(c) The value of m for dz2 is zero energy level of an atom is : [2011]
(d) The electronic configuration of N atom is (a) 8 (b) 16
2p1x 2p1y 2p1z (c) 32 (d) 4
1s2 2s2
46. Which of the following is not permissible
arrangement of electrons in an atom? [2009]
(a) n = 5, l = 3, m = 0, s = + 1/2
38. Two electrons occupying the same orbital are
(b) n = 3, l = 2, m = – 3, s = – 1/2
distinguished by [2016]
(c) n = 3, l = 2, m = – 2, s = – 1/2
(a) Principal quantum number
(d) n = 4, l = 0, m = 0, s = – 1/2
(b) Magnetic quantum number
(c) Azimuthal quantum number 47. Maximum number of electrons in a subshell of
(d) Spin quantum number an atom is determined by the following: [2009]
39. What is the maximum number of orbitals that (a) 2 l + 1 (b) 4 l – 2
can be identified with the following quantum (c) 2 n2 (d) 4 l + 2
numbers? [2014] 48. Consider the following sets of quantum numbers:
n = 3, l = 1, ml = 0 n l m s
(a) 1 (b) 2 (i) 3 0 0 + 1/2
(c) 3 (d) 4 (ii) 2 2 1 + 1/2
40. What is the maximum numbers of electrons that (iii) 4 3 –2 – 1/2
can be associated with the following set of (iv) 1 0 –1 – 1/2
quantum numbers? [NEET 2013] (v) 3 2 3 + 1/2
n = 3, l = 1 and m = –1 Which of the following sets of quantum number
(a) 6 (b) 4 is not possible? [2007]
(c) 2 (d) 10 (a) (i), (ii), (iii) and (iv) (b) (ii), (iv) and (v)
41. The orbital angular momentum of a p-electron (c) (i) and (iii) (d) (ii), (iii) and (iv)
is given as : [2012 M] 49. The orientation of an atomic orbital is governed
h h by [2006]
(a) (b) 3 (a) Spin quantum number
2p 2p
(b) Magnetic quantum number
3h h (c) Principal quantum number
(c) (d) 6.
2p 2p (d) Azimuthal quantum number
50. The ions O2– , F– , Na +, Mg2+ and Al 3+ are 58. Which of the following species has four lone
isoelectronic. Their ionic radii show [2003] pairs of electrons ? [1993]
2– –
(a) A decrease from O to F and then increase
from Na+ to Al3+ (a) I (b) O -
(b) A significant increase from O2– to Al3+ (c) Cl– (d) He
(c) A significant decrease from O2– to Al3+ 59. The order of filling of electrons in the orbitals of
(d) An increase from O 2– to F– and then an atom will be [1991]
decrease from Na+ to Al3+ (a) 3d, 4s, 4p, 4d, 5s (b) 4s, 3d, 4p, 5s, 4d
51. Which of the following is isoelectronic?[2002]
(c) 5s, 4p, 3d, 4d, 5s (d) 3d, 4p, 4s, 4d, 5s
(a) CO2, NO2 (b) NO2–, CO2
– 60. For azimuthal quantum number l = 3, the
(c) CN , CO (d) SO2, CO2
maximum number of electrons will be [1991]
52. The following quantum numbers are possible
for how many orbital (s) n = 3, l = 2, m = +2 ? (a) 2 (b) 6
[2001] (c) 0 (d) 14.
(a) 1 (b) 3 61. In a given atom no two electrons can have the
(c) 2 (d) 4 same values for all the four quantum numbers.
53. Set of isoelectronic species is [2000] This is called [1991]
(a) Hund’s Rule
(a) N 2 , CO2 , CN- , O2 (b) N, H 2S, CO
(b) Aufbau principle
(c) N 2 , CO, CN - , O 2+2 (d) Ca , Mg, Cl (c) Uncertainty principle
54. The ion that is isoelectronic with CO is [1997] (d) Pauli’s Exclusion principle.
(a) CN– (b) O2+ 62. An ion has 18 electrons in the outermost shell, it
(c) O2 – (d) N2+ is [1990]
55. The orbitals are called degenerate when (a) Cu+ (b) Th4+
[1996]
(c) Cs+ (d) K+
(a) they have the same wave functions
(b) they have the same wave functions but 63. The total number of electrons that can be
different energies accommodated in all the orbitals having principal
(c) they have different wave functions but quantum number 2 and azimuthal quantum
same energy number 1 is [1990]
(d) they have the same energy (a) 2 (b) 4
56. If electron has spin quantum number + 1/2 and (c) 6 (d) 8
a magnetic quantum number – 1, it cannot be 64. The maximum number of electrons in a subshell
present in [1994] is given by the expression [1989]
(a) d-orbital (b) f-orbital
(a) 4l – 2 (b) 4l + 2
(c) p-orbital (d) s-orbital.
(c) 2l + 2 (d) 2n2
57. For which one of the following sets of four
quantum numbers, an electron will have the 65. Number of unpaired electrons in N2+ is [1989]
highest energy? [1994] (a) 2 (b) 0
n l m s (c) 1 (d) 34
(a) 3 2 1 1/2 66. The number of spherical nodes in 3p orbitals are
(b) 4 2 –1 1/2
(a) one (b) three [1988]
(c) 4 1 0 –1/2
(c) none (d) two
(d) 5 0 0 –1/2
EBD_8336
16 CHEMISTRY
ANSWER KEY
1 (d) 8 (c) 15 (c) 22 (a) 29 (d) 36 (a) 43 (a) 50 (c) 57 (b) 64 (b)
2 (b) 9 (b) 16 (a) 23 (b) 30 (d) 37 (d) 44 (a) 51 (c) 58 (c) 65 (c)
3 (b) 10 (b) 17 (c) 24 (c) 31 (c) 38 (d) 45 (b) 52 (a) 59 (b) 66 (a)
4 (b) 11 (b) 18 (d) 25 (c) 32 (a) 39 (a) 46 (b) 53 (c) 60 (d)
5 (d) 12 (c) 19 (a) 26 (d) 33 (b) 40 (c) 47 (d) 54 (a) 61 (d)
6 (d) 13 (c) 20 (a) 27 (a) 34 (d) 41 (a) 48 (b) 55 (d) 62 (a)
7 (c) 14 (b) 21 (c) 28 (a) 35 (d) 42 (c) 49 (b) 56 (d) 63 (c)
Hints & Solutions

- 34
hc 6.63 ´ 10 ´ 3 ´ 108 6. (d) E = hn =
hc
or l = c
1. (d) E = = l
l 45 ´ 10 - 9 n
= 4.42 × 10 J – 18
3 ´ 10 8
hc Þl= 15
= 3.75 ´ 10 - 8 m
2. (b) E = ´ NA 8 ´ 10
l
In nanometer l = 3.75× 10 which is closest to 4 × 101
6.62 ´ 10-27 ´ 3 ´ 1010 ´ 6.02 ´ 10 23 7. (c) The energy of photon,
=
l hc
1.19 ´ 108 E = = 3.03 ´ 10-19
= ergs mol–1 l
l 6.626 ´ 10 -34 ´ 3 ´ 108
Law of photochemical equivalence is the
or l =
3.03 ´ 10 -19
fundamental principle relating to chemical reactions
19.878
induced by light which states that for every mole or l = ´ 10 -7 = 6.56 × 10–7m= 656 nm
of a substance that reacts 6.022 × 1023 quanta of 3.03
light are absorbed. The photochemical equivalence 8. (c) K.E. of emitted electron is smaller than the
law is also sometimes called the stark-Einstein law. incident photon.
3. (b) c = u l K.E of emitted electron = hu – hu0
c 3 ´ 10 17 where hu0 = work function.
l= = = 50 nm [work function is the minimum energy required to
u 6 ´ 1015 remove an electron from the surface of the
4. (b) Given E1 = 25eV E2 = 50 eV material.]
Energy of the incident photon = hu
hc hc E1 l 2 maximum kinetic energy of the photoelectrons
E1 = E = \ =
l1 2 l 2 E2 l1 depend upon the frequency of the light not on the
intensity of light.
l 25 1
\ 2 = = \ l1 = 2l 2 9. (b) Wave nature of electron was shown by
l1 50 2 Davisson and Germer. Davisson and Germer
5. (d) K.E per atom demonstrated the physical reality of the wave
nature of electrons by showing that a beam of
=
( 4.4 ×10 ) – ( 4.0 ×10 )
–19 –19
electrons could also be diffracted by crystals
2 just like light of x-rays.
10. (b) Cathode rays are not electromagnetic waves.
–19
0.4×10 –20 11. (b) Balmer series
= = 2.0 ´ 10 J
2
12. (c) The electrons has more negative energy in Therefore the centripetal force is supplied by
lower orbits that in higher orbit and also the electrostatic force of attraction between the
electrons are more tightly bound in the smallest electron and nucleus i.e.
allowed orbit. mn2 Ze2
= 2
Energy of an electron at infinite distance from the r r
nucleus is zero. As an electron approaches the
Ze2
nucleus, the electron attraction increases and hence or mn2 =
the energy of electron decreases and thus becomes r
negative. Thus as the value of n decreases, i.e.
1 1 Ze 2
lower the orbit is, more negative is the energy of or mn2 = = K.E
the electron in it. 2 2 r
now total energy (En) = K.E + P.E
13. (c) Energy of photon obtained from th e in first excited state
transition n = 6 to n = 5 will have least energy.
1 é Ze 2 ù
æ 1 1 ö E = mv 2 + ê - ú
DE = 13.6Z 2 - 2 êë r úû
çè n 2 n 2 ÷ø
1 2
1 Ze2 Ze2
æ Zö
2 =+ -
14. (b) E n = E1 ´ ç ÷ 2 r r
è nø
1 Ze 2
E1 -3.4 eV = -
E 2 = 2 = -328kJ/mol 2 r
2
1 Ze 2
E \ K .E = = +3.4 eV
E 4 = 21 2 r
4
For Bohr orbit, kinetic energy = –Total energy and
E 4 22 1 Potential energy = 2 × Total energy.
Þ = 2 = 2
E2 4 2
E -328 17. (c) Energy of electron in 2nd orbit of Li +2
Þ E4 = 2 = kJ /mol = -82 kj /mol
22 4 Z2
= -13.6 2
15. (c) I.E. = E1 – E ¥ n
2.18 × 10–18 = E1 – 0 - 13.6 ´ (3) 2
E1 = 2.18 × 10–18 J-atom–1 = = –30.6 eV
(2) 2
æ 1 1 ö Energy required = 0 – (–30.6) = 30.6 eV
DE = E1 ç 2 - 2 ÷ 18. (d) Radius of hydrogen atom = 0.530 Å, Number
è n1 n 2 ø of excited state (n) = 2 and atomic number of
æ1 1ö hydrogen atom (Z) = 1. We know that the Bohr
Þ hv = 2.18 × 10–18 ç 2 - 2 ÷
è1 4 ø radius.
n2 (2)2
15 (r ) = ´ Bohr Radius of atom = ´ 0.530
Þ 6.625 × 10–34 × v = 2.18 × 10–18 × Z 1
16 = 4 ´ 0.530 = 2.12 Å
2.18 ´ 10 –18
´ 15 19. (a) State of hydrogen atom (n) = 1
Þ v= -34 (due to ground state)
6.625 ´ 10 ´ 16 Radius of hydrogen atom (r) = 0.53 Å. Atomic
Þ v = 3.08 × 1015 s–1 number of Li (Z) = 3.
16. (a) Suppose the nucleus of hydrogen atom Radius of Li2+ ion
have charge of one proton +e. The electron n2 (1) 2
revolves in an orbit of radius r around it. =r´ = 0.53 ´ = 0.17Å.
Z 3
EBD_8336
18 CHEMISTRY
20. (a) The ionization energy of any hydrogen like h

species (having one electron only) is given by 28. (a) We know Dp.Dx ³
4p
the equation
h
2 2 4
or m.Dv.Dx = [\ Dp = mDv]
2p Z m e 4p
I.E = or I.E µ Z 2
since Dp = Dx (given)
h2
Since the atomic number of H is 1 and that of He h h
is 2, therefore, the I.E. of He+ is four times (22) the \ Dp.Dp = or mDv mDv =
4p 4p
I.E. of H i.e., 13.6 × 4 = 54.4 eV
h
or ( Dv ) =
2
For H-like particles, 4pm2
21.8 ´ 10-19 2 h 1 h
En = - Z J/atom
or Dv = =
h2 2 2m p
4 pm
1312 2
= - 2 Z kJ/mol h
n 29. (d) We know that Dx . Dp ³
4p
I.E = Ea o – E1 = 0 – (– I.EHZ2)
= Z2 × I.EH h
Dx . m Dv >
Now for He+, Z=2 \ I.E = 4 × I.EH 4p
for Li2+, Z=3 \ I.E = 9 × I.EH h
Dv >
21. (c) Energy of an electron in Bohr's orbit is given 4 pDxm
13.6 6.626 ´ 10 -34

by the relationship. En = - eV. Dv =
n2 4 p ´ 0.1 ´ 10 -10 ´ 9.11 ´ 10 -31
th 2
22. (a) Radius of n orbit = r1 n . (for H-atom) 66
= ´ 10 7 = 5.79 ´ 10 6 m / sec
23. (b) Both He and Li+ contain 2 electrons each, 4p ´ 9
therefore their spectrum will be similar. 30. (d) By Heisenberg uncertainty Principle
24. (c) nl = 2pr h
Dx ´ Dp = (which is constant)
2p 4p
l= r As Dx for electron and helium atom is same thus
n
momentum of electron and helium will also be
rn = a0n2
same and the uncertainty in momentum of helium
r2 = 52.9 × (2)2 pm
atom is equal to 5 × 10–26 kg ms–1.
2p 31. (c) Acc. to de-Broglie,
\ l= × 52.9 × 4
2
l = 211.6 p pm h h 6.625 ´ 10-34
l= Þ mv = =
25. (c) For hydrogen like atoms energy of mv l 10-17
2s-orbital and 2p-orbital is equal. Þ p = 6.625 × 10–17 kg m/s
h 6.6 ´ 10 -34 32. (a) Given mass of an electron(m) = 9.1 × 10–28 g;
26. (d) l = = = 1 ´ 10 -35 m Velocity of electron (v ) = 3 ´ 10 4 cm /s;
mv 0.66 ´ 100
27. (a) Dp = mDv
Substituting the given values of Dx and m, we get Accuracy in velocity = 0.001% = 0.001 ;
100
1×10–18 gcms–1 = 9×10–28 g × Dv Actual velocity of the electron
1 ´ 10-18 0.001
or Dv = ( Dv ) = 3 ´ 104 ´ = 0.3cm/s .
9 ´ 10-28 100
Planck’s constant (h) = 6.626×10–27erg-sec.
= 1.1 × 109 cm s–1 ; 1×109 cm s–1
\ Uncertainty in the position of the electron 41. (a) Orbital angular momentum
,27
h 6.626´10 ´7
( Dx ) = < =
h
l(l + 1)
,
4 pmDv 4´ 22´(9.1´10 )´ 0.3
28
2p
=1.93cm
For p orbital l = 1
r
Ze 2
Ze2
33. (b) P.E. = work done = ò - 2 dr = - . h h
r r So, = 2 =
¥
2p 2p
Kinetic and potential energy of atoms results from
the motion of electrons. When electrons are excited 42. (c) Electronic configuration of Rb = [Kr] 5s1
they move to a higher energy orbital farther away Set of quantum numbers, n = 5
from the atom. The further the orbital is from the l = 0, \ s-orbital
nucleus, the higher the potential energy of an
electron at that energy level. When the electron m = 0, s = + 1/2
returns to a low energy state, it releases potential The other possible answer is 5, 0, 0, –1/2 In and
energy in the form of kinetic energy.
orbital any electron can take the value of ± 1/2
34. (d) It is uncertainty principle which was given and the other elctron of the same orbital, takes the
by Heisenberg and not Bohr’s postulate. value with opposite sign.
35. (d) Total number of nodes = (n – 1) 43. (a) (n = 4, l = 3) Þ 4f subshell
3= n–1 Þ n=4 Since, maximum no. of electrons in a subshell
Number of angular nodes = l = 3 Þ f-subshell = 2(2l + 1)
36. (a) 5 f 5+3=8 So, total no. of electron in 4f subshell
6p 6+1=7
= 2 (2 × 3 + 1) = 14 electrons.
5p 5+1=6
44. (a)
4d 4+2=6
5f > 6p > 5p > 4d 1s
37. (d) The correct configuration of 'N' is 2s 2p
1s2 2s 2 2p1x 2p1y 2p1z
3s 3p 3d
4s 4p 4d 4f
38. (d) Two electrons occupying the same orbital
should have opposite spins i.e. they differ in 5s 5p 5d 5f
spin quantum number.
39. (a) Given: n = 3, l = 1, m = 0 6s 6p 6d 6f
Hence orbital is 3p
–1 0 +1 When n = 6, the sequence of filling of electrons:
6s ¾¾ ® 4f ¾¾ ® 5d ¾¾ ® 6p
or ns ¾¾ ® (n – 2)f ¾¾ ® (n – 1)d ¾¾ ® np
hence the number of orbital identified by m = 0
45. (b) Total no. of atomic orbital in a shell = n2.
can be one only.
Given n = 4; hence number of atomic orbitals in
40. (c) n = 3 ® 3rd shell
4th shell will be 16.
l = 1 ® p sub shell.
46. (b) m = 2 l +1, thus for l = 2, m = 5, hence values
m = – 1 is possible for two electrons present in
of m will be – 2, –1, 0, + 1, + 2.
an orbital.
Therefore for l = 2, m cannot have the value – 3.
m = 0 is fixed for Pz orbital but Px and Py orbital 47. (d) The number of subshell is (2 l + 1). The
can take any value among ± 1. maximum number of electrons in the sub shell is
2 (2 l + 1) = (4 l + 2)
EBD_8336
20 CHEMISTRY
48. (b) (ii) is not possible for any value of n because 58. (c) Outer electronic configuration of Cl
2 2 2 1
l varies from 0 to (n – 1) thus for n = 2, l can be = 3s 3 p x 3 p y 3 p z
only 0 and 1. Outer electronic configuration of
(iv) is not possible because for l = 0, m = 0. Cl– =3s 2 3px2 3p y 2 3pz 2
(v) is not possible because for l = 2, m varies
hence, Cl– contains four lone pairs of electrons.
from –2 to +2.
59. (b) The sub-shell with lowest value of (n + l) is
49. (b) Magnetic quantum no. represents the filled up first. When two or more sub-shells have
orientation of atomic orbitals in an atom. For same (n + l) value the subshell with lowest value
example px, py & pz have orientation along of 'n' is filled up first therefore the correct order is
X-axis, Y-axis & Z-axis. orbital 4s 3d 4p 5s 4d
50. (c) Amongst isoelectronic species, ionic radii n+l 4 + 0 3 + 2 4 +1 5 + 0 4 + 2
of anion is more than that of cations. Further value =4 5 5 5 6
size of anion increases with increase in –ve 60. (d) l = 3 means f-subshell. Maximum no. of
charge and size of cation decreases with increase electrons = 4l + 2 = 4 × 3 + 2 = 14
in + ve charge. Hence, ionic radii decreases from 61. (d) This is as per the definition of Pauli’s
Exclusion principle.
O– to Al3+.
62. (a) Cu+ = 29 – 1 = 28 e–
51. (c) Both CN– and CO have 14 electrons.
thus the electronic configuration of Cu+ is
52. (a) Quantum number n = 3, l = 2, m = +2 represent
one of the 3d-orbitals with = 1s 2 2s 2 2p 6 3s 2 3p6 3d10
144244 3
1 18e -
s=±
2 63. (c) n = 2, l = 1 means 2 p – orbital. Electrons that
can be accommodated = 6 as p sub-shell has 3
which is possible only for one orbital.
orbitals and each orbital contains 2 electrons.
53. (c) The molecule which contains same number
64. (b) No. of orbitals in a sub-shell = 2l + 1
of electrons are called isoelectronic. eg.
Þ No. of electrons = 2(2l + 1) = 4l + 2
N2 = CO = CN - = O +2 2 = 14e– 65. (c) N(7) = 1s2 2s2 2p3
54. (a) We know that ions which have the same N 2+ = 1s 2 , 2s 2 2 p1x
number of electrons are called isoelectronic. We
Unpaired electrons = 1.
also know that both CO and CN– have 14
66. (a) No. of radial nodes in 3p-orbital
electrons, therefore these are isoelectronic.
= (n – l – 1)
55. (d) The orbitals which have same energy are
[for p ortbital l = 1]
called degenerate orbitals eg. px , p y , pz .
=3–1–1=1
56. (d) For s-orbital; l = 0
Thus value of m must be zero, which is given as There are two types of nodes, angular nodes and
radial notes. Angular nodes are typically flat plane.
–1 in the question. Hence, the electron can not The quantum number l determines the number of
be present in s-orbital. angular nodes in an orbital. Radial nodes are spheres
57. (b) The sub-shell are 3d, 4d, 4p and 5s, 4d has that occurs as the principal quantum number
highest energy as n + l value is maximum for increases. Total nodes of an orbital is the sum of
angular and radial nodes which is given by
this. N=n–l–1
3 Classification of Elements
and Periodicity in Properties
2020 2019 2018 2017 2016

modern periodic
2 E 1 E
Modern periodic table
table Electronic
1 A
configuration
I.E/ionic,atomic
Periodic trends in size/electron gain 1 A 1 A
properties of enthalpy trend
elements Ionisation enthalpy
1 A
trend
Topic 1: Modern Periodic Table 3. The element Z = 114 has been discovered recently.
It will belong to which of the following family/
1. Identify the incorrect match. [2020] group and electronic configuration ? [2017]
Name IUPAC Official (a) Carbon family, [Rn] 5f 14 6d10 7s2 7p2
Name (b) Oxygen family, [Rn] 5f 14 6d10 7s2 7p4
(A) Unnilunium (i) Mendelevium (c) Nitrogen family, [Rn] 5f 14 6d10 7s2 7p6
(B) Unniltrium (ii) Lawrencium (d) Halogen family, [Rn] 5f 14 6d10 7s2 7p5
(C) Unnilhexium (iii) Seaborgium 4. An atom has electronic configuration 1s2 2s2 2p6
(D) Unununnium (iv) Darmstadtium 3s2 3p6 3d3 4s2, you will place it in which group?
(a) (B), (ii) (b) (C), (iii) (a) Fifth (b) Fifteenth [2002]
(c) (D), (iv) (d) (A), (i) (c) Second (d) Third
2. Match the following : [2020] 5. The element, with atomic number 118, will be
(a) alkali (b) noble gas [1996]
Oxide Nature
(c) lanthanide (d) transition element
(A) CO (i) Basic 6. The electronic configuration of an element is
(B) BaO (ii) Neutral
(C) Al2O3 (iii) Acidic 1s 2 2s 2 2 p6 3s 2 3 p3. What is the atomic number
(D) Cl2O7 (iv) Amphoteric of the element, which is just below the above
Which of the following is correct option? element in the periodic table? [1995]
(A) (B) (C) (D) (a) 33 (b) 34
(a) (ii) (i) (iv) (iii) (c) 36 (d) 49
(b) (iii) (iv) (i) (ii) 7. If the atomic number of an element is 33, it will
(c) (iv) (iii) (ii) (i) be placed in the periodic table in the [1993]
(a) First group (b) Third group
(d) (i) (ii) (iii) (iv) (c) Fifth group (d) Seventh group.
EBD_8336
22 CHEMISTRY
Topic 2: Periodic Trends in Properties of Thus process of formation of O2– in gas phase
Elements is unfavourable even though O2– is isoelectronic
with neon. It is due to the fact that [2015 RS]
8. Match the oxide given in column A with its (a) Electron repulsion outweighs the stability
property given in column B [NEET Odisha, 2019] gained by achieving noble gas configuration
Column-A Column-B (b) O– ion has comparatively smaller size than
(i) Na2O (A) Neutral oxygen atom
(ii) Al2O3 (B) Basic (c) Oxygen is more electronegative
(iii) N2O (C) Acidic
(d) Addition of electron in oxygen results in
(iv) Cl2O7 (D) Amphoteric
larger size of the ion.
Which of the following options has all correct
14. Which of the following orders of ionic radii is
pairs?
(a) (i)-(B), (ii)-(D), (iii)-(A), (iv)-(C) correctly represented ? [2014]
(b) (i)-(B), (ii)-(A), (iii)-(D), (iv)-(C) (a) H– > H+ > H (b) Na+ > F– > O2–
(c) (i)-(C), (ii)-(B), (iii)-(A), (iv)-(D) (c) F– > O2– > Na+ (d) Al3+> Mg2+> N3–
(d) (i)-(A), (ii)-(D), (iii)-(B), (iv)-(C) 15. Which one of the following arrangements
9. For the second period elements the correct represents the correct order of least negative to
increasing order of first ionisation enthalpy is : most negative electron gain enthalpy for C, Ca,
(a) Li < Be < B < C < N < O < F < Ne [2019] Al, F and O? [NEET Kar. 2013]
(b) Li < B < Be < C < O < N < F < Ne (a) Ca < Al < C < O < F(b) Al < Ca < O < C < F
(c) Li < B < Be < C < N < O < F < Ne (c) Al < O < C < Ca < F (d) C < F < O < Al < Ca
(d) Li < Be < B < C < O < N < F < Ne 16. Identify the wrong statement in the following:
10. The correct order of atomic radii in group 13 [2012]
elements is [2018] (a) Amongst isoelectronic species, smaller the
(a) B < Al < In < Ga < Tl positive charge on the cation, smaller is
(b) B < Al < Ga < In < Tl the ionic radius.
(c) B < Ga < Al < In < Tl (b) Amongst isoelectronic species, greater the
(d) B < Ga < Al < Tl < In negative charge on the anion, larger is the
11. In which of the following options the order of ionic radius.
arrangement does not agree with the variation (c) Atomic radius of the elements increases as
of property indicated against it ? [2016] one moves down the first group of the
(a) Al3+ < Mg2+ < Na+ < F– (increasing ionic periodic table.
size) (d) Atomic radius of the elements decreases
(b) B < C < N < O (increasing first ionisation as one moves across from left to right in
enthalpy) the 2nd period of the periodic table.
(c) I < Br < F < Cl (increasing electron gain 17. What is the value of electron gain enthalpy of
enthalpy) Na+ if IE1 of Na = 5.1 eV ? [2011M]
(d) Li < Na < K < Rb (increasing metallic radius) (a) –5.1 eV (b) –10.2 eV
12. The species Ar, K+ and Ca2+ contain the same
(c) +2.55 eV (d) +10.2 eV
number of electrons. In which order do their radii
18. Among the elements Ca, Mg, P and Cl, the order
increase ? [2015]
of increasing atomic radii is : [2010]
(a) Ca 2+ < Ar < K + (b) Ca 2+ < K + < Ar (a) Ca < Mg < P < Cl (b) Mg < Ca < Cl < P
(c) K + < Ar < Ca 2+ (d) Ar < K + < Ca 2+ (c) Cl < P < Mg < Ca (d) P < Cl < Ca < Mg
13. The formation of the oxide ion O2–(g), from 19. Which of the following represents the correct
oxygen atom requires first an exothermic and order of increasing electron gain enthalpy with
then an endothermic step as shown below : negative sign for the elements O, S, F and Cl ?
[2005, 2010]
O(g) + e– ® O–(g); Df H = –141 kJ mol–1
(a) Cl < F < O < S (b) O < S < F < Cl
O– (g) + e– ® O2– (g); Df H = +780 kJ mol–1 (c) F < S < O < Cl (d) S < O < Cl < F
Classification of Elements and Periodicity in Properties 23
20. The correct order of the decreasing ionic radii 29. Which of the following statements is true? [2002]
among the following isoelectronic species are : (a) Silicon exhibits 4 coordination number in
(a) Ca 2+ > K + > S2– > Cl – [2010] its compound
– 2-
(b) Cl > S > Ca > K 2+ + (b) Bond energy of F2 is less than Cl2
(c) S2– > Cl – > K + > Ca 2+ (c) Mn(III) oxidation state is more stable than
Mn(II) in aqueous state
(d) K + > Ca 2+ > Cl – > S 2–
21. Amongst the elements with following electronic (d) Elements of 15th group shows only +3 and
configurations, which one of them may have the +5 oxidation states
highest ionization energy? [2009] 30. Which of the following order is wrong? [2002]
(a) Ne [3s23p2] (b) Ar [3d104s24p3 ] (a) NH3 < PH3 < AsH3 – Acidic
(c) Ne [3s23p1] (d) Ne [3s23p3] (b) Li < Be < B < C – First IP
22. The stability of + 1 oxidation state increases in (c) Al2O3 < MgO < Na2O < K2O – Basic
the sequence: [2009] (d) Li+ < Na+ < K+ < Cs+ – Ionic radius
(a) Tl < In < Ga < Al (b) In < Tl < Ga < Al 31. Correct order of first IP among following
(c) Ga < In < Al < Tl (d) Al < Ga < In < Tl elements Be, B, C, N, O is [2001]
23. Which one of the following ionic species has the (a) B < Be < C < O < N (b) B < Be < C < N < O
greatest proton affinity to form stable compound? (c) Be < B < C < N < O (d) Be < B < C < O < N
(a) NH -2 (b) F– [2007] 32. Of the given electronic configurations for the
elements, which electronic configuration
(c) I– (d) HS–
indicates that there will be abnormally high
24. Which of the following electronic configuration
difference in the second and third ionization
of an atom has the lowest ionisation enthalpy?
energy for the element? [1999]
[2007]
(a) 1s2 2s2 2p6 3s2 (b) 1s2 2s2 2p6 3s1
(a) 1s2 2s2 2p3 (b) 1s2 2s2 2p5 3s1
(c) 1s2 2s2 2p6 3s2 3p1(d) 1s2 2s2 2p6 3s2 3p2
(c) 1s2 2s2 2p6 (d) 1s2 2s2 2p5
33. The first ionization potentials (eV) of Be and B
25. Identify the correct order of the size of the following:
respectively are [1998]
(a) Ca2+ < K+ < Ar < Cl– < S2– [2007]
(a) 8.29, 9.32 (b) 9.32, 9.32
(b) Ar < Ca2+ < K+ < Cl– < S2–
(c) 8.29, 8.29 (d) 9.32, 8.29
(c) Ca2+ < Ar < K+ < Cl– < S2–
34. Which of the following does not represent the
(d) Ca2+ < K+ < Ar < S2– < Cl–
correct order of the properties indicated [1997]
26. Which one of the following oxides is expected
(a) Ni2+ > Cr2+ > Fe2+ > Mn2+ (size)
to exhibit paramagnetic behaviour? [2005]
(b) Sc > Ti > Cr > Mn (size)
(a) CO2 (b) SiO2
(c) Mn2+ > Ni2+ < Co2+ <Fe2+ (unpaired electron)
(c) SO2 (d) ClO2
(d) Fe2+ > Co2+ > Ni2+ > Cu2+ (unpaired electron)
27. Ionic radii are [2004]
35. Which one of the following ions will be the
(a) inversely proportional to effective nuclear
smallest in size? [1996]
charge
(a) Na+ (b) Mg2+
(b) inversely proportional to squar e of
(c) F– (d) O2 –
effective nuclear charge
36. Among the following oxides, the one which is
(c) directly proportional to effective nuclear
most basic is [1994]
charge
(a) ZnO (b) MgO
(d) directly proportional to square of effective
(c) Al2O3 (d) N2O5
nuclear charge
37. One of the characteristic properties of non-
28. Among K, Ca, Fe and Zn, the element which can
metals is that they [1993]
form more than one binary compound with
(a) Are reducing agents
chlorine is [2004]
(b) Form basic oxides
(a) Fe (b) Zn
(c) Form cations by electron gain
(c) K (d) Ca
(d) Are electronegative
EBD_8336
24 CHEMISTRY
38. Which electronic configuration of an element (a) Ga, In, Tl (b) Na, Mg, Al
has abnormally high difference between second (c) N, O, F (d) V, Cr, Mn
and third ionization energy? [1993] 43. Elements of which of the following groups will
(a) 1 s2, 2 s2, 2 p6, 3 s1 form anions most readily ? [1992]
(b) 1 s2, 2 s2, 2 p6, 3 s1 3 p1 (a) Oxygen family (b) Nitrogen family
(c) 1 s2, 2 s2, 2 p6, 3 s2 3 p2 (c) Halogens (d) Alkali metals
(d) 1 s2, 2 s2, 2 p6, 3 s2 44. In the periodic table, with the increase in atomic
39. In the periodic table from left to right in a period, number, the metallic character of an element
the atomic volume [1993] [1989]
(a) Decreases (a) Decreases in a period and increases in a group
(b) Increases (b) Increases in a period and decreases in a group
(c) Remains same (c) Increases both in a period and the group
(d) First decrease then increases (d) Decreases in a period and the group.
40. Na+, Mg++, Al3+ and Si4+ are isoelectronic. The 45. The electronic configuration of four elements are
order of their ionic size is [1993] given below. Which element does not belong to
(a) Na+ > Mg++ < Al3 + < Si4+ the same family as others ? [1989]
(b) Na+ < Mg++ > Al3+ > Si4+ (a) [Xe]4f 145d101s2 (b) [Kr]4d 10 5s 2
(c) Na+ > Mg++ > Al3+ > Si4+
(c) [Ne]3s23p5 (d) [Ar] 3d10 4s2
(d) Na+ < Mg++ > Al3+ < Si4+
46. Pauling’s electronegativity values for elements
41. One would expect proton to have very large
are useful in predicting [1989]
[1993]
(a) Polarity of the molecules
(a) Charge (b) Ionization potential
(b) Position in the E.M.F. series
(c) Hydration energy (d) Radius.
(c) Coordination numbers
42. Which of the following sets has strongest
(d) Dipole moments.
tendency to form anions ? [1993]
ANSWER KEY
1 (c) 6 (a) 11 (b) 16 (a) 21 (d) 26 (d) 31 (a) 36 (b) 41 (c) 46 (a)
2 (a) 7 (c) 12 (b) 17 (a) 22 (d) 27 (a) 32 (a) 37 (a) 42 (c)
3 (a) 8 (a) 13 (a) 18 (c) 23 (a) 28 (a) 33 (d) 38 (d) 43 (c)
4 (a) 9 (b) 14 (N) 19 (b) 24 (b) 29 (b) 34 (a) 39 (d) 44 (a)
5 (b) 10 (c) 15 (a) 20 (c) 25 (a) 30 (b) 35 (b) 40 (c) 45 (c)
Hints & Solutions

1. (c) Unununium (Z = 111), it is Roentgenium 10. (c) Due to poor shiel ding effect of 3d
(Rg) not Darmstadtium. electrons in Ga, the atomic radii of Ga < Al.
2. (a) CO : Neutral oxide Thus, the correct order of atomic radii is B <
BaO : Basic oxide Ga < Al < In < Tl.
Al2O3 : Amphoteric oxide 11. (b) The correct order is B < C < O < N
Cl2O7 : Acidic oxide Generally ionisation energy increases across a
3. (a) After 86Rn (Group 18), elements from atomic period. But here first I.E. of O is less than the first
number 89 to 103 (actinides) are in group 3 I.E. of N. This is due to the half-filled 2p orbital in
114 = 103 + 11. Thus, element with atomic N(1s2, 2s2, 2p3) which is more stable than the 2p
number 114 will be in group (3 + 11) or group 14 orbital in O (1s2, 2s2, 2p4).
(carbon family). (c) The correct order of electron affinity is
The outer shell configuration of group 14 is I < Br < F < Cl
ns2 = np2. Halogens have high electron affinities which
Hence, only option (a) is correct. decreases on moving down the group. However,
4. (a) The electronic configuration clearly suggest fluorine has lower value than chlorine which is due
that it is a d-block element (having configuration to its small size and repulsion between the electron
added and electrons already present.
(n – 1) d 1– 10 ns 0 – 2 ) which starts from group 3
and goes till group 12. Hence with d3 configuration 12. (b) In isoelectronic species the radius decrease
it would be classified in the fifth group. with increase in nuclear charge hence increasing
5. (b) Electronic configuration of element with order of radius is Ca+2 < K+ < Ar
atomic number 118 will be [Rn]5f 146d10 7s27p6. 13. (a) Incoming electrons occupies the smaller n
Since its elctronic configuration in the outer most = 2 shell, also negative charge on oxygen (O–) is
orbit (ns2np6) resemble with that of inert or noble another factor due to which incoming electron
gases, therefore it will be noble gas element. feel repulsion.
6. (a) Atomic number of the given element is 15 Hence, electron repulsion outweigh the stability
and it belongs to 5th group. Therefore atomic gained by achieving noble gas configuration.
number of the element below the above element 14. (N) All answers are incorrect.
= 15 + 18 = 33.
7. (c) Element with Z = 33 H– > H > H+; O2– > F– < Na+
O2– > F– > Na+; N3– > Mg2+ > Al3+
(1s 2 2s2 p6 3s2 p6d10 4s2 p3 ) lies in fifth (or 15th) For isoelectronic species the size is
group. determined by Zeffe. Higher the Zeffe. lower is
8. (a) Na2O basic oxide the size of the ions/species.
Al2O3 amphoteric oxide 15. (a) As the nuclear charge increases, the force
N2O neutral of attraction between the nucleus and the
Cl2O7 acidic oxide incoming electron increases and hence the
elecron gain enthalpy becomes more negative,
Elements of gp.1 and 2 form besicoxides while
gp. 13 and 14 elements form amphoteric hence the correct order is
oxides. Elements of gp. 16 and 17 form acidic Ca < Al < C < O < F
oxides. Acidic character of oxides increases 16. (a) As the positive charge increases on metal
from left to right in the periodic table. cation, radius decreases. This is due to the fact
9. (b) Consider the stability of electronic that nuclear charge in the case of a cation is
configuration after loss of one electron. acting on lesser number of electrons and pulls
them closer.
EBD_8336
26 CHEMISTRY
17. (a) IE1 of Na = – Electron gain enthalpy of Na + 25. (a) For isoelectronic species, size of anion
= – 5.1 eV. increases as negative charge increases whereas
size of cation decreases with increase in positive
In this question, temperature is to be defined as
absolute zero. This is due to the fact that ionization charge. Further ionic radii of anions is more than
energy and electron affinity are defined at absolute that of cations. Thus the correct order is
zero temperature. Ca2+ < K+ < Ar < Cl– < S2–
5 26. (d) Due to odd number of electrons in ClO2, it
Ionization enthalpy = ionization energy + RT
2 is expected to exhibit paramagnetic behaviour.
5 Cl
Electron gain enthalpy = electron affinity - RT
2
18. (c) 12 Mg P Cl Ca O O
15 17 20 Paramagnetic
160 110 99 197 (pm) 27. (a) Ionic radii are inversely proportional to
So, the order will be: Cl < P < Mg < Ca effective nuclear charge.
19. (b) O < S < F < Cl Ionic radii in the nth orbit is given as
Electron gain enthalpy of given elements are
n2 a0 1
– 141, – 200, – 333 and – 349 kJ mol–1 respectively. rn = or rn µ
Z Z
Due to small size of atom, addition of an electron when n = principal quantum number
is not easy. This is the reason why the magnitude
of electron gain enthalpy of oxygen and fluorine is Z=effective nuclear charge.
less than that of sulphur and chlorine respectively. 28. (a) Among the given options, only Fe shows
20. (c) Among the isoelectronic species, size variable oxidation states so it can form two
increases with the increase in negative charge. chlorides, viz. FeCl2 and FeCl3.
Thus S2– has the highest negative charge and 29. (b) This is because of inter-electronic
hence largest in size followed by Cl–, K+ and Ca2+. replusions between lone pairs.
21. (d) The smaller the atomic size, larger is the B.E. : F–F Cl – Cl
value of ionisation potential. Further the atoms (kJ mol–1) : 158.8
.. ..
242.6
«
having half filled or fully filled orbitals are : .F. - F

« ..:
comparatively more stable, hence more energy 30. (b) Along the period, I.P. generally increases
is required to remove the electron from such but not regularly. Be and B are exceptions. First
atoms. I.P. increases in moving from left to right in a period,
22. (d) The stability of +1 oxidation state increases but I.P. of B is lower than Be.
from aluminium to thallium i.e. 31. (a) Be – 1s22s2; B – 1s22s22p1; C – 1s22s22p2;
Al < Ga < In < Tl N – 1s22s22p3; O – 1s22s22p4. IP increases along
the period. But IP of Be > B. Further IP of O < N
Inert pair effect is generally exhibited by some
heavier nucleus p-block elements with common because atoms with fully or partly filled orbitals are
molecular formula ns2np1–6. These elements have most stable and hence have high ionisation energy.
less tendency to leave their outer most s-electrons
at the time of chemical reaction i.e. electrons 32. (a) Mg = 1s 2 2 s 2 2 p 6 3s 2
present in s-orbital does not participate in the bond After the removal of 2 electrons, the magnesium
formation. For example Tl, Po, Sn, Pb, Bi.
ion will acquire noble gas configuration hence
23. (a) Proton affinity decreases in moving across removal of 3rd electron will require large amount
the period from left to right due to increase in of energy.
charge, within a group the proton affinities 33. (d) First ionisation potential of Be is greater
decreases from top to bottom. than boron due to following configuration
Nitrogen family > Oxygen family > Halogens 2 2 2 2 1
4Be=1s ,2s 5B=1s ,2s 2p
24. (b) 1s 2 , 2s 2 , 2p 5 , 3s 1 is an unstable
Order of attraction of electrons towards nucleus
configuration with the outermost electron in 3rd
2s > 2p, so more amount of energy is required to
orbit. Hence, it has lowest ionisation enthalpy.
remove the electron in 2s-orbital in comparison electronegative non metals and will have the
to 2p orbital. strongest tendency to form anions by gaining
34. (a) In a period on moving from left to right ionic electrons from metal atoms.
radii decreases. 43. (c) Elements of halogen group form anions most
So order of cationic radii is Cr2+ > Mn2+ > Fe2+ > Ni2+ readily.
35. (b) Greater is the positive charge on atom, larger Electron affinity values are high in case of halogen
will be the effective nuclear charge. Hence smaller
because halogens have seven electrons ( ns 2 np 5 )
is the size. in the valence shell, they have a strong tendency
36. (b) N2O5 is strongly acidic, ZnO and Al2 O3 are to acquire the nearest inert gas configuration by
amphoteric, therefore, MgO is most basic. gaining an electron from the metallic atom and form
halide ions easily.
37. (a) Non metals form oxides with oxygen and
thus reduce oxides of metals behaving as 44. (a) Metallic character decreases in a period and
reducing agents. increases in a group.
45. (c) Elements (a), (b) and (d) belong to the same
38. (d) Abnormally high difference between 2nd group since each one of them has two electrons
and 3rd ionization energy means that the element in the s-sub shell. In contrast, element (c) has
has two valence electrons. seven electrons in the valence shell and hence
39. (d) Atomic volume is the volume occupied by does not lie in the same group.
one mole of an element. Within a period from left 46. (a) Paulings electronegativity values for elements
to right, atomic volume first decreases and then are useful in predicting polarity of the molecule.
increases due to increase in nuclear charge and
increase in molar mass. Pauling scale of electronegativity was helpful in
predicting :
40. (c) Amongst isoelectronic ions, the size of the (i) Nature of bond between two atoms
cation decreases as the magnitude of the charge (ii) Stability of bond
increases. By calculating the difference in electro-negativities,
41. (c) Proton (H+) being very small in size would polarity of bond can be calculated.
have very large hydration energy.
42. (c) N, O and F (p-block elements) are highly
EBD_8336
28 CHEMISTRY
4 Chemical Bonding and

Molecular Structure
2020 2019 2018 2017 2016

Dipole moment and dipole moment 1 A
bond polarity
structure and
VSEPR theory and 2 A 2 A
hybridisation
hybridisation
VSEPR theory 2 E
Valence bond and molecular orbital
1 A 1 A 1 A 1 A
molecular orbital theory/bond order
theory valence bond theory 1 A
Topic 1: Electrovalent, Covalent and 5. Among the following electron deficient

Co-ordinate Bonding compound is : [2000]
1. Which of the following is electron - deficient? (a) BCl3 (b) CCl4
[NEET 2013] (c) PCl5 (d) PCl3
6. Which of the following compounds has a
(a) (SiH3)2 (b) (BH3)2
3-centre bond? [1996]
(c) PH3 (d) (CH3)2 (a) Diborane (b) Carbon dioxide
2. The correct sequence of increasing covalent (c) Boron trifluroide (d) Ammonia
character is represented by [2005] 7. Linus Pauling received the Nobel Prize for his
(a) LiCl < NaCl < BeCl2 work on [1994]
(b) BeCl2 < LiCl < NaCl (a) atomic structure (b) photosynthesis
(c) NaCl < LiCl < BeCl2 (c) chemical bonds (d) thermodynamics
(d) BeCl2 < NaCl < LiCl 8. Which of the following pairs will form the most
stable ionic bond ? [1994]
3. Which of the following is the electron (a) Na and Cl (b) Mg and F
deficient molecule? [2005] (c) Li and F (d) Na and F
(a) C2H6 (b) B2H6 9. The weakest among the following types of bonds
(c) SiH4 (d) PH3 is [1994]
4. Cation and anion combines in a crystal to form (a) ionic (b) covalent
following type of compound. [2000] (c) metallic (d) H–bond.
10. Strongest bond is in between [1993]
(a) ionic (b) metallic (a) CsF (b) NaCl
(c) covalent (d) dipole-dipole (c) Both (a) and (b) (d) None of above
Chemical Bonding and Molecular Structure 29
11. Among the following which compound will 17. In X — H — Y, X and Y both are electronegative
show the highest lattice energy ? [1993] elements
(a) KF (b) NaF (a) Electron density on X will increase and on
(c) CsF (d) RbF H will decrease [2001]
12. Among LiCl, BeCl2 BCl3 and CCl4, the covalent (b) In both electron density will decrease
bond character follows the order [1990] (c) In both electron density will increase
(a) LiCl < BeCl2 > BCl3 > CCl4 (d) Electron density will decrease on X and will
(b) BeCl2 < BCl3 < CCl4 < LiCl increase on H
(c) LiCl < BeCl2 < BCl3 < CCl4 18. Which one of the following molecules will form
(d) LiCl > BeCl2 > BCl3 > CCl4 a linear polymeric structure due to hydrogen
13. Which of the following does not apply to metallic bonding? [2000]
bond ? [1989] (a) NH3 (b) H2O
(a) Overlapping valence orbitals (c) HCl (d) HF
(b) Mobile valency electrons 19. In PO43– ion, the formal charge on each oxygen
atom and P—O bond order respectively are
(c) Delocalized electrons
[1998]
(d) Highly directed bonds.
(a) –0.75, 0.6 (b) – 0.75, 1.0
Topic 2: Octet rule, Resonance and (c) – 0.75, 1.25 (d) –3, 1.25
Hydrogen Bonding 20. The low density of ice compared to water is due
to [1997]
14. Which of the following structures is the most (a) hydrogen-bonding interactions
preferred and hence of lowest energy for SO3? (b) dipole-dipole interactions
[2011 M] (c) dipole-induced dipole interactions
(d) induced dipole-induced dipole interactions
21. The boiling point of p-nitrophenol is higher than
(a) (b) that of o-nitrophenol because [1994]
(a) NO2 group at p-position behave in a
different way from that at o-position.
(b) intramolecular hydrogen bonding exists in
p-nitrophenol
(c) there is intermolecular hydrogen bonding
(c) (d)
in p-nitrophenol
(d) p-nitrophenol has a higher molecular
15. What is the dominant intermolecular force or weight than o-nitrophenol.
bond that must be overcome in converting liquid 22. Which one of the following is the correct order
CH3OH to a gas? [2009]
of interactions ? [1993]
(a) Dipole-dipole interaction
(a) Covalent < hydrogen bonding < van der
(b) Covalent bonds
Waals < dipole-dipole
(c) London dispersion force
(d) Hydrogen bonding (b) van der Waals < hydrogen bonding <
16. Which of the following is not a correct dipole-dipole < covalent
statement? [2006] (c) van der Waals < dipole-dipole < hydrogen
(a) The cannonical structures have no real bonding < covalent
existence (d) Dipole-dipole < van der Waals < hydrogen
(b) Every AB 5 molecule does in fact have bonding < covalent.
square pyramidal structure 23. Strongest hydrogen bond is shown by [1992]
(c) Multiple bonds are always shorter than (a) Water
corresponding single bonds (b) Ammonia
(d) The electron-deficient molecules can act (c) Hydrogen fluoride
as Lewis acids (d) Hydrogen sulphide.
EBD_8336
30 CHEMISTRY
24. Which one of the following formulae does not 30. The electronegativity difference between N and
correctly represent the bonding capacities of the F is greater than that between N and H yet the
two atoms involved ? [1990] dipole moment of NH3 (1.5 D) is larger than that
+
of NF3 (0.2D). This is because [2006]
é H ù (a) in NH3 the atomic dipole and bond dipole
ê | ú are in the same direction whereas in NF3
(a) êH — P — H ú
ê |
ú these are in opposite directions
ë H û (b) in NH3 as well as NF3 the atomic dipole
(b) F F and bond dipole are in opposite directions
(c) in NH3 the atomic dipole and bond dipole
O
O are in the opposite directions whereas in
(c) O¬ N NF3 these are in the same direction
O–H (d) in NH3 as well as in NF3 the atomic dipole
O and bond dipole are in the same direction
31. Wh ich of th e followi ng woul d ha ve a
(d) H – C = C permanent dipole moment? [2005]
O–H
(a) SiF4 (b) SF 4
25. Which one shows maximum hydrogen bonding?
(c) XeF4 (d) BF3
(a) H2O (b) H2Se [1990]
32. The correct order of the O–O bond length in O2,
(c) H2S (d) HF.
H2O2 and O3 is [1995, 2005]
Topic 3: Dipole Moment and Bond Polarity (a) O 2 > O 3 > H 2O 2
26. Which of the following set of molecules will (b) O 3 > H 2O 2 > O 2
have zero dipole moment? [2020]
(c) O 2 > H 2O 2 > O 3
(a) Boron trifluoride, hydrogen fluoride,
carbon dioxide, 1,3-dichlorobenzene (d) H 2 O 2 > O 3 > O 2
(b) Nitrogen trifluoride, beryllium difluoride, 33. H2O is dipolar, whereas BeF2 is not. It is because
water, 1,3-dichlorobenzene [2004]
(c) Boron trifluoride, beryllium difluoride, (a) the electronegativity of F is greater than
carbon dioxide, 1,4-dichlorobenzene that of O
(d) Ammonia, beryllium difluoride, water, (b) H2O involves hydrogen bonding whereas
1,4-dichlorobenzene BeF2 is a discrete molecule
27. Which of the following is the correct order of (c) H2O is linear and BeF2 is angular
(d) H2O is angular and BeF2 is linear
dipole moment? [NEET Odisha 2019]
34. The dipole moments of diatomic molecules AB
(a) H2O < NF3 < NH3 < BF3 and CD are 10.41D and 10.27 D, respectively
(b) NH3 < BF3 < NF3 < H2O while their bond distances are 2.82 and 2.67 Å,
(c) BF3 < NF3 < NH3 < H2O respectively. This indicates that [1999]
(a) bonding is 100% ionic in both the molecules
(d) BF3 < NH3 < NF3 < H2O
(b) AB has more ionic bond character than CD
28. Which of the following molecules has the (c) AB has lesser ionic bond character than
maximum dipole moment ? [2014] CD
(a) CO2 (b) CH4 (d) bonding is nearly covalent in both the
(c) NH3 (d) NF3 molecules
29. Which of the following is a polar molecule ? 35. Which of the following bonds will be most polar?
[NEET 2013] [1992]
(a) SF4 (b) SiF4 (a) N – Cl (b) O – F
(c) XeF4 (d) BF3 (c) N – F (d) N – N
36. H2O has a non zero dipole moment while BeF2 (b) lone pair - lone pair > bond pair - bond pair
has zero dipole moment because [1989] > lone pair - bond pair
(a) H2O molecule is linear while BeF2 is bent (c) bond pair - bond pair > lone pair - bond
(b) BeF2 molecule is linear while H2O is bent pair > lone pair - lone pair
(c) Fluorine has more electronegativity than (d) lone pair - bond pair > bond pair - bond
oxygen pair > lone pair - lone pair
(d) Beryllium has more electronegativity than 43. Which of the following pairs of ions are
oxygen. isoelectronic and isostructural ? [2015]
Topic 4: VSEPR Theory and Hybridisation (a) ClO3– , CO32– (b) SO32– , NO3–
37. In the structure of ClF3, the number of lone pair
of electrons on central atom ‘Cl’ is [2018]
(c) ClO3– , SO32– (d) CO32– , SO32–
(a) One (b) Two 44. Maximum bond angle at nitrogen is present in
(c) Three (d) Four which of the following ? [2015]
38. Which of the following molecules represents (a) NO 2– (b) NO +2
the order of hybridisation sp2, sp2, sp, sp from
left to right atoms? [2018] (c) NO3– (d) NO 2
(a) HC º C – C º CH 45. In which of the following pairs, both the species
(b) CH2 = CH – C º CH are not isostructural ? [2015 RS]
(c) CH3 – CH = CH – CH3
(d) CH2 = CH – CH = CH2 (a) SiCl4 , PCl+
4
39. Which of the following pairs of compounds is (b) diamond, silicon carbide
isoelectronic and isostructural ? [2017] (c) NH3, PH3
(a) TeI2,XeF2 (b) IBr2- , XeF2 (d) XeF4, XeO4
(c) IF3, XeF2 (d) BeCl2,XeF2 46. Be2+ is isoelectronic with which of the following
40. The species, having bond angles of 120° is :- ions? [2014]
[2017] (a) H+ (b) Li+
(a) CIF3 (b) NCl3 (c) Na+ (d) Mg2+
(c) BCl3 (d) PH3 47. Which one of the following species has plane
41. Consider the molecules CH4, NH3 and H2O. triangular shape ? [2014]
(a) N3 – (b) NO3 –
Which of the given statements is false? [2016]
(a) The H–C–H bond angle in CH4, the H–N–H (c) NO2– (d) CO2
bond angle in NH3, and the H–O–H bond 48. In which of the following pair both the species
angle in H2O are all greater than 90° have sp3 hybridization? [NEET Kar. 2013]
(b) The H–O–H bond angle in H2 O is larger (a) H2S, BF3 (b) SiF4, BeH2
than the H–C–H bond angle in CH4. (c) NF3, H2O (d) NF3, BF3
(c) The H–O–H bond angle in H2O is smaller 49. XeF2 is isostructural with [NEET 2013]
than the H–N–H bond angle in NH3. (a) ICl2– (b) SbCl3
(d) The H–C–H bond angle in CH4 is larger (c) BaCl2 (d) TeF2
than the H–N–H bond angle in NH3. 50. Which of the following species contains three
42. Predict the correct order of electron repulsion bond pairs and one lone pair around the central
among the following : [2016] atom ? [2012]
(a) lone pair- lone pair > lone pair - bond pair > (a) H2O (b) BF3
–
bond pair - bond pair (c) NH2 (d) PCl3
EBD_8336
32 CHEMISTRY
51. Which one of the following pairs is isostructural (a) NO -2 and NH 3 (b) BF3 and NO -2
(i.e., having the same shape and hybridization)? (c) NH -2 and H 2 O (d) BF3 and NH -2
(a) é BCl3 and BrCl3- ù [2012] 58. In which of the following molecules / ions
ë û
-ù
BF3, NO2- , NH 2- and H2O , [2009]
é
(b) ë NH3 and NO3 û
the central atom is sp2 hybridized ?
(c) [ NF3 and BF3 ] (a) NH 2- and H2O (b) NO2- and H2O
é BF4- and NH +4 ù (c) BF3 and NO 2- (d) NO 2- and NH 2-
(d) ë û 59. The correct order of increasing bond angles in
52. Which of the two ions from the list given below the following triatomic species is : [2008]
that have the geometry that is explained by the (a) NO-2 < NO+2 < NO 2
same hybridization of orbitals, NO2–, NO3– , (b) NO-2 < NO2 < NO2+
NH2–, NH4+, SCN– ? [2011]
(a) NO2– and NO3– (b) NH4+ and NO3– (c) NO+2 < NO 2 < NO2-
(c) SCN– and NH2– (d) NO2– and NH2– (d) NO +2 < NO-2 < NO
53. Considering the state of hybridization of carbon 60. In which of the following pairs, the two species
atoms, find out the molecule among the following are isostructural? [2007]
which is linear ? [2011] (a) SO32– and NO3– (b) BF3 an NF3
(a) CH3– CH = CH–CH3 (c) BrO3– and XeO3 (d) SF4 and XeF4
(b) CH3 – C º C – CH3 61. Which of the following is not isostructural with
(c) CH2 = CH – CH2 – C º CH SiCl4? [2006]
(d) CH3 – CH2 – CH2 – CH3 (a) SO42– (b) PO43–
54. In which of the following molecules the central (c) NH4+ (d) SCl4
atom does not have sp3 hybridization? [2010] 62. Which of the following species has a linear shape ?
(a) SO2 (b) NO2+ [2006]
(a) NH +4 (b) CH4 (c) O3 (d) NO2–
(c) SF4 (d) BF4– 63. In which of the following molecules all the bonds
55. Some of the properties of the two species, NO3- are not equal? [2006]
and H3O+ are described below. Which one of (a) BF3 (b) AlF3
them is correct? [2010] (c) NF3 (d) ClF3
(a) Similar in hybridization for the central atom 64. Which of the following molecules has trigonal
with different structures. planar geometry? [2005]
(a) BF3 (b) NH3
(b) Dissimilar in hybridization for the central
(c) PCl3 (d) IF3
atom with different structures.
65. In BrF 3 molecule, the lone pairs occupy
(c) isostructural with same hybridization for
equatorial positions to minimize [2004]
the central atom.
(a) lone pair - bond pair repulsion only
(d) Isostructural with different hybridization (b) bond pair - bond pair repulsion only
for the central atom. (c) lone pair - lone pair repulsion and lone pair
56. In which one of the following species the central - bond pair repulsion
atom has the type of hybridization which is not (d) lone pair - lone pair repulsion only
the same as that present in the other three? 66. In an octahedral structure, the pair of d orbitals
(a) SF4 (b) I3– [2010] involved in d 2 sp3 hybridization is [2004]
(c) SbCl52– (d) PCl5 (a) d d (b) d xz, d 2 2
57. In which of the following pairs of molecules/ x2 - y 2 , z 2 x -y
ions, the central atoms have sp2 hybridization? (c) d d (d) d xy , d yz
[2010] z 2 , xz
67. In a regular octahedral molecule, MX6 the number 77. The BCl3 is a planar molecule whereas NCl 3 is
of X - M - X bonds at 180° is [2004] pyramidal because [1995]
(a) three (b) two (a) B-Cl bond is more polar than N-Cl bond
(c) six (d) four (b) N-Cl bond is more covalent than B-Cl bond
68. Which of the following has pp – dp bonding? (c) nitrogen atom is smaller than boron atom
(a) NO3– (b) SO32– [2002] (d) BCl3 has no lone pair but NCl3 has a lone
(c) BO33– (d) CO32– pair of electrons
69. Main axis of a diatomic molecule is z, molecular 78. The distance between the two adjacent carbon
orbital px and py overlap to form which of the atoms is largest in [1994]
following orbital? [2001] (a) benzene (b) ethene
(a) p - molecular orbital (c) butane (d) ethyne
(b) s - molecular orbital 79. Among the following orbital bonds, the angle is
(c) d - molecular orbital minimum between [1994]
(d) No bond will be formed
(a) sp3 bonds (b) px and py orbitals
70. Which of the following two are isostructural?
(c) H – O – H in water (d) sp bonds.
[2001]
80. Which of the following does not have a
(a) NH3, BF3 (b) PCl5, ICl5
tetrahedral structure? [1994]
(c) XeF2, IF2– (d) CO3–2, SO3–2
(a) BH –4 (b) BH3
71. In which of the following, the bond angle is
maximum? [2001] (c) NH +4 (d) H 2 O.
(a) NH3 (b) SCl2 81. Which of the following statements is not correct ?
(c) NH4+ (d) PCl3 [1993]
72. Among the following ions the pp–dp overlap (a) Double bond is shorter than a single bond
could be present in [2000] (b) Sigma bond is weaker than a p (pi) bond
(a) NO -2 (b) NO 3- (c) Double bond is stronger than a single bond
(d) Covalent bond is stronger than hydrogen
(c) PO34- (d) CO 23-
bond.
73. Which one of the following has the pyramidal 82. Which structure is linear ? [1992]
shape? [1999] (a) SO2 (b) CO2
(a) CO32– (b) SO3
(c) BF3 (d) PF3 (c) CO 32- (d) SO 24 -
74. Which of the following molecules is planar? 83. Which one of the following has the shortest
(a) SF4 (b) XeF4 [1998] carbon carbon bond length ? [1992]
(c) NF3 (d) SiF4 (a) Benzene (b) Ethene
75. The AsF5 molecule is trigonal bipyramidal. The (c) Ethyne (d) Ethane
hybrid orbitals used by the As atom for bonding are 84. In compound X, all the bond angles are exactly
d 109°28; X is [1991]
(a) 2 , d 2 , s, p x , p y [1997]
x2 - y z (a) Chloromethane
(b) dxy, s, px, py, pz
(b) Carbon tetrachloride
(c) s, px, py, pz, d (c) Iodoform
z2
(d) d , s, px, py, pz (d) Chloroform.
x2 - y 2
85. Which statement is NOT correct ? [1990]
76. The cylindrical shape of an alkyne is due to the (a) A sigma bond is weaker than a p -bond.
fact that it has [1997] (b) A sigma bond is stronger than a p -bond.
(a) three sigma C – C bonds (c) A double bond is stronger than a single
(b) two sigma C – C and one 'p' C – C bond bond.
(c) three 'p' C – C bonds (d) A double bond is shorter than a single
(d) one sigma C– C and two 'p' C – C bonds bond.
EBD_8336
34 CHEMISTRY
86. In which one of the following molecules the (a) NO (b) CN–
central atom said to adopt sp2 hybridization? (c) CN (d) CN+
(a) BeF2 (b) BF3 [1989] 95. Which of the following pairs of species have
(c) C2H2 (d) NH3 the same bond order ? [2017]
87. Which of the following molecule does not have (a) O2, NO + –
(b) CN , CO
a linear arrangement of atoms ? [1989] (c) N 2 , O 2- (d) CO, NO
(a) H2S (b) C2H2
96. The correct bond order in the following species
(c) BeH2 (d) CO2
is: [2015]
88. Equilateral shape has [1988]
(a) sp hybridisation (b) sp2 hybridisation (a) O 22+ < O 2– < O2+ (b) O +2 < O 2– < O 22+
(c) sp3 hybridisaiton (d) sp3 hybridisation
89. The angle between the overlapping of one (c) O 2– < O +2 < O 22+ (d) O 22+ < O 2+ < O 2–
s-orbital and one p-orbital is [1988] 97. Which of the following options represents the
(a) 180° (b) 120° correct bond order ? [2015]
(c) 109°28' (d) 120° 60' (a) O 2– < O 2 < O 2+ (b) O –2 > O2 < O 2+
Topic 5: Valence Bond and Molecular
Orbital Theory (c) O 2– < O2 > O 2+ (d) O –2 > O2 > O2+
90. Identify a molecule which does not exist. [2020] 98. Which of the following species contains equal
(a) Li2 (b) C2 number of s- and p-bonds : [2015]
(c) O2 (d) He2 (a) XeO4 (b) (CN)2
91. Which of the following is paramagnetic? (c) CH2(CN)2 (d) HCO3–
[NEET Odisha 2019]
99. Decreasing order of stability of O2, O- +
2 ,O 2 and
(a) O2 (b) N2
(c) H2 (d) Li2 O 22- is : [2015 RS]
92. The manganate and permanganate ions are
tetrahedral, due to: [2019]
(a) O+ - 2-
2 > O2 > O2 > O2
(a) The p-bonding involves overlap of p- (b) O 22- > O- +
2 > O2 > O2
orbitals of oxygen with d-orbitals of
manganese (c) O2 > O+ 2- -
2 > O2 > O2
(b) There is no p-bonding
(d) O- 2- +
2 > O2 > O2 > O2
(c) The p-bonding involves overlap of p-orbital
of oxygen with p-orbitals of manganese 100. The hybridization in volved in complex
(d) The p- bonding involves overlap of d- [Ni(CN)4]2–. is (At. No. Ni = 28) [2015 RS]
orbital of oxygen with d-orbitals of (a) dsp 2 (b) sp3
manganese (c) d 2 sp2 (d) d 2 sp3
93. Which of the following diatomic molecular 101. The outer orbitals of C in ethene molecule can
species has only p–bonds accordin g to be considered to be hybridized to give three
Molecular Orbital Theory ? [2019] equivalent sp2 orbitals. The total number of sigma
(a) O2 (b) N2 (s) and pi (p) bonds in ethene molecule is
(c) C2 (d) Be2 [NEET Kar. 2013]
94. Consider the following species : (a) 1 sigma (s) and 2 pi (p) bonds
CN+, CN–, NO and CN (b) 3 sigma (s) and 2 pi (p) bonds
Which one of these will have the highest bond (c) 4 sigma (s) and 1 pi (p) bonds
order? [2018] (d) 5 sigma (s) and 1 pi (p) bonds
102. In which of the following ionisation processes 111. Which of the following has the minimum bond
the bond energy increases and the magnetic length ? [2011]
behaviour changes from paramagnetic to (a) O2+ (b) O2 –
diamagnetic? [NEET Kar. 2013] (c) O2 2– (d) O2
(a) N2 ® N2+ (b) O2 ® O2+ 112. Which one of the following species does not
(c) C2 ® C2+ (d) NO ® NO+ exist under normal conditions? [2010]
103. The pair of species that has the same bond order (a) Be+2 (b) Be2
in the following is: [NEET Kar. 2013] (c) B 2 (d) Li 2
(a) O2, B2 (b) CO, NO+ 113. According to MO theory which of the following
(c) NO–, CN– (d) O2, N2 lists ranks the nitrogen species in terms of
104. Which of the following is paramagnetic ? increasing bond order? [2009]
[NEET 2013] (a) N 2–2 < N –
2 < N 2 (b) N 2 < N 2–
2 < N2
–
(a) O -2 (b) CN– (c) N 2– < N 2– – 2–
2 < N 2 (d) N 2 < N 2 < N 2
(c) NO+ (d) CO 114. The angular shape of ozone molecule (O 3 )
105. Which one of the following molecules contains consists of : [2008]
no p bond? [NEET 2013] (a) 1 sigma and 2 pi bonds
(a) H2O (b) SO2 (b) 2 sigma and 2 pi bonds
(c) NO2 (d) CO2 (c) 1 sigma and 1 pi bonds
106. Four diatomic species are listed below. Identify (d) 2 sigma and 1 pi bonds
the correct order in which the bond order is 115. The correct order of C–O bond length among
increasing in them: [2008, 2012 M] CO, CO32 - , CO2 is [2007]
(a) NO < O2-< C 22 - < He +2 2– 2–
(a) CO < CO3 < CO2 (b) CO3 < CO2 < CO
(b) O -2 < NO < C22 - < He 2+ (c) CO < CO2 < CO32– (d) CO2 < CO32– < CO
116. The number of unpaired electrons in a
(c) C22 - < He 2+ < O2- < NO paramagnetic diatomic molecule of an element
(d) He+2 < O2- < NO < C 22 - with atomic number 16 is [2006]
(a) 3 (b) 4
107. During change of O2 to O 2- ion, the electron (c) 1 (d) 2
adds on which one of the following orbitals ? 117. Among the following the pair in which the two
[2012 M] species are not isostructural is [2004]
(a) p* orbital (b) p orbital
(a) SiF4 and SF4 (b) IO3- and XeO 3
(c) s* orbital (d) s orbital
108. The pair of species with the same bond order is : (c) BH -4 and NH +4 (d) PF6- and SF6
O2–
(a) (b) O+2 , NO+ [2012] 118. Which of the following statements is not correct
2 , B2
for sigma and pi-bonds formed between two
(c) NO, CO (d) N2, O2 carbon atoms? [2003]
109. Bond order of 1.5 is shown by : [2012] (a) Sigma-bond determines the direction
+
(a) O 2 (b) O 2 -
between carbon atoms but a pi-bond has
(c) O 22 - (d) O2 no primary effect in this regard
(b) Sigma-bond is stronger than a pi-bond
110. The pairs of species of oxygen and their (c) Bond energies of sigma- and pi-bonds are
magnetic behaviours are noted below. Which of of the order of 264 kJ/mol and 347 kJ/mol,
the following presents the correct description ? respectively
(a) O -2 , O 22 - – Both diamagnetic [2011 M] (d) Free rotation of atoms about a sigma-bond
is allowed but not in case of a pi-bond
(b) O + ,O22 - – Both paramagnetic 119. In NO3– ion, number of bond pair and lone pair
(c) O+2 ,O2 – Both paramagnetic of electrons on nitrogen atom respectively are
(a) 2, 2 (b) 3, 1 [2002]
(d) O,O 22 - – Both paramagnetic (c) 1, 3 (d) 4, 0
EBD_8336
36 CHEMISTRY
120. The relationship between the dissociation 125. The correct order of N–O bond lengths in NO,
energy of N2 and N2+ is : [2000] NO2–, NO3– and N2O4 is [1996]
(a) Dissociation energy of N2+ > dissociation (a) N 2 O 4 > NO -2 > NO 3- > NO
energy of N2 (b) NO > NO 3- > N 2 O 4 > NO -2
(b) Dissociation energy of N2 = dissociation (c) NO 3- > NO -2 > N 2 O 4 > NO
energy of N2+ (d) NO > N 2 O 4 > NO-2 > NO3-
(c) Dissociation energy of N2 > dissociation
126. The ground state electronic configuration of
energy of N2+ valence shell electrons in nitrogen molecule (N2)
(d) Dissociation energy of N2 can either be
lower or higher than the dissociation energy is written as KK s 2 s 2 , s * 2 s 2 , p 2 p x2 , p 2 p 2y s 2 pz2
of N2+ Bond order in nitrogen molecule is [1995]
121. Which one of the following arrangements rep- (a) 0 (b) 1
resents the increasing bond orders of the given (c) 2 (d) 3
species? [1999] 127. Which of the following species is paramagnetic?
(a) NO+ < NO < NO– < O2– (a) O 22- (b) NO [1995]
(b) O2– < NO– < NO <NO+ (c) CO (d) CN–
(c) NO– < O2– < NO < NO+ 128. Mark the incorrect statement in the following
(d) NO < NO+ < O2– < NO– [1994]
122. Amon g the followin g which one is not (a) The bond order in the species O2, O2+ and
paramagnetic? [Atomic numbers : Be = 4, O2– decreases as O +2 > O 2 > O -2
Ne = 10, As = 33, Cl = 17] [1998]
(b) The bond energy in a diatomic molecule
(a) Cl– (b) Be+ (c) Ne+2 (d) As +
always increases when an electron is lost
123. The number of anti-bonding electron pairs in
(c) Electrons in antibonding M.O. contribute
O 2- 2 molecular ion on the basis of molecular to repulsion between two atoms.
orbital theory is, (Atomic number of O is 8) [1998] (d) With increase in bond order, bond length
(a) 5 (b) 2 (c) 3 (d) 4 decreases and bond strength increases.
124. N2 and O2 are converted into monoanions, N2– 129. Linear combination of two hybridized orbitals
and O2– respectively. Which of the following belonging to two atoms and each having one
statements is wrong ? [1997] electron leads to a [1990]
(a) In N2, the N—N bond weakens (a) Sigma bond
(b) In O2, the O—O bond order increases (b) Double bond
(c) In O2, bond length decreases (c) Co-ordinate covalent bond
(d) N2– becomes diamagnetic (d) Pi bond.
ANSWER KEY
1 (b) 14 (d) 27 (c) 40 (c) 53 (b) 66 (a) 79 (b) 92 (a) 105 (a) 118 (c)
2 (c) 15 (d) 28 (c) 41 (b) 54 (c) 67 (a) 80 (b) 93 (c) 106 (d) 119 (d)
3 (b) 16 (b) 29 (a) 42 (a) 55 (b) 68 (b) 81 (b) 94 (b) 107 (a) 120 (c)
4 (a) 17 (a) 30 (a) 43 (c) 56 (c) 69 (a) 82 (b) 95 (b) 108 (a) 121 (b)
5 (a) 18 (d) 31 (b) 44 (b) 57 (b) 70 (c) 83 (c) 96 (c) 109 (b) 122 (a)
6 (a) 19 (c) 32 (d) 45 (d) 58 (c) 71 (c) 84 (b) 97 (a) 110 (c) 123 (d)
7 (c) 20 (a) 33 (d) 46 (b) 59 (b) 72 (c) 85 (a) 98 (a) 111 (a) 124 (b)
8 (b) 21 (c) 34 (c) 47 (b) 60 (c) 73 (d) 86 (b) 99 (a) 112 (b) 125 (c)
9 (d) 22 (b) 35 (c) 48 (c) 61 (d) 74 (b) 87 (a) 100 (a) 113 (a) 126 (d)
10 (a) 23 (c) 36 (b) 49 (a) 62 (b) 75 (c) 88 (b) 101 (d) 114 (d) 127 (b)
11 (b) 24 (d) 37 (b) 50 (d) 63 (d) 76 (d) 89 (a) 102 (d) 115 (c) 128 (b)
12 (c) 25 (d) 38 (b) 51 (d) 64 (a) 77 (d) 90 (d) 103 (b) 116 (d) 129 (a)
13 (d) 26 (c) 39 (b) 52 (a) 65 (c) 78 (c) 91 (a) 104 (a) 117 (a)
Hints & Solutions

1. (b) (BH3)2 or (B2H6) 9. (d) H-bond is the weakest.
H H H 10. (a) According to Fajan's rule, ionic character
B B increases with increase in size of the cation and
H H H decrease in size of the anion. Thus, CsF has
It contains two, 3 centre - 2 electron bonds that higher ionic character than NaCl and hence bond
are present above and below the plane of strength of CsF is stronger than NaCl.
molecules. Compounds which do not have 11. (b) For compounds containing ions of same
sufficient number of electrons to form normal charge, lattice energy increases as the size the
covalent bonds are called electron deficient ions decrease. Thus, NaF has highest lattice
molecules. energy. The size of cation is in the order Na+ <
2. (c) As difference of electronegativity increases K+ < Rb+ < Cs+.
% ionic character increases and covalent 12. (c) As we move in period from Li ® Be ®
character decreases i.e., as electronegativity B ® C, the electronegativity (EN) increases and
difference decreases covalent character increases. hence the EN difference between the element
Further greater the charge on the cation more and Cl decreases and accordingly the covalent
will be its covalent character. Be has maximum character increases.Thus LiCl < BeCl2 < BCl3<
(+2) charge. CCl4 is correct.
3. (b) The compound, of which central atom is 13. (d) In metallic bonds each ion is surrounded
octetless known as electron deficient compound. by equal no. of oppositely charged ions hence
Hence B2H6 is electron deficient compound. have electrostatic attraction on all sides and
4. (a) Cation and anion form ionic bond in hence do not have directional characteristics.
crystal. 14. (d) The lowest energy structure is the one with
The electrostatic force that binds the oppositely the smallest formal charges on the atoms.
charged ions which are formed by transfer of Option (b) and (c) are not possible structures of
electron from one atom to another is called ionic SO3.
bond.
Option (a) :
5. (a) Boron in BCl3 has 6 electrons in outer most (0)
shell. Hence BCl3 is an electron pair deficient :O:
compound. ×× S
O (+2) O:(–1)
:
6. (a) H H H (–1)
:
Formal charge = total no. of valence e– in the

free atom – total no. of non-bonding (lone pair)
B B 1
e - - (total no. of bonding e–).
2
1
H H H Formal charge on S stom = 6 – 0 – (8) = +2
The bond represented by dots form the 3-centred 2
Similarly, formal charges on coordinated bonded
electron pair bond. oxygen atom and covalently bonded oxygen atom
The idea of three centred electron pair bond are –1 and 0 respectively.
B–H–B bridges is necessary because diborane does :O:
not have sufficient electrons to form normal Option (d) : S :
:
covalent bonds. It has only 12 electrons instead of O O

:
:
14 that are required to give simple ethane like Formal charge on S atom
structure. 1
= 6 – 0 – (12) = 0
7. (c) Chemical bonds. 2
Formal charge on O atom
8. (b) The stability of the ionic bond depends upon 1
the lattice energy which is expected to be more = 6 – 4 – (4) = 0
2
between Mg and F due to +2 charge on Mg atom.
EBD_8336
38 CHEMISTRY
15. (d) Due to intermolecular hydrogen bonding Intramolecular Hydrogen bonding in o-nitrophenol
in methanol, it exist as assosiated molecule. is a interaction with in the molecule whereas the
16. (b) Statement (a), (c), (d) are correct. Statement intermolecular H-bonding in p-nitrophenol is a
(b) is incorrect statement. interaction between the molecules which results
AB5 may have two structures as follows : into higher boiling point. Intermolecular hydrogen
bonding also results in a stronger driving force for
B
cystal formation in other molecules generating
higher melting temperature e.g. p-hydroxy benzoic
B B acid.
A
B B 22. (b) The strength of the interactions follows the
A order: van der Waal’s < hydrogen – bonding <
B B dipole-dipole < covalent.
B B 23. (c) Hydrogen fluoride shows str ongest
B hydrogen bonding due to high electronegativity
Square Pyramidal Trigonal Bipyramidal of fluorine.
O
Individual cannonical structures do not exist. The ||
molecule as such has a single structure, which is
the resonance hybrid of the cannonical forms. 24. (d) H - C = C* - O - H
The star marked carbon has a valency of 5 and
17. (a) In X — H - - - Y, X and Y both are hence this formula is not correct.
electronegative elements (i.e attracts the 25. (d) As F is most electronegative thus HF shows
electron pair) then electron density on X will maximum strength of hydrogen bond.
increase and on H will decrease. With the increase of electronegativity and decrease
18. (d) F—H-----F—H-----F—H-----F in size of the atom to which hydrogen is covalently
HF form linear polymer structure due to linked, the strength of hydrogen bond increases.
hydrogen bonding.
19. (c) Bond order between P – O 26. (c) BF3, BeF2, CO2 and 1, 4-dichlorobenzene
all are symmetrical molecules.
no. of bonds in all possible direction 5
= = = 1.25 F
total no. of resonating structures 4
µ=0
O O
– B
–
F F
O P O–
–
O P O
Be µ=0
O– O– F F
O– O–
O C O µ=0
–
O P O– –
O P O
O O– Cl Cl µ = 0
3
or Formal charge on oxygen = - = -0.75 27. (c) Dipole moment of a molecule is the vector
4
sum of dipoles of bonds. So based on molecular
20. (a) We know that due to polar nature, water geometry of following molecules,
molecules are held together by intermolecular
hydrogen bonds. The structure of ice is open
with large number of vacant spaces, therefore
the density of ice is less than water.
21. (c) The b.p. of p-nitrophenol is higher than
that of o-nitrophenol because in p-nitrophenol Three equal vectors Vectors not alligned in
there is intermolecular H-bonding but in at 120° has resultant the same direction of
o-nitrophenol it is intramolecular H-bonding. dipole moment = 0, so lone pair, so less dipole
non-polar molecule m o m en t
O2 molecule which has purely double bond

(O O). Hence, the correct order is:
H2O2 > O3 > O2 (bond length of O — O)
33. (d) In a linear symmetrical molecule like BeF2,
the bond angle between three atoms is 180°,
Vectors alligned Maximum dipole hence the polarity due to one bond is cancelled
in same direction moment of lone pair by the equal polarity due to other bond. H2O is
angular.
28. (c) Dipole moment of NH3 > NF3
34. (c) As dipole moment = electric charge × bond
d+
d –. . N length
N
D. M. of AB molecules
d+ H H –F
(d ) F
F –
(d )
= 4.8 ´ 10 -10 ´ 2.82 ´ 10 - 8 = 13.53D
H –
(d ) D.M. of CD molecules
m = 1.4D m = 0.23D
(F is more electronegative than N) = 4.8 ´ 10 -10 ´ 2.67 ´ 10 -10 = 12.81D
now % ionic character
29. (a) SF4 has 4 bond pairs and 1 lone pair
of electrons, sp3d hybridisation leads to irregular Actual dipole moment of the bond
=
F Dipole moment of pure ionic compound
| F % ionic character in
shape S and resultant m ¹ 0.
|
10.41
F AB = ´ 100 = 76.94%
F 13.53
30. (a) In NH3 the atomic dipole and bond dipole % ionic character in
are in the same direction whereas in NF3 these 10.27
CD = ´ 100 = 80.23%
are in opposite direction so in the former case 12.81
they are added up whereas in the latter case net 35. (c) As the electronegativity difference
result is reduction of dipole moment. It has been between N and F is maximum hence, this bond is
shown in the following figure : most polar.
Polarity of the bond depends upon the
electronegativity difference of the two atoms
.. ..
N forming the bond. Greater the electronegativity
N
difference, more is the polarity of the bond.
N – Cl O–F N–F N–N
F 3.0–3.0 3.5–4.0 3.0–4.0 3.0–3.0
H H F F 36. (b) BeF2 is linear and hence has zero dipole
H
moment while H2O, being a bent molecule, has a
31. (b) SF4 has permanent dipole moment. finite or non-zero dipole moment.
SF4 has sp3d hybridization and see saw shape 37. (b) The structure of ClF3 is
(irregular geometry).
m¹ 0 F
Whereas XeF4 shows square planar geometry,
SiF4 has tetrahedral shape and BF3 has Trigonal F Cl
planar shape. All these are symmetric molecules.
Hence m = 0.
32. (d) In H — O — O — H, the O – O bond is F
purely single. O3 molecule is a resonance hybrid The number of lone pair of electrons on
of two structures : O O ® O and O ¬ O central Cl is 2.
O. Thus, its bond length will be longer than sp2 sp2 sp sp
38. (b) CH2 = CH – C CH
EBD_8336
40 CHEMISTRY
39. (b) IBr2- , XeF2 1

47. (b) Hybridization of NO3– = (5 + 0 + 1 - 0)
2
Total number of valence electrons are equal in
6
both the species and both the species exhibit = = 3 = sp 2 hence geometry is trigonal
linear shape. 2
planner.
40. (c) BCl3 is trigonal planar and hence the bond
angle is 120°. NO2– (nitrite ion) also has sp2 hybridization and
gives a trigonal planner geometry but because there
Cl are only two outer atoms, the molecular geometry
is bent with Ð120º bond angles.
120°
B 48. (c) Applying VSEPR theory, both NF3 and H2O
Cl Cl are sp3 hybridized.
49. (a) F ¾ Xe ¾ F sp3d and Linear
41. (b) CH4 NH3 H2O
–
H CI ¾ I ¾ CI sp3d and Linear
50. (d) PCl3
C 109°28' N H
7°
H H H P
10
H H H 104.3° H Cl
Cl Cl
Tetrahedral; Trigonal Bent
pyramidal
51. (d) BF4- hybridisation sp3, tetrahedral structure.
The geometry of H2O should have been tetrahedral
if there are all bond pairs. But due to presence of NH +4 hybridisation sp3, tetrahedral structure.
two lone pairs the shape is distorted tetrahedral.
Hence bond angle reduced to 104.5° from 109.5°. 52. (a)
42. (a) According to VSEPR theory order of 1

NO2– , H= [5 + 0 + 1 - 0] = 3 = sp 2
repulsion in between lp – lp, lp – bp and bp – 2
bp is as under 1
lp – lp > lp – bp > bp – bp NO3– , H= [5 + 0 + 1 - 0] = 3 = sp 2
2
43. (c) ClO3– and SO3–2 both have same number
1
of electrons (42) and central atom in each being NH2– , H= [5 + 2 + 1 + 0] = 4 = sp3
sp3 hybridised. Both are having one lone pair 2
on central atom hence they are pyramidal. 1
44. (b) NO2+ has sp hybridisation so it is linear NH4+, H= [5 + 4 + 0 - 1] = 4 = sp3
2
with bond angle = 180°.
45. (d) XeF4, XeO4 1
SCN–, H = [4 + 0 + 0 + 0] = 2 = sp
2
O \ NO2– and NO3– have same hybridisation.
F F Xe
Xe 1
Hybridisation = [No. of valence electrons of
O O 2
F F O central atom + no. of monovalent atoms attached
(Square planar) [Tetrahedral] to it + Negative charge if any – positive charge if
any]
46. (b) Be2+ = (4 – 2) = 2
is isoelectronic with Li+ (3 – 1 = 2) sp 3 sp sp sp 3
Since both have same number of electrons in 53. (b) H3C — C º C — CH3
their outermost shell. linear
60. (c) Hybridization of Br in BrO3–

It is important to note that in but-2-yne, the
1
hydrogen atoms are not linear. H = ( 7 + 0 - 0 +1) = 4
2
H sp3 sp3 sp3 sp3 H hybridization = sp3
H C–C C–C H Hybridization of Xe in XeO3.
H H
1
Linear part of molecule H = (8 + 0 - 0 + 0 ) = 4
2
54. (c) (a) NH +4 : sp3 hybridisation Hybridization = sp3
In both cases, the structure is trigonal pyramidal.
(b) CH4: sp3 hybridisation
61. (d) In SiCl4 there is sp3 hybridisation, so the
(c) SF4: sp3 d hybridisation structure is tetrahedral. In SO42–, PO43–, NH4+
(d) BF4– : sp3 hybridisation the structure is tetrahedral with sp 3
hybridisation. But in SCl4, sp3d hybridisation is
55. (b) In NO3- , nitrogen is in sp2 hybridisation, present, so its shape is different i.e., see saw.
thus planar in shape. In H3 O + , oxygen is in sp3 62. (b) NO2+ will have linear shape as it will have
sp hybridisation.
hybridisation, thus trigonal pyramidal in shape.
63. (d) In BF3, AlF3 & NF3 all fluoride atoms are
5+5+2
56. (c) SbCl52– : = 6 means sp 3 d 2 symmetrically oriented with respect to central
2 metal atom but in ClF3 three fluorine atoms are
hybridisation arranged as follows :
I3– , SF4 , and PCl5 ; all have sp3d hybridization. F
3+3
57. (b) BF3 : = 3 means sp2 hybridisation Cl F
2
5 +1
NO-2 : = 3 means sp2 hybridisation F
2
Here two bonds are in equatorial plane & one
58. (c) We find that in the given molecules
bond is in axial plane.
hybridisation is
64. (a) BF3 is sp2 hybridised. So, it is trigonal
BF3 ® sp2
planar. NH3, PCl3 has sp3 hybridisation hence
NO -2 ® sp2 has trigonal pyramidal shape, IF3, has sp3d
NH 2- ® sp3 hydridization and is T-shaped.
65. (c) The possible structures are:
H2O ® sp3
F
59. (b) From the structure of three species we can F F
determine the number of lone pair electrons on Br F Br F Br
F F
central atom (i.e. N atom) and thus the bond F
F
angle.
I II III
90° lp – lp
...O... ..
N N +
O..
O¬ N=O
O O NO+2 repulsion 0 0 1
- 90° lp – bp
NO 2 NO 2
We know that higher the number of lone pair of repulsion 4 6 3
electron on central atom, greater is the lp – lp 90° bp – bp
repulsion between Nitrogen and oxygen atoms. repulsion 2 0 2
Thus smaller is bond angle. The first structure is minimizing the lp – lp
The correct order of bond angle is repulsion if we compare it with III. The same is
minimizing the lp – bp repulsions if we compare
+
NO2- < NO2 < NO2 it with II. Also it can be noted that, I structure is
not minimizing the bp – bp repulsions.
EBD_8336
42 CHEMISTRY
69. (a) For p-overlap the lobes of the atomic

66. (a) d , d orbitals are involved in d2sp3
x2 – y 2 z2 orbitals are perpendicular to the line joining the
hybridisation. nuclei.
Only those d orbitals whose lobes are directed 70. (c) In XeF2 and IF2- . Both XeF2 and IF2– are
along X, Y and Z directions hybridise with s and p
orbitals. In other three d orbitals namely sp3d hybridized and have linear shape.
dxy , d yz and d xz , the lobes are at an angle of 45° 71. (c) In all the species, the center atom is sp3
from both axis, hence the extent of their overlap hybridized. But only in NH4+, no lone pair of
with s and p orbitals is much lesser than d 2 2 electrons are present. Thus, it has maximum
x -y
bond angle.
and d 2 orbitals.
z 72. (c) In P–O bond, p bond is formed by the
sidewise overlapping of d-orbital of P and p-
67. (a) X5
orbital of oxygen. Hence it is formed by pp and
X4 X1 dp overlapping.
O
M s p
P
– –
O – O
O
X3 X2 73. (d) PF3 has pyramidal shape
X6
Phosphorus exist in sp3 hybridiation state hence
Thus here bond angles between
it exist in tetrahedral geometry. But due to
X 4 - M - X 2 = 180° presence of lone pair its shape is pyramidal.
X1 - M - X 3 = 180° 1
74. (b) XeF4 hybridisation is = (V + X - C + A)
X 5 - M - X 6 = 180° 2
hence V = 8 (no. of valence e– )
68. (b) In SO3-2 X = 4 (no of monovalent atom)
O
– 1 (8 + 4 + 0 - 0) = 6, sp3d2
–p s
O s=S : –
2
s O C = 0 charge on cation
S is sp3 hybridised, so A = 0 (charge on anion).
F F
2 2 6 2 1 1 1
16 S = 1s 2 s 2 p 3s 3 p x 3 p y 3 p z 3d1xy
1442443 { The shape is Xe Square planar shape.
3
sp hybridisation unhybride
F F
In 'S' unhybride d-orbital is present, which will 75. (c) The electronic configuration of As is
involved in p bond formation with oxygen atom.
2 2 6 1 1 1 1 1
8O = 1s 2 2 s 2 2 p 2x 2 p1y 2 p1z As = 1s 2 s 2 p 3s 3 p x 3 p y 3 p z 3d
144424443
In oxygen two unpaired p-orbital is present in ¯ sp3d hybridisation
these one is involved in s bond formation while
other is used in p bond formation So, the hybrid orbitals used by As atom in AsF5
molecule are s, px, py, pz, dz2.
Thus in SO 32 - , pp and dp orbitals are involved
In the formation of a stable trigonal pyramid, the
for pp - d p bonding. two axial bonds above and below the equatorial
xy-plane have to be equally strong. Thus, the dz2
orbital is used.
76. (d) In alkynes the hybridisation is sp i.e each 85. (a) A s - bond is stronger than a p -bond
carbon atom undergoes sp hybridisation to form hence option (a) is not correct.
two sp-hybrid orbitals. The two 2p-orbitals
Sigma (s) bonds are formed by head on overlap of
remain unhybridised. Hybrid orbitals form one unhybridised s–s, p–p or s–p orbitals and
sigma and two unhybridised orbitals form p- hybridised orbitals (sp, sp2, sp3, sp3d and sp3d 2)
bonds. hence s bonds are strong bonds where as Pi (p)-
bonds are formed by side ways overlap of
. . . . unhybridised p- and d-orbitals hence p bonds are
weak bonds.
C . . C
86. (b) BF3 involves sp2-hybridization.
87. (a) For linear arrangement of atoms the
hybridisation should be sp(linear shape, 180°
. . . .
angle). Only H2 S has sp3 -hybridization and
Hence two p bond and one sigma bond between hence has angular shape while C2H2, BeH2 and
C — C lead to cylindrical shape. CO2 all involve sp-hybridization and hence have
77. (d) As there is no lone pair on boron in BCl 3 linear arrangement of atoms.
therefore no repulsion takes place. But there is 88. (b) Equilateral or triangular planar shape
a lone pair on nitrogen in NCl 3. Therefore involves sp2 hybridization.
repulsion takes place. Thus, BCl3 is planar 89. (a)
molecule but NCl3 is a pyramidal molecule.
78. (c) The C–C bond distance decreases as the s-orbital p-orbital
multiplicity of the bond increases. Thus, bond The overlap between s- and p-orbitals occurs
distance decreases in the order: butane (1.54 Å) along internuclear axis and hence the angle is 180°.
> benzene (1.39 Å) > ethene (1.34) Å > ethyne 90. (d) For He2 molecule, Electronic configuration
(1.20 Å). Thus in butane, C – C bond distance is is s1s 2 , s *1s 2
the largest.
79. (b) The angle between the bonds formed by 1 1
Bond order = ( N b - N a ) = (2 - 2) = 0
px and py orbitals is the minimum i.e. 90°. 2 2
80. (b) BH3 has sp2 hybridization and hence does Since, bond order of He2 is zero, so it does not
not have tetrahedral structure while all others exist.
have tetrahedral structures. 91. (a) Molecular orbital configuration of O2 is
81. (b) Sigma bond is stronger than p-bond. The given as :
electrons in the p bond are loosely held. The O2 (16 e–) : s1s2 s*1s2 s2s2 s*2s2 s2p2z
bond is easily broken and is more reactive than
s -bond. Energy released during sigma bond p 2 p 2x = p 2 p 2y p * 2 p1x = p * 2 p1y
formation is always more than p bond because So, in O2 molecule, there are two (2) unpaired
of greater extent of overlapping. electrons, so, it is a “paramagnetic”
82. (b) CO 2 has sp-hybridization and is linear. SO2 substance in nature.
and CO 32- are planar (sp2 ) while SO 24 - is 92. (a) O O–
tetrahedral (sp3).
Mn Mn
83. (c) The bond length decreases in the order
sp3 > sp2 > sp. O – O
O– O O O
Because of the triple bond, the carbon-carbon
Manganate ion Permanganate ion
bond distance in ethyne is shortest.
84. (b) All compounds have sp3 hybridisation, but 93. (c) Only p bond is present in C2 molecule.
in CCl4, all bonded atoms are same. Hence, the s1s2 s*1s2 s2s2 s*2s2 p2p2x = p2p2y
bond angle will be exactly 109°28°
EBD_8336
44 CHEMISTRY
94. (b) NO : (s1s)2, (s*1s)2, (s2s)2,(s*2s)2,(s2pz)2, O 2– (Super oxide ion): Total number of electrons
(p2px)2 = (p2py)2,(p*2px)1 = (p*2py)0 (16 + 1) = 17 .
10 - 5 Electronic configuration
B.O. = = 2.5
2
CN : (s1s) , (s*1s)2, (s2s)2,(s*2s)2,
– 2 s1s 2 < s*1s 2 < s 2s 2 < s* 2s 2 < s 2 p x2
(p2px)2 = (p2py)2, (s2pz)2 < p 2 p 2y = p 2 pz2 < p* 2 p y2 = p* 2 p1z
10 - 4 (Nb - Na ) 10 - 7 3 1
B.O. = =3 Bond order = = = =1
2 2 2 2 2
CN : (s1s)2, (s*1s)2, (s2s)2,(s*2s)2,
O+22 ion: Total number of electrons
(p2px)2 = (p2py)2,(s2pz)1
= (16 – 2) = 14 Electronic configuration
9-4
B.O. = = 2.5 s1s2 < s*1s2 < s2s2 < s*2s2 < s2px2 < p2py2
2 = p2pz2
CN : (s1s) , (s*1s)2, (s2s)2,(s*2s)2,
+ 2
(p2px)2 = (p2py)2 (N b – Na ) 10 – 4 6
Bond order = = = =3
2 2 2
8-4
B.O. = =2 So bond order: O2– < O2+ < O22+
2
97. (a) Oxygen molecule (O2) – Total number of
Hence, option (2) should be the right
answer. electrons = 16 and electronic configuration is
95. (b) CN– and CO have same no. of electrons and s1s 2 < s*1s 2 < s 2s 2 < s* 2s 2 < s 2 p x2
have same bond order equal to 3.
Short cut trick to calculate the bond order: < p 2 p 2y = p 2 pz2 < p* 2 p1y = p* 2 p1z
N2 has 14 electrons and its bond order is 3. We
have to remember this concept that every electron N b - N a 10 - 6 4
added or subtracted to 14, reduces the bond order Bond order = = = =2
by 0.5. For example 2 2 2
CN– Þ no. of electrons = 6 + 7 + 1 = 14
\ bond order = 3 O +2 ion - Total number of electrons (16 – 1) = 15.
CO Þ no. of electrons = 6 + 8 = 14 Electronic configuration
\ bond order = 3
NO Þ no. of electrons = 7 + 8 = 15
s1s 2 < s*1s 2 < s 2s 2 < s* 2s 2 < s 2 p x2
\ bond order = 3 – 0.5 = 2.5
NO+ Þ no. of electrons = 7 + 8 – 1 = 14
\ bond order = 3 < p 2 p 2y = p2 pz2 < p* 2 p1y
O2– Þ no. of electrons = 8 + 8 + 1 = 17
\ bond order = 3 – 1.5 N b - Na 10 - 5 5 1
Please note that this method will work for any Bond order = = = =2
species that have electrons between 10 and 18. 2 2 2 2
96. (c) O +2 ion - Total number of electrons O2– (Super oxide ion) Total number of electrons
(16 – 1) = 15. (16 + 1) = 17 . Electronic configuration
Electronic configuration
σ1s2 < σ*1s2 < σ2s2 < σ* 2s 2 < σ2p2x
s1s 2 < s*1s 2 < s 2 s 2 < s * 2 s 2 < s 2 p x2
< p 2 p 2y = p 2 pz2 < p * 2 p1y < π2p2y = π2p2z < π* 2p 2y = π* 2p1z
N b - N a 10 - 5 5 1 (Nb - Na ) 10 - 7 3 1
Bond order = = = =2 Bond order = = = =1
2 2 2 2 2 2 2 2
O (c) ® C2+
C2 ¾¾
98. (a) Xe B.O. 2 2.5
Bond energy decreases
O O O
Magnetic behaviour changes from diamagnetic
Number of s bonds = 4 to paramagnetic
Number of p bonds = 4 (d) NO ¾¾ ® NO+
99. (a) According to molecular orbital theory as
bond order decreases stability of the molecule B.O. 2 2.5
decreases bond energy increases
Magnetic behaviour changes from paramagnetic
1
Bond order = (N b – Na ) to diamagnetic
2 103. (b) No. of electrons in CO = 6 + 8 = 14
1 No. of electrons in NO+ = 7 + 8 – 1 = 14
Bond order for O2+ = (10- 5) = 2.5
2 \ CO and NO+ are isoelectronic species.
1 Isoelectronic species have identical bond order.
Bond order for O 2 = (10 - 6) = 2
2 104. (a) Molecular orbital configuration of O-2 is
1
Bond order for O -2 = (10 - 7) = 1.5
2 O-2 (17) = s1s2, s*1s2, s2s2, s*2s2,
2- 1 s2pz2, p2px2 = p2py2, p*2px2 = p*2py1
Bond order for O2 = (10 - 8) = 1.0
2 O
105. (a) s
hence the correct order is H s H
O+2 > O2 > > O 2–
O2– 2 s s s s
O ¬ S=O O ¬ N =O O = C = O
100. (a) Ni2+ = [Ar] 3d 8, 4s0 p p p p
In the presence of strong ligand CN–, pairing of 106. (d) Calculating the bond order of various
electrons will occur: species.
2+
Ni = G.S. O2- : KK s 2s 2 s* 2 s 2 s2 p 2z
3d 4s 4p
E.S. p 2 px2 p 2 p 2y p* 2 px2 p* 2 p1y
dsp 2 Number of electrons in bonding -

s Number of electrons in non-bonding
101. (d) s C = C —H
H— s B.O. =
p 2
s | | s
H H 8-5
= or 1.5
2
102. (d) (a) ® N +2
N 2 ¾¾
2 * 2
NO : KK s 2s s 2s p2 px » p2 p2y s 2 pz2 p* 2 p1x
2
B.O. 3 2.5
Bond energy decreases Nb - Na 8 - 2
Magnetic behaviour changes from diamagnetic B.O. = = or 2.5
2 2
to paramagnetic
C 22- : kk s 2 s 2 s* 2 s 2 p 2 p x2 p 2 p 2y s 2 p 2z
(b) ® O 2+
O 2 ¾¾
B.O. 2 2.5 Nb - Na 8 - 2
B.O. = = or 3
Bond energy increases 2 2
Magnetic behaviour does not change. He 2+ = s1s 2 s *1s1
EBD_8336
46 CHEMISTRY
N - Na 2 - 1 110. (c) MOT configurations of O2 and O2+ :

B. O. = b = or 0.5 O2+ : (s1s)2 (s*1s)2 (s2s)2 (s*2s)2 (s2pz)2
2 2
From these values we find the correct order of (p2p2 x = p2p2y ) (p*2px1 = p*2p1y )
increasing bond order is Number of unpaired electrons = 2, so paramagnetic.
O2 : (s1s)2 (s*1s)2 (s2s)2 (s*2s)2 (s2pz)2
He22+ < O -2 < NO < C22-
(p2p2x = p2p2y ) (p*2px1 = p*2p0y)
107. (a) O2 = KK (s 2s)2 (s* 2s)2 (s 2pz)2
Number of unpaired electrons = 2, so
(p 2px)2 (p 2py)2 (p* 2px)1 (p* 2py)1
paramagnetic.
O2- = KK (s 2s)2 (s* 2s)2 (s 2pz)2 111. (a) O2 (16) : KK (s2s)2 (s*2s)2 (s2pz)2 (p2px)2
(p 2px)2 (p 2py)2 (p* 2px)2 (p* 2py)1 (p2py)2, (p* 2 py)1 = (p* 2 px)1, B.O.: 2
108. (a) Both O2–
2 and B2 has bond order equal to 1. O2+ (15) : Remove one electron from p *2 p y from
B2 (10) = [s 1s s 1s s 2s s 2s p2 p
2 * 2 2 * 2 1 1
y p2 p z ]
O2 , B.O.: 2.5
Nb - Na 6-4 2 O2 – (17) : KK (s2s)2 (s*2s)2 (s2pz)2 (p2px)2

Bond order = = = =1 (p2py)2, (p*2px)2 (p*2py)1, B.O.: 1.5
2 2 2
B2 is known to be in the gas phase. O22– (18) : KK (s2s)2 (s*2s)2 (s2pz)2 (p2px)2
O2 2 - = s1s 2 s *1s 2 s 2s 2 s *2 s 2 s2 p z 2 (p2py)2, (p*2px)2 (p*2py)2
Since, the bond length decreases as the bond order
p2 px 2p 2 p y 2 p* 2 px 2p* 2 p y 2
increases, hence, O2+ have least bond length.
1
Bond order = (10 - 8) = 1 112. (b) Bond order of Be2 = 0, hence Be2 cannot
2 exist.
109. (b) (O2) = s1s 2 s*1s 2 s 2s 2 s* 2s 2 s 2 pz2 p2 px2 113. (a) Molecular orbital configuration of
N 2– 2 2 2 2
2 = s1s s *1s s 2 s s * 2 s –
= p2 p 2y p* 2 p1x = p* 2 p1y
ìïp 2 p 2y ìïp * 2 p1y
N - N a 10 - 6 4 í s 2 p x2 í
Bond order = b = = =2 2 1
2 2 2 îïp 2 p z îï p * 2 p z
(O +
2 ion ) = s1s 2
s*1s 2 s 2 s 2 s * 2 s 2
Bond order =
10 – 6
=2
*
s 2 p z2 p 2 p x2 = p2 p 2y p 2 p1x 2
N - N a 10 - 5 5 1 N 2– = s1s 2 s *1s 2 s 2 s 2 s * 2 s 2
Bond order = b = = =2
2 2 2 2 ìp 2 p 2y ìp * 2 p1y
( )
O 2- = s1s 2 s*1s 2 s 2s 2 s* 2s 2 s 2 Pz2
ï
í
2
s 2 p x2
ï
í
0
îïp 2 p z îïp * 2 p z
p2 px2 = p2 p 2y p* 2 px2 p* 2 p1y
10 - 5
Bond order = = 2.5
( N - N a ) 10 - 7 3 1 2
Bond order = b = = =1
2 2 2 2 ìïp 2 p 2y
( ) = s1s s 1s
O22- 2 * 2 2
s 2s s 2s * 2
s 2 pz2 p2 px2 N 2 = s1s 2 s *1s 2 s2 s 2 s * 2 s 2 í
îïp 2 p z
2
, s2 p x2
= p2 p 2y p* 2 px2 = p* 2 p y2 10 – 4
Bond order = =3
Nb - N a 10 - 8 2 2
Bond order = = =1 The correct order is = N 2– –
2 2 2 \ 2 < N2 < N2
114. (d) The shape of ozone molecule is

To form NO 3- , nitrogen uses one p-electron
+ + for p-bond formation and two p-electrons for
..
..
O O s-bond formation. 2s electrons are used for
– O .. .. .. O . .O..– coordinate bond formation. Thus there is no
..
.. ..
O lone pair on nitrogen and four bond pairs are
.. ..
present.
In it we find 2 s and 1p bond, i.e., option (d) is
O
correct.
115. (c) All these structures exhibits resonance
and can be represented by the following
resonating structures. N
+ ..
(i) : C º O : ¬¾
® : C = O: O O
– –
120. (c) Dissociation energy of any molecules
O O O depends upon bond order. Bond order in N2
(ii) C C C molecule is 3 while bond order in N +2 is 2.5.
– – – –
O O O O O O Further we know that more the Bond order, more
is the stability and more is the BDE.
+ ..
-
(iii) : O
..
=C=O
..
: ¬¾
®:O -C º O
..
: 121. (b) NO+ = s1s 2 s *1s 2 s 2 s 2s * 2 s 2 s2 p x 2
.. + p 2 p y 2 = p 2 pz 2
-
¬¾
® :O
..
º C-O:
1
Bond order of NO+ = (N b - N a )
More is the single bond character. More will be 2
the bond length. Hence, the corret order is :
1 1
CO < CO2 < CO32– = (10 - 4) = ´ 6 = 3
2 2
116. (d) Electronic configuration of the molecule
according to molecular orbital theory, is 1
Similarly, Bond order of NO = (10 - 5)
s1s2s*1s2s2s2s*2s2s2pz2 (p2px2 = s2py2) 2
(p*2px2 = p2py2) s*2pz2s3s2s*3s2s3pz2 1
= (5) = 2.5
(p3px2 = p3py2) (p*3px1 = 3py1) 2
Last two electrons are unpaired. So no. of 1 1
unpaired electron is 2. Bond order of NO– = (10 - 6) = (4) = 2
2 2
117. (a) SiF4 has symmetrical tetrahedral shape which
is due to sp3 hybridisation of silicon atom in its 1 1
excited state while SF4 has distorted tetrahedral Bond order of O -2 = (10 - 7) = (3) = 1.5
2 2
or sea-saw geometry which arises due to sp3d By above calculation, we get
hybridisation of sulphur atom and one lone pair Decreasing bond order
of e–s in one of the equatorial hybrid orbital.
118. (c) As sigma bond is stronger than the p (pi) NO+ > NO > NO– > O -2
bond, so it must be having higher bond energy 122. (a) Paramagnetic character is based upon
than p (pi) bond. presence of unpaired electron
Cl – = 1s 2 2s 2 2 p6 3s 2 3 px2 3 p 2y 3 p 2z
119. (d) N :
1s 2 2s 2 2p3 Be + = 1s 2 2 s1
EBD_8336
48 CHEMISTRY
126. (d) In this configuration, there are four

Ne 2+ = 1s 2 2s 2 2 px2 2 p1y 2 p1z
completely filled bonding molecular orbitals and
As+ = 1s 2 2 s 2 2 p 6 3s 2 3 p 6 3d 10 one completely filled antibonding molecular
orbital. So that Nb = 8 and N a = 2 .
4 s 2 4 p1x 4 p1y 4 p1z
1 1
Hence only Cl– do not have unpaired electrons. \ Bond order = ( N b - N a ) = (8 - 2) = 3.
2 2
123. (d) Total no. of electrons in O 2 2 - = 16 + 2 = 18 127. (b) The structure of NO:
Distribution of electrons in molecular orbital N
: :
O
×
×
×
2 * 2 2 * 2
s1s , s 1s , s2s , s 2s , s2 px2 , p2 p 2y In NO, the presence of unpaired electron is clear.
p2 pz2 , p* 2 px2 p* 2 p 2y Therefore, it is paramagnetic.
Anti bonding electron = 8 (4 pairs) 128. (b) The removal of an electron from a diatomic
124. (b) We know that in O2 bond, the order is 2 molecule may increase or decrease the bond
and in O2– bond, the order is 1.5. Therefore, the order.
wrong statements is (b). Removal of an electron from bonding orbital results
125. (c) The N–O bond length decreases in the order in decrease of bond order, hence reduces bond
O strength while removal of an electron from
antibonding orbital results into increase in bond
—
—
order hence increases the bond strength.

O N > O—
—N
—
O O 129. (a) Linear combination of two hybridized

O orbitals leads to the formation of sigma bond.
— N—N —
> O— — O > N—
—O
O
States of Matter 49
5 States of Matter
2020 2019 2018 2017 2016

Graham's law of
1 A
Gas law and ideal gas diffusion
equation Dalton's law of
1 A
partial pressure
van der Waal's
van der Waal's 1 A 1 A
equation
equation and
liquefaction of
liquefaction of gases 1 A
gases
Topic 1: Gas laws and Ideal gas Equation 27°C in identical conditions. The ratio of the
volumes of gases H2 : O2 : methane would be :
1. A mixture of N2 and Ar gases in a cylinder (a) 8 : 16 : 1 (b) 16 : 8 : 1 [2014]
contains 7 g of N2 and 8 g of Ar. If the total (c) 16 : 1 : 2 (d) 8 : 1 : 2
pressure of the mixture of the gases in the 5. Dipole-induced dipole interactions are present
cylinder is 27 bar, the partial pressure of N2 is: in which of the following pairs : [NEET 2013]
[Use atomic masses (in g mol–1) : N = 14, Ar = 40] (a) Cl2 and CCl4 (b) HCl and He atoms
(a) 12 bar (b) 15 bar [2020] (c) SiF4 and He atoms (d) H2O and alcohol
(c) 18 bar (d) 9 bar 6. 50 mL of each gas A and of gas B takes 150 and
2. The volume occupied by 1.8 g of water vapour 200 seconds respectively for effusing through a
at 374°C and 1 bar pressure will be pin hole under the similar condition. If molecular
[Use R = 0.083 bar LK–1 mol–1] mass of gas B is 36, the molecular mass of gas A
[NEET Odisha 2019] will be : [2012]
(a) 5.37 L (b) 96.66 L (a) 96 (b) 128
(c) 55.87 L (d) 3.10 L (c) 32 (d) 64
3. Equal moles of hydrogen and oxygen gases are 7. A certain gas takes three times as long to effuse
placed in a container with a pin-hole through out as helium. Its molecular mass will be :
which both can escape. What fraction of the (a) 27 u (b) 36 u [2012 M]
oxygen escapes in the time required for one-half (c) 64 u (d) 9 u
of the hydrogen to escape ? [2016] 8. Two gases A and B having the same volume
(a) 1/8 (b) 1/4 diffuse through a porous partition in 20 and 10
(c) 3/8 (d) 1/2 seconds respectively. The molecular mass of A
4. Equal masses of H2,O2 and methane have been is 49 u. Molecular mass of B will be : [2011]
taken in a container of volume V at temperature
EBD_8336
50 CHEMISTRY
(a) 50.00 u (b) 12.25 u (b) Volume always remains constant.

(c) 6.50 u (d) 25.00 u (c) Pressure always remains constant.
9. A bubble of air is underwater at temperature 15°C (d) The product of pressure and volume
and the pressure 1.5 bar. If the bubble rises to always remains constant.
the surface where the temperature is 25°C and 17. Pressure remaining the same, the volume of a
the pressure is 1.0 bar, what will happen to the given mass of an ideal gas increases for every
volume of the bubble ? [2011M] degree centigrade rise in temperature by definite
(a) Volume will become greater by a factor of 1.6. fraction of its volume at [1989]
(b) Volume will become greater by a factor of 1.1. (a) 0°C
(c ) Volume will become smaller by a factor of 0.70. (b) its critical temperature
(d) Volume will become greater by a factor of 2.5. (c) absolute zero
10. From a heated mixture of nitrogen, oxygen and (d) its Boyle temperature
carbon, two compounds (out of the many
Topic 2: Kinetic Theory of Gases and
obtained) are isolated. The rates of diffusion of
Molecular Speeds
the two isolated compounds are almost identical.
The two compounds are [1999] 18. By what factor does the average velocity of a
(a) N2O and CO2 (b) CO and NO gaseous molecule increase when the temperature
(c) CO2 and NO2 (d) N2O and CO (in Kelvin) is doubled ? [2011]
11. If 500 mL of gas A at 400 torr and 666.6 mL of B (a) 2.0 (b) 2.8
at 600 torr are placed in a 3 litre flask, the pressure (c) 4.0 (d) 1.4
of the system will be [1999] 19. If a gas expands at constant temperature, it
(a) 200 torr (b) 100 torr indicates that : [2008]
(c) 550 torr (d) 366 torr (a) kinetic energy of molecules decreases
12. A gaseous mixture contains H2 and O2 in the (b) pressure of the gas increases
molar ratio 8 : 1. The ratio of H2 : O2 by weight in (c) kinetic energy of molecules remains the same
this mixture would be [1999] (d) number of the molecules of gas increases
(a) 4 : 1 (b) 1 : 8 20. Which of the following expressions correctly
(c) 8 : 1 (d) 1 : 2 represents the relationship between the average
13. 500 mL of nitrogen at 27°C is cooled to –5°C at molar kinetic energy, KE, of CO and N2 molecules
the same pressure. The new volume becomes at the same temperature ? [2000]
[1995] (a) KECO < KE N 2
(a) 326.32 mL (b) 446.66 mL
(b) KECO > KE N 2
(c) 546.32 mL (d) 771.56 mL
14. 600 c.c. of a gas at a pressure of 750 mm is (c) KECO = KE N2
compressed to 500 c.c. Taking the temperature (d) cannot be predicted unless volumes of the
to remain constant, the increase in pressure, is gases are given
(a) 150 mm (b) 250 mm [1995] 21. The temperature of the gas is raised from 27°C to
(c) 350 mm (d) 450 mm 927°C, the root mean square velocity is [1994]
15. The correct value of the gas constant ‘R’ is close (a) 927 / 27 time the earlier value
to : [1992] (b) same as before
(a) 0.082 litre-atmosphere K (c) halved
(b) 0.082 litre-atmosphere K–1 mol–1 (d) doubled
(c) 0.082 litre – atmosphere–1 K mol–1 22. At STP, 0.50 mol H2 gas and 1.0 mol He gas
(d) 0.082 litre –1 atmosphere – 1 K mol (a) have equal average kinetic energies [1993]
16. At constant temperature, for a given mass of an (b) have equal molecular speeds
ideal gas [1991] (c) occupy equal volumes
(a) The ratio of pressure and volume always (d) have equal effusion rates
remains constant.
States of Matter 51
23. Internal energy and pressure of a gas per unit (c) Z < 1 and attractive forces are dominant
volume are related as : [1993] (d) Z < 1 and repulsive forces are dominant
3 31. The correction factor ‘a’ to the ideal gas equation
(a) P = 2 E (b) P = E
3 2 corresponds to [2018]
1 (a) Density of the gas molecules
(c) P = E (d) P = 2 E (b) Volume of the gas molecules
2
24. The ratio among most probable velocity, mean (c) Forces of attraction between the gas molecules
velocity and root mean square velocity is given (d) Electric field present between the gas molecules
by [1993] 32. Given van der Waals constants for NH3, H2, O2
and CO2 are respectively 4.17, 0.244, 1.36 and
(a) 1 : 2 : 3 (b) 1 : 2. 3 3.59, which one of the following gases is most
(c) 2 : 3 : 8/ p (d) 2 : 8/p : 3 easily liquefied? [2018]
25. A closed flask contains water in all its three (a) NH3 (b) H2
states solid, liquid and vapour at 0°C. In this (c) CO2 (d) O2
situation, the average kinetic energy of water 33. A gas such as carbon monoxide would be most
molecules will be [1992] likely to obey the ideal gas law at : [2015 RS]
(a) the greatest in all the three states (a) high temperatures and low pressures.
(b) the greatest in vapour state (b) low temperatures and high pressures.
(c) the greatest in the liquid state (c) high temperatures and low pressures.
(d) the greatest in the solid state (d) low temperatures and low pressures.
26. In a closed flask of 5 litres, 1.0 g of H2 is heated 34. Maximum deviation from ideal gas is expected
from 300 to 600 K. Which statement is not correct? from : [NEET 2013]
(a) Pressure of the gas increases [1991] (a) N2(g) (b) CH4(g)
(b) The rate of collision increases (c) NH3 (g) (d) H2(g)
(c) The number of moles of gas increases 35. What is the density of N2 gas at 227°C and
(d) The energy of gaseous molecules increases 5.00 atm pressure? (R = 0.0821 atm K–1 mol–1)
27. The root mean square speeds at STP for the [NEET Kar. 2013]
gases H2, N2, O2 and HBr are in the order : [1991] (a) 0.29 g/ml (b) 1.40 g/ml
(a) H2< N2< O2 < HBr (b) HBr < O2 < N2 < H2 (c) 2.81 g/ml (d) 3.41 g/ml
(c) H2 < N2 = O2< HBr (d) HBr < O2 < H2 < N2. 36. For real gases, van der Waals equation is written as
28. Root mean square velocity of a gas molecule is æ an2 ö
proportional to [1990] çè p + 2 ÷ø (V - nb) = nRT
V
(a) m1/2 (b) m0
where ‘a’ and ‘b’ are van der Waals constants.
(c) m–1/2 (d) m
Two sets of gases are :
29. Absolute zero is defined as the temperature
(I) O2, CO2, H2 and He (II) CH4, O2 and H2
(a) at which all molecular motion ceases
The gases given in set-I in increasing order of
(b) at which liquid helium boils [1990]
‘b’ and gases given in set-II in decreasing order
(c) at which ether boils
of ‘a’, are arranged below. Select the correct
(d) all of the above
order from the following : [2012 M]
Topic 3 : van der Waal's Equation and
(a) (I) He < H2 < CO2 < O2 (II) CH4 > H2 > O2
liquefaction of Gases
(b) (I) O2 < He < H2 < CO2 (II) H2 > O2 > CH4
30. A gas at 350 K and 15 bar has molar volume 20 (c) (I) H2 < He < O2 < CO2 (II) CH4 > O2 > H2
percent smaller than that for an ideal gas under the (d) (I) H2 < O2 < He < CO2 (II) O2 > CH4 > H2
same conditions. The correct option about the gas 37. A gaseous mixture was prepared by taking equal
and its compressibility factor (Z) is: [2019] mole of CO and N2. If the total pressure of the
(a) Z > 1 and attractive forces are dominant mixture was found 1 atmosphere, the partial
(b) Z > 1 and repulsive forces are dominant pressure of the nitrogen (N2) in the mixture is :
EBD_8336
52 CHEMISTRY
(a) 0.5 atm (b) 0.8 atm [2011] (b) There is no interaction between the molecules
(c) 0.9 atm (d) 1 atm (c) All molecules of the gas move with same speed
38. The pressure exerted by 6.0 g of methane gas in (d) At a given temperature, PV is proportional
a 0.03 m3 vessel at 129°C is (Atomic masses : to the amount of the gas
C = 12.01, H = 1.01 and R = 8.314 JK–1 mol –1) 45. An ideal gas can’t be liquefied because [1992]
(a) 31684 Pa (b) 215216 Pa [2010] (a) its critical temperature is always above 0°C
(c) 13409 Pa (d) 41648 Pa (b) its molecules are relatively smaller in size
39. van der Waal's real gas, act as an ideal gas, at (c) it solidifies before becoming a liquid
which conditions? [2002] (d) forces operated between its molecules are
(a) High temperature, low pressure negligible
(b) Low temperature, high pressure 46. Select one correct statement. In the gas equation,
(c) High temperature, high pressure PV = nRT [1992]
(d) Low temperature, low pressure (a) n is the number of molecules of a gas
40. Cyclopropane and oxygen at partial pressures (b) V denotes volume of one mole of the gas
170 torr and 570 torr respectively are mixed in a (c) n moles of the gas have a volume V
gas cylinder. What is the ratio of the number of (d) P is the pressure of the gas when only one
moles of cyclopropane to the number of moles mole of gas is present.
of oxygen (nC3H6/nO2)? [1996] 47. A gas is said to behave like an ideal gas when
170 ´ 42 the relation PV/T = constant. When do you
(a) = 0.39 expect a real gas to behave like an ideal gas ?
570 ´ 32
170 æ 170 570 ö (a) When the temperature is low [1991]
(b) ç + ÷ » 0.19 (b) When both the temperature and pressure
42 è 42 32 ø
are low
170 (c) When both the temperature and pressure
(c) = 0.23
740 are high
170 (d) When the temperature is high and pressure
(d) = 0.30
570 is low
41. At which one of the following temperature - 48. In van der Waal's equation of state for a non-
pressure conditions the deviation of a gas from ideal gas, the term that accounts for
ideal behaviour is expected to be minimum? [1996] intermolecular forces is : [1990]
(a) 350 K and 3 atm. (b) 550 K and 1 atm. (a) (V – b) (b) (RT)–1
(c) 250 K and 4 atm. (d) 450 K and 2 atm.
æ a ö
42. Under what conditions will a pure sample of an (c) çè P + 2 ÷ø (d) RT
ideal gas not only exhibit a pressure of 1 atm but V
also a concentration of 1 mole litre–1 ? 49. If P, V, M, T and R are pressure, Volume, molar
(R = 0.082 litre atm mol–1deg–1) [1993] mass, temperature and gas constant respectively,
(a) At STP then for an ideal gas, the density is given by
(b) When V = 22.4 litres [1989]
(c) When T = 12 K RT P
(a) (b)
(d) Impossible under any conditions PM RT
43. When is deviation more in the behaviour of a M PM
(c) (d)
gas from the ideal gas equation PV = nRT ? [1993] V RT
(a) At high temperature and low pressure 50. Correct gas equation is : [1989]
(b) At low temperature and high pressure
(c) At high temperature and high pressure V1T2 V2T1 PV
1 1 = T1
(a) = (b)
(d) At low temperature and low high pressure P1 P2 P2V2 T2
44. Which is not true in case of an ideal gas ? [1992] PT
1 2 = P2V2 V1V2
= P1P2
(a) It cannot be converted into a liquid (c) (d)
V1 T2 T1T2
States of Matter 53
Topic 4: Liquid State (a) In fixed ratio with that in the lower layer
(b) Same as the lower layer
51. The surface tension of which of the following
(c) Lower than the lower layer
liquid is maximum? [2005]
(d) Higher than the lower layer.
(a) C2H5OH (b) CH3OH
53. A liquid can exist only : [1994]
(c) H2O (d) C6H6
(a) between triple point and critical temperature
52. In a pair of immiscible liquids, a common solute
(b) at any temperature above the melting point
dissolves in both and the equilibrium is reached.
(c) between melting point and critical
Then the concentration of the solute in upper
temperature
layer is [1994]
(d) between boiling and melting temperature.
ANSWER KEY
1 (b) 7 (b) 13 (b) 19 (c) 25 (b) 31 (c) 37 (a) 43 (b) 49 (d)
2 (a) 8 (b) 14 (a) 20 (c) 26 (c) 32 (a) 38 (d) 44 (c) 50 (b)
3 (a) 9 (a) 15 (b) 21 (d) 27 (b) 33 (a) 39 (a) 45 (d) 51 (c)
4 (c) 10 (a) 16 (d) 22 (a) 28 (c) 34 (c) 40 (d) 46 (c) 52 (a)
5 (b) 11 (a) 17 (a) 23 (a) 29 (a) 35 (d) 41 (b) 47 (d) 53 (d)
6 (N) 12 (d) 18 (d) 24 (d) 30 (c) 36 (c) 42 (c) 48 (c)
Hints & Solutions

7 1 rH 2 v /t MO 2 32
1. (b) nN 2 = = = 0.25 = 1 1 Þ =
28 4 rO2 v2 / t2 MH 2 2
8 1
nAr = = = 0.20 1/ 2
40 5 = 16 = 4
Now, applying Dalton's law of partial pressure, 1/ x
pN 2 = mole fraction of N 2 × PTotal x

=4
2
0.25 5 \x=8
´ 27 = ´ 27 = 15 bar
0.45 9 \ Fraction of O2 = 1/8
4. (c) According to Avogadro’s law "At same
2. (a) According to ideal gas equation.
temperature and pressure. Volume µ no. of moles"
PV = nRT
w w w
W æ RT ö nH 2 = ; nO = ; nCH =
2 2 32 4 16
V= ç ÷
Mè P ø
Q VH : VO : VCH = nH2 : nO2 : nCH4
2 2 4
1.8 0.083 ´ 647
V= ´ = 5.37 L w w w
18 1 = : : = 16 : 1 : 2
2 32 16
3. (a) Given, nH2 = nO2 and tH2 = tO2 5. (b) HCl is polar (m ¹ 0) and He is non-polar (m = 0),
According to Graham's law of diffusion for two thus gives dipole-induced dipole interaction.
different gases.
EBD_8336
54 CHEMISTRY
Induced dipole forces result when an ion or a dipole r1 M2

= Þ r1 = r2 if M1 = M2
induces a dipole in an atom or a molecule with no r2 M1
dipole. These are weak forces. These are of two
types namely. Ion-induced dipole force and dipole- Hence compounds are N2O and CO2 as both
induced force. Ion-induced dipole force: when the have same molar mass i.e. 22
approach of an ion induces a dipole in an atom by 11. (a) Applying Boyle's law P1 V1 = P2 V2 for both
disturbing the arrangement of electrons. gases
Dipole induced dipole force: when a polar molecule
induces a dipole in an atom or in a non-polar 500 200
´ 400 = P ´ 3 Þ P =
molecule. 1000 3
VA VB MB 666.6 400
6. (N) = 600 ´ = P¢ ´ 3 Þ P¢ =
tA tB MA 1000 3
200 36 200 400 600

tB 4 36 Þ PT = P + P ¢ = + = = 200 torr
Þ = Þ = 3 3 3
tA 150 MA 3 MA
Real life application of Boyle's law:
16 36 81
Þ = Þ MA = = 20.25 when we fill bike tier with air with pump, the gas
9 MA 4 molecules inside the tire get compressed and
7. (b) According to Graham’s law of diffusion packed closer together. This increase the pressure
of the gas and it starts to push against the wall of
1 1 r1 M2 the tire and the tires becomes tighter.
rµ Þ r = M
d M 2 1 Moles of H 2 8
12. (d) = (Given)
Moles of O 2 1
3r1 M2 M2
= Þ 9=
r1 4 4 æ M.W. of O 2 ö æ weight of H 2 ö 8
ç ÷ç ÷
ç M.W. of H ÷ . ç weight of O ÷ = 1
M2 = 36 u è 2ø è 2ø
rA MB weight of H 2 8 ´ 2 1
= = =
8. (b) weight of O 2 32 ´ 1 2
rB MA
13. (b) Given initial volume (V1) = 500 mL ; Initial
V temperature (T1) = 27ºC = 300 K and final
20 = MB 1 MB
Þ = temperature (T2) = –5ºC = 268 K.
V 49 2 49 From Charle’s law :
10
1 V1 V2 500 V2
MB = ´ 49 = 12.25u = or =
4 T1 T2 300 268
9. (a) Given Where V2 = New volume of gas
P1 = 1.5 bar, T1 = 273 + 15 = 288 K, V1 = V 500
P2 = 1.0 bar, T2 = 273 + 25 = 298K, V2 = ? V2 = ´ 268 = 446.66 ml.
300
PV
1 1 = P2V2 14. (a) Given initial volume (V1) = 600 c.c.; Initial
T1 T2 pressure (P 1 ) = 750 mm and final volume
(V2) = 500 c.c. According to Boyle’s law,
1.5 ´ V 1 ´ V2 P1V1 = P2V2
=
288 298 Þ 750 × 600 = P2 × 500
V2 = 1.55 V i.e., volume of bubble will be almost
1.6 time to initial volume of bubble. 750 ´ 600
or P2 = = 900 mm .
10. (a) Rate of diffusion depend upon molecular 500
weight Therefore increase in pressure = (900 – 750)
= 150 mm.
States of Matter 55
15. (b) R = 0.082 litre atm K–1 mol–1 . 8RT

16. (d) According to Boyle’s law at constant Mean velocity (v ) =
pM
1 3RT
temperature, P µ or PV = constant
V Root mean square velocity (u) =
M
17. (a) Charle’s Law - The volume of the given
2 RT 8RT 3RT
1 \ a :v :u = : :
mass of a gas increases or decreases by of M pM M
273
its volume at 0°C for each degree rise or fall of 8
= 2: : 3
temperature at constant pressure. p
25. (b) In vapour state, the molecules are free to
æ t ö move with highest average kinetic energy.
V t = V 0 ç1 + at constant Pressure
è 273 ÷ø 26. (c) The number of moles of gas do not changes.
8RT Volume is constant and the mass of H2 is fixed so
18. (d) Average velocity =
pM the number of moles of the gas do not change. As
temperature increases the pressure also increases
i.e., v µ T and the rate of collision among the gas molecules
V2 2T and their energy also increases.
\ = = 1.41
V1 T 1 2 1 2
27. (b) PV = m N u = M u
19. (c) At any constant temperature the K.E. of 3 3
gaseous molecules remains same.
or u = 3PV / M .
The molar kinetic energy of a gas is proportional
to its temperature and the proportionality constant 1
3 At STP, u µ
is times the gas constant R. M
2
i.e. higher will be the molar mass, lower will be
3
E m = RT the value of urms.
2
Molecular masses of H2, N2, O2 and HBr are 2,
3 28, 32 and 81. Hence the correct order of urms
20. (c) Average molar kinetic energy = kT
2 will be HBr < O2 < N2 < H2
As temperature is same hence average kinetic 28. (c) According to kinetic gas equation
energy of CO and N2 will be same. 1
PV = mNu 2 , u = root mean square velocity
21. (d) u µ T or u1 / u 2 = T1 / T2 3
1
1 -
2 3PV
27 + 273 300 1 Þ u = or u µ i.e u µ m 2
= = = mN m
927 + 273 1200 2
29. (a) Absolute zero is the temperature at which
\ u2 = 2u1
kinetic energy of gas molecules becomes zero
22. (a) Average kinetic energy depends only on
i.e. all molecular motion ceases.
temperature æç K.E. = kT ö÷
3
PV
è 2 ø 30. (c) Compressibility factor, Z =
nRT
1 1
23. (a) PV = mnu 2 = Mu 2 Given: At 350 K and 15 bar,
3 3 molar volume < volume of ideal gas
2 1 2 2 2 \ Z< 1
= . M u = E or P = E per unit vol.
3 2 3 3 Therefore, attractive forces are dominant and
2 RT the gas can be compressed easily.
24. (d) Most probable velocity (a ) =
M
EBD_8336
56 CHEMISTRY
31. (c) In real gas equation, van der Wall constant

1 = n1RT
PV
(a) µ forces of attraction.
32. (a) van der Waal constant ‘a’, signifies n1 µ P1 and n2 µ P2
intermolecular forces of attraction.
n1 P1 n 170
Higher is the value of ‘a’, easier will be the = Þ 1 = = 0.30
liquefaction of gas. n2 P2 n2 570
33. (a) At high temperature and low pressure. 41. (b) At low pressure and high temperature, real
34. (c) Higher the critical temperature more easily gas nearly behave like ideal gas. Hence, deviation
will be the gas liquify. Now since most easily is minimum from ideal behaviour.
liquefiable gas show larger deviation, NH3 will AlAt high temperature and low pressure, the
show maximum deviation from ideal behaviour. correction terms (an2/V2) and (nb) become negligible
PM 5 ´ 28 and thus, the deviation from ideal behaviour will
35. (d) Density = = = 3.41g/mL be minimum.
RT 0.0821 ´ 500
36. (c) Set-I : O2, CO2, H2, He for 'b' values n
42. (c) PV = nRT or P = RT = CRT.
Set-II : CH4, O2, H2, for 'a' values V
Value of van der Waals constant 'b' increases Hence 1 = 1 × 0.082 × T
with increase in molecular volume. Clearly, the
1
increasing order of molecular volume (size of \ T= = 12 K
molecule) is: 0.082
He < H2 < O2 < CO2 43. (b) At low temperature and high pressure.
Value of 'a' increases with increase in 44. (c) Molecules of an ideal gas move with
intermolecular attraction. CH4 is a polar molecule, different speeds.
thus, it will possess highest value of 'a'. O2 and 45. (d) In an ideal gas, the intermolecular forces of
H2, both are non-polar molecules. The van der attraction are negligible and hence, it cannot be
Waals force µ molecular mass. Hence, the correct liquefied.
order of value of 'b' is : CH4 > O2 > H2. 46. (c) In the equation PV = nRT, n moles of the
From the given options, (c) is most suitable. gas have volume V.
37. (a) Given nCO = nN 2 In van der Waals equation, n moles of gas occupies
volume V and exert pressure P at a temperature T.
PCO + PN2 = 1 atm
Partial pressure of a gas = mole fraction of gas × 47. (d) At low pressure and high temperature
total pressure correction for 1 mole of a gas is negligible, i.e
the effect of a/v2 and b becomes negligible.
nN 2 nN 2 Thus, the gas equation becomes
\ PN 2 = ´1 = ´1 PV = nRT
nCO + nN 2 2nN 2
PV
1 PV = RT or = 1 [Ideal gas equation]
= = 0.5 atm. RT
2
\ Z = 1, and gas shows ideal behaviour.
nRT w RT 48. (c) van der Waal's equation for 1 mole :
38. (d) P = =
V m V æ a ö
çè P + 2 ÷ø (V - b) = RT
6 ´8.314 ´ 402 V
= ; 41648Pa
16.05 0.03
Here, æç P + a ö÷ represent the intermolecular
39. (a) At higher temperature and low pressure è V2ø
real gas acts as an ideal gas.
40. (d) By Ideal gas equation forces and (V – b) is the corrected volume.
States of Matter 57
m Hydrogen bonding is in order H2O > C2H5OH >

49. (d) PV = nRT = RT CH3OH.
M
52. (a) By definition of Nernst distribution law.
m PM
or PM = RT = dRT Þ d = When a solute is shaken with two immiscible
V RT liquids, having solubility in both, the solute
PV PV PV distributes itself between the two liquids in such
50. (b) = constant or 1 1 = 2 2 a way that the ratio of its concentrations in two
T T1 T2
liquids is constant at a given temperature,
PV
1 1 = T1 provided the molecular state of the solute
Þ
P2V2 T2 remains the same in both the liquids.
51. (c) Due to intermolecular H-bonding the 53. (d) A substance exists as a liquid above its
surface tension of H2O is more than other given m. pt. and below its b. pt.
liquids. One H2O molecule is joined with 4
another H2O molecule through H–bond.
EBD_8336
58 CHEMISTRY
6 Thermodynamics
2020 2019 2018 2017 2016

First law and basic first law of
1 A 1 A 1 A
fundamentals of thermodynamics
thermodynamics
bond di ssociation
Laws of 1 D
energy
thermochemistry
second law of
Entropy and second 1 A
thermodynamics
law of thermodynamics
entropy 1 E
Spontaneity and Gibb's spontaniety 1 A 1 E
free energy
Topic 1: First Law and Basic Fundamentals

of Thermodynamics
1. The correct option for free expansion of an ideal
gas under adiabatic condition is [2020]
(a) q = 0, DT < 0 and w > 0
(b) q < 0, DT = 0 and w = 0
(c) q > 0, DT > 0 and w > 0
(d) q = 0, DT = 0 and w = 0 AB ® Isothermal expansion
2. An ideal gas expands isothermally from 10–3 m3 AC ® Adiabatic expansion
to 10–2 m3 at 300 K against a constant pressure Which of the following options is not correct?
of 105 Nm–2. The work done on the gas is (a) TC > TA (b) DSisothermal > DSadiabatic
[NEET Odisha 2019] (c) TA = TB (d) Wisothermal > Wadiabatic
(a) –900 kJ (b) +270 kJ 4. Under isothermal condition, a gas at 300 K
(c) –900 J (d) +900 kJ expands front 0.1 L to 0.25 L against a constant
3. Reversible expansion of an ideal gas under external pressure of 2 bar. The work done by
isothermal and adiabatic conditions are as the gas is [Given that 1 L bar = 100 J] [2019]
(a) –30 J (b) 5 kJ
shown in the figure. [NEET Odisha 2019] (c) 25 J (d) 30 J
Thermodynamics 59
5. A gas is allowed to expand in a well insulated 13. Adiabatic expansions of an ideal gas is
container against a constant external pressure accompanied by [1999]
of 2.5 atm from an initial volume of 2.50 L to a (a) decrease in DE
final volume of 4.50 L. The change in internal (b) increase in temperature
energy DU of the gas in joules will be:- [2017]
(c) decrease in DS
(a) – 500 J (b) – 505 J
(c) + 505 J (d) 1136.25 J (d) no change in any one of the above properties
6. The heat of combustion of carbon to CO2 is Topic 2: Laws of Thermochemistry
–393.5 kJ/mol. The heat released upon formation
of 35.2 g of CO2 from carbon and oxygen gas is 14. The bond dissociation energies of X2, Y2 and
[2015 RS] XY are in the ratio of 1 : 0.5 : 1. DH for the formation
(a) –315 kJ (b) +315 kJ of XY is –200 kJ mol–1. The bond dissociation
(c) –630 kJ (d) –3.15 kJ energy of X2 will be [2018]
7. When 5 litres of a gas mixture of methane and
(a) 200 kJ mol–1 (b) 100 kJ mol–1
propane is perfectly combusted at 0°C and 1
atmosphere, 16 litre of oxygen at the same (c) 400 kJ mol–1 (d) 800 kJ mol–1
temperature and pressure is consumed. The 15. Three thermochemical equations are given below:
amount of heat released from this combustion in (i) C(graphite) + O2(g) ® CO2(g);
kJ (DHcomb (CH4) = 890 kJ mol–1, DHcomb (C3H8) = DrH° = x kJ mol–1
2220 kJ mol–1) is [NEET Kar. 2013] 1
(a) 32 (b) 38 (ii) C(graphite) + O2(g) ® CO(g);
2
(c) 317 (d) 477 DrH° = y kJ mol–1
8. Which of the following is correct option for free
expansion of an ideal gas under adiabatic 1
(iii) CO(g) + O2(g) ® CO2(g);
condition ? [2011] 2
(a) q = 0, DT ¹ 0, w = 0 DrH° = z kJ mol–1
(b) q ¹ 0, DT = 0, w = 0 Based on the above equations, find out which
(c) q = 0, DT = 0, w = 0 of the relationship given below is correct?
(d) q = 0, DT < 0, w ¹ 0 [NEET Kar. 2013]
9. Three moles of an ideal gas expanded (a) x = y – z (b) z = x + y
spontaneously into vacuum. The work done will
(c) x = y + z (d) y = 2z – x
be : [2010]
(a) Zero (b) Infinite 16. Standard enthalpy of vapourisation Dvap H° for
(c) 3 Joules (d) 9 Joules water at 100°C is 40.66 kJ mol–1. The internal
10. Which of the following are not state functions ? energy of vaporisation of water at 100°C
(I) q + w (II) q [2008] (in kJ mol–1) is : [2012]
(III) w (IV) H - TS (a) + 37.56 (b) – 43.76
(a) (I) and (IV) (b) (II), (III) and (IV) (c) + 43.76 (d) + 40.66
(c) (I), (II) and (III) (d) (II) and (III) (Assume water vapour to behave like an ideal gas).
11. In a closed insulated container, a liquid is stirred 17. Equal volumes of two monoatomic gases, A and
with a paddle to increase the temperature, which B, at same temperature and pressure are mixed.
of the following is true? [2002]
The ratio of specific heats (Cp/Cv) of the mixture
(a) DE = W ¹ 0, q = 0 (b) DE = W = q ¹ 0
(c) DE = 0, W = q ¹ 0 (d) W = 0, DE = q ¹ 0 will be : [2012 M]
12. When 1 mol of a gas is heated at constant (a) 0.83 (b) 1.50
volume, temperature is raised from 298 to 308 K. (c) 3.3 (d) 1.67
If heat supplied to the gas is 500 J, then which 18. Enthalpy change for the reaction, [2011]
statement is correct ? [2001] 4H(g) ¾¾ ® 2H 2 (g) is – 869.6 kJ.
(a) q = w = 500 J, DU = 0 The dissociation energy of H–H bond is :
(b) q = DU = 500 J, w = 0 (a) – 434.8 kJ (b) – 869.6 kJ
(c) q = –w = 500 J, DU = 0
(c) + 434.8 kJ (d) + 217.4 kJ
(d) DU = 0, q = w = –500 J
EBD_8336
60 CHEMISTRY
19. Consider the following processes : Enthalpy of formation of H2O (l) is

DH (kJ/mol) (a) + X3 kJ mol– 1 (b) – X4 kJ mol– 1
1/2 A ® B +150 (c) + X1 kJ mol– 1 (d) – X2 kJ mol– 1
3B ® 2C + D –125 24. Given that bond energies of H – H and Cl – Cl
E + A ® 2D +350 are 430 kJ mol– 1 and 240 kJ mol–1 respectively
For B + D ® E + 2C, DH will be : [2011M] and DHf for HCl is – 90 kJ mol– 1, bond enthalpy
(a) 525 kJ/mol (b) – 175 kJ/mol of HCl is [2007]
(c) – 325 kJ/mol (d) 325 kJ/mol (a) 380 kJ mol–1 (b) 425 kJ mol–1
20. The following two reactions are known : [2010] (c) 245 kJ mol–1 (d) 290 kJ mol–1
Fe2O3(s) + 3CO (g) ¾¾ ® 2Fe (s) + 3CO2(g); 25. The enthalpy of hydrogenation of cyclohexene
DH = –26.8 kJ is – 119.5 kJ mol–1. If resonance energy of benzene
FeO (s) + CO (g) ¾¾ ® Fe (s) + CO2(g); is –150.4 kJ mol–1, its enthalpy of hydrogenation
DH = –16.5 kJ would be [2006]
The value of D H for the following reaction (a) – 208.1 kJ mol–1 (b) – 269.9 kJ mol–1
Fe2O3(s) + CO(g) ¾¾ ® 2FeO(s) + CO2(g) is; (c) – 358.5 kJ mol–1 (d) – 508.9 kJ mol–1
26. Assume each reaction is carried out in an open
(a) + 6.2 kJ (b) + 10.3 kJ container. For which reaction will DH = DE ?
(c) – 43.3 kJ (d) – 10.3 kJ [2006]
21. From the following bond energies: [2009] (a) C(s) + 2H2O (g) ® 2H2 (g) + CO2 (g)
H – H bond energy: 431.37 kJ mol–1 (b) PCl5 (g) ® PCl3 (g) + Cl2 (g)
C = C bond energy: 606.10 kJ mol–1 (c) 2CO (g) + O2 (g) ® 2CO2 (g)
C – C bond energy: 336.49 kJ mol–1 (d) H2 (g) + Br 2 (g) ® 2 HBr (g)
C – H bond energy: 410.50 kJ mol–1 27. The absolute enthalpy of neutralisation of the
Enthalpy for the reaction, reaction:
H H H H MgO (s) + 2HCl (aq) ¾® MgCl2 (aq) + H2O (l)
| | | | will be: [2005]
C = C + H - H ¾¾
® H - C- C - H (a) -57.33 kJ mol-1
| | | | (b) Greater than -57.33 kJ mol- 1
H H H H (c) Less than -57.33 kJ mol-1
will be: (d) 57.33 kJ mol-1
(a) – 243.6 kJ mol–1 (b) –120.0 kJ mol–1 28. If the bond energies of H - H, Br - Br, and
(c) 553.0 kJ mol –1 (d) 1523.6 kJ mol–1 H-Br are 433, 192 and 364 kJ mol–1 respectively,
22. Bond dissociation enthalpy of H2, Cl2 and HCl the DH° for the reaction [2004]
are 434, 242 and 431 kJ mol–1 respectively. H 2 (g) + Br2 (g) ® 2HBr (g) is
Enthalpy of formation of HCl is : [2008]
(a) 93 kJ mol–1 (b) – 245 kJ mol–1 (a) – 261 kJ (b) + 103 kJ
(c) – 93 kJ mol–1 (d) 245 kJ mol–1 (c) + 261kJ (d) – 103 kJ
23. Consider the following reactions: [2007] 29. The work done during the expansion of a
(i) H +(aq) + OH–(aq) = H2O(l), gas from a volume of 4 dm3 to 6 dm3 against
DH = – X1 kJ mol–1 a constant external pressure of 3 atm is
(1 L atm = 101.32 J) [2004]
1
(ii) H2(g) + O2(g) = H2O(l), (a) – 6 J (b) – 608 J
2 (c) + 304 J (d) – 304 J
DH = – X2 kJ mol–1 30. The molar heat capacity of water at constant
(iii) CO2(g) + H2(g) = CO(g) + H2O, pressure is 75 JK–1 mol–1. When 1kJ of heat is
DH = – X3 kJ mol–1 supplied to 100 g of water, which is free to
5 expand, the increase in temperature of water is
(iv) C2 H2 (g) + O2 (g) = 2CO2(g) + H2O(l)’
2 (a) 6.6 K (b) 1.2 K [2003]
DH = + 4X4 kJ mol–1 (c) 2.4 K (d) 4.8 K
Thermodynamics 61
31. The densities of graphite and diamond at 298 K (a) DH < DE (b) DH = DS
are 2.25 and 3.31 g cm–3, respectively. If the (c) DH = DE (d) DH = DG
standard free energy difference (DGº) is equal 40. One mole of an ideal gas at 300 K is expanded
to 1895 J mol–1, the pressure at which graphite isothermally from an initial volume of 1 litre to
will be transformed into diamond at 298 K is 10 litres. The DE for this process is
[2003] (R = 2 cal. mol–1 K–1) [1998]
(a) 9.92 × 105 Pa (b) 9.92 × 108 Pa (a) 163.7 cal (b) zero
(c) 9.92 × 107 Pa (d) 9.92 × 106 Pa (c) 1381.1 cal (d) 9 lit. atm
32. For which one of the following equations is
DHºreact equal to DHf º for the product? [2003] 41. Given that C + O2 ® CO 2 : DHº = - x kJ
(a) 2 CO(g) + O 2 (g) ® 2 CO 2 (g) 2CO + O2 ® 2CO 2 : DHº = - y kJ
(b) N 2 (g) + O3 (g) ® N 2 O 3 (g) the enthalpy of formation of carbon monoxide
(c) CH 4 ( g ) + 2Cl ( g ) ® CH 2 Cl 2 l + 2HCl ( g ) will be [1997]
()
2x - y y - 2x
(d) Xe(g) + 2F2 (g) ® XeF4 (g) (a) (b)
33. For the reaction 2 2
C3 H8 ( g ) + 5O2 ( g ) ® 3CO2 ( g ) + 4 H 2O(l ) (c) 2x – y (d) y – 2x
at constant temperature, DH – DE is [2003] 42. Hydrogen has an ionisation energy of 1311 kJ
(a) – RT (b) + RT mol –1 and for chlorine it is 1256 kJ mol –1.
(c) – 3 RT (d) + 3 RT Hydrogen forms H+ (aq) ions but chlorine does
34. Heat of combustion DHº for C (s), H2 (g) and not form Cl+ (aq) ions because [1996]
CH4 (g) are –94, –68 and –213 kcal/mol, then (a) H+ has lower hydration enthalpy
(b) Cl+ has lower hydration enthalpy
DHº for C(s) + 2H 2 (g) ® CH 4 (g) is [2002]
(c) Cl has high electron affinity
(a) –17 kcal (b) – 111 kcal (d) Cl has high electronegativity
(c) –170 kcal (d) –85 kcal
1 43. If enthalpies of formation of C2 H 4( g ) , CO2(g)
35. Enthalpy of CH 4 + O 2 ® CH 3 OH is
2 and H 2 O(l) at 25°C and 1atm pressure are 52,
negative. If enthalpy of combustion of CH4 and
CH3OH are x and y respectively, then which – 394 and – 286 kJ/mol respectively, the
relation is correct [2001] enthalpy of combustion of C2H4 is equal to
(a) x > y (b) x < y [1995]
(c) x = y (d) x ³ y (a) – 141.2 kJ/mol (b) – 1412 kJ/mol
36. What is the enthalpy change for, (c) + 14.2 kJ/mol (d) + 1412 kJ/mol
44. Equal volumes of molar hydrochloric acid and
2H 2O 2 (l) ® 2 H 2 O(l) + O 2 (g) if heat of sulphuric acid are neutralized by dil. NaOH
formation of H2O2 (l) and H2O (l) are –188 and solution and x kcal and y kcal of heat are liberated
–286 kJ/mol respectively? [2001] respectively. Which of the following is true ?
(a) –196 kJ/mol (b) + 948 kJ/mol [1994]
(c) + 196 kJ/mol (d) –948 kJ/mol 1
37. The values of heat of formation of SO2 and SO3 (a) x = y (b) x = y
are –298.2 kJ and –98.2 kJ. The heat of formation 2
(c) x = 2y (d) None of these
of the reaction [2000] 45. For the reaction [1994]
SO 2 + (1 / 2) O 2 ® SO 3 will be N 2 + 3H 2 2NH3, D H = ?
(a) –200 kJ (b) –356.2 kJ
(c) + 200 kJ (d) – 396.2 kJ (a) D E + 2RT (b) D E –2RT
38. For a cyclic process, which of the following is (c) D H = RT (d) D E – RT.
not true? [1999] 46. During isothermal expansion of an ideal gas, its
(a) DH = 0 (b) DE = 0 [1991, 94]
(c) DG = 0 (d) Total W = 0 (a) internal energy increases
39. For a reaction in which all reactants and (b) enthalpy decreases
products are liquids, which one of the following (c) enthalpy remains unaffected
equations is most applicable ? [1999] (d) enthalpy reduces to zero.
EBD_8336
62 CHEMISTRY
47. If DH is the change in enthalpy and DE , the 54. What is the entropy change (in JK–1 mol–1) when
change in internal energy accompanying a one mole of ice is converted into water at 0º C?
gaseous reaction, then [1990] (The enthalpy change for the conversion of ice
to liquid water is 6.0 kJ mol–1 at 0ºC) [2003]
(a) DH is always greater than DE , (a) 21.98 (b) 20.13
(b) DH < D E only if the number of moles of (c) 2.013 (d) 2.198
the products is greater than the number of 55. 2 mole of an ideal gas at 27ºC temperature is
moles of the reactants expanded reversibly from 2 lit to 20 lit. Find the
(c) D H is always less than D E entropy change (R = 2 cal/mol K) [2002]
(d) D H < D E only if the number of moles of (a) 92.1 (b) 0
products is less than the number of moles (c) 4 (d) 9.2
of the reactants. 56. Unit of entropy is [2002]
Topic 3: Entropy and Second Law of (a) JK–1 mol–1 (b) J mol–1
Thermodynamics (c) J–1 K–1 mol–1 (d) JK mol–1
57. The entropy change in the fusion of one mole
48. For the reaction, 2Cl(g) ¾® Cl2(g), the correct of a solid melting at 27ºC (Latent heat of fusion,
option is : [2020] 2930 J mol–1) is : [2000]
(a) DrH > 0 and DrS < 0 (a) 9.77 J K mol
–1 –1 (b) 10.73 J K mol–1
–1
(b) DrH < 0 and DrS > 0 (c) 2930 J K mol–1 –1 (d) 108.5 J K–1 mol–1
(c) DrH < 0 and DrS < 0 58. Identify the correct statement regarding
(d) DrH > 0 and DrS > 0 entropy: [1998]
(a) At absolute zero of temperature, entropy
49. In which case change in entropy is negative ? of a perfectly crystalline substance is taken
[2019] to be zero
(a) Evaporation of water (b) At absolute zero of temperature, the
(b) Expansion of a gas at constant temperature entropy of a perfectly crystalline substance
(c) Sublimation of solid to gas is +ve
(d) 2H(g) ® H2(g) (c) At absolute zero of temperature, the
50. The enthalpy of fusion of water is 1.435 kcal/mol. entropy of all crystalline substances is
The molar entropy change for the melting of ice taken to be zero
at 0°C is : [2012] (d) At 0ºC, the entropy of a perfectly
crystalline substance is taken to be zero
(a) 10.52 cal / (mol K) (b) 21.04 cal / (mol K)
59. According to the third law of thermodynamics
(c) 5.260 cal / (mol K) (d) 0.526 cal / (mol K)
which one of the following quantities for a
51. If the enthalpy change for the transition of liquid perfectly crystalline solid is zero at absolute
water to steam is 30 kJ mol–1 at 27ºC, the entropy zero? [1996]
change for the process would be : [2011] (a) Free energy (b) Entropy
(a) 10 J mol –1 K–1 (b) 1.0 J mol–1 K–1
(c) 0.1 J mol–1 K–1 (d) 100 J mol–1 K–1 (c) Enthalpy (d) Internal energy
52. Standard entropies of X2, Y2 and XY3 are 60, 40 60. Given the following entropy values (in J K–1 mol–1)
and 50 JK–1mol–1 respectively. For the reaction at 298 K and 1 atm :H2 (g) : 130.6, Cl2 (g) : 223.0,
1 3 HCl (g) : 186.7. The entropy change (in J K–1
X 2 + Y2 XY3 , DH = – 30 kJ mol–1) for the reaction
2 2
to be at equilibrium, the temperature should be: H 2 (g) + Cl2 (g) ¾¾
® 2HCl(g) is [1996]
[2010] (a) +540.3 (b) +727.0
(a) 750 K (b) 1000 K (c) –166.9 (d) +19.8
(c) 1250 K (d) 500 K 61. A chemical reaction will be spontaneous if it is
53. For the gas phase reaction, [2008] accompanied by a decrease of [1994]

PCl5(g) PCl3(g) + Cl2(g) (a) entropy of the system
which of the following conditions are correct ? (b) enthalpy of the system
(a) DH = 0 and DS < 0 (b) DH > 0 and DS > 0 (c) internal energy of the system
(c) DH < 0 and DS < 0 (d) DH > 0 and DS < 0 (d) free energy of the system
Thermodynamics 63
Topic 4: Spontaneity and Gibb's Free Energy Options:

(1) (2) (3) (4)
62. For a given reaction, DH = 35.5 kJ mol-1 and
DS = 83.6 JK-1 mol-1. The reaction is spontaneous (a) (ii) (i) (iv) (iii)
at: (Assume that DH and DS do not vary with (b) (i) (ii) (iii) (iv)
temperature) [2017] (c) (iii) (iv) (ii) (i)
(a) T > 425 K (b) All temperatures (d) (iv) (i) (ii) (iii)
(c) T > 298 K (d) T < 425 K 68. The values of DH and DS for the reaction,
63. The correct thermodynamic conditions for the C(graphite) + CO2(g) ® 2CO(g) are 170 kJ and
spontaneous reaction at all tempertures is
[2016] 170 JK–1, respectively. This reaction will be
(a) DH > 0 and DS > 0 (b) DH > 0 and DS < 0 spontaneous at [2009]
(c) DH < 0 and DS > 0 (d) DH < 0 and DS < 0 (a) 910 K (b) 1110 K
64. For the reaction : [2014] (c) 510 K (d) 710 K
X2O4(l) ® 2XO2(g) 69. The enthalpy and entropy change for the
DU = 2.1 k cal, DS = 20 cal K–1 at 300 K reaction
Hence DG is:- Br2(l) + Cl2 (g) ® 2 BrCl (g)
(a) 2.7 k cal (b) – 2.7 k cal are 30kJ mol–1 and 105 JK–1 mol–1 respectively.
(c) 9.3 k cal (d) – 9.3 k cal The temperature at which the reaction will be in
65. In which of the following reactions, standard equilibrium is [2006]
entropy change (DS°) is positive and standard (a) 273 K (b) 450 K
Gibb’s energy change (DG°) decreases sharply
(c) 300 K (d) 285.7 K
with increasing temperature ? [2012]
70. Identify the correct statement for change of Gibbs
1 energy for a system (DG system) at constant
(a) C (graphite) + O2(g) ® CO(g)
2 temperature and pressure : [2006]
1 (a) If DGsystem = 0, the system has attained
(b) CO(g) + O (g) ® CO2(g) equilibrium
2 2
(b) If DGsystem = 0, the system is still moving in
1 a particular direction
(c) Mg(s) + O (g) ® MgO(s)
2 2 (c) If DGsystem < 0, the process is not spontaneous
(d) If DGsystem > 0, the process is spontaneous
1 1 1
(d) C (graphite) + O2(g) ® CO2(g) 71. A reaction occurs spontaneously if [2005]
2 2 2 (a) TDS < DH and both DH and DS are + ve
66. For vaporization of water at 1 atmospheric (b) TDS > DH and DH is + ve and DS is - ve
pressure, the values of DH and DS are 40.63 (c) TDS > DH and both DH and DS are + ve
kJmol–1 and 108.8 JK–1 mol–1, respectively. The (d) TDS = DH and both DH and DS are + ve
temperature when Gibbs energy change (DG) 72. Which of the following pairs of a chemical
for this transformation will be zero, is: [2010] reaction is certain to result in a spontaneous
(a) 293.4 K (b) 273.4 K reaction? [2005]
(c) 393.4 K (d) 373.4 K. (a) Exothermic and increasing disorder
67. Match List -I (Equations) with List-II (Type of (b) Exothermic and decreasing disorder
processes) and select the correct option. [2010] (c) Endothermic and increasing disorder
List I List II (d) Endothermic and decreasing disorder
Equations Type of processes 73. Stan dard enthalpy and standard entropy
(1) Kp > Q (i) Non-spontaneous changes for the oxidation of ammonia at 298 K
(2) DG° < RT In Q (ii) Equilibrium are – 382.64 kJ mol–1 and -145.6 JK–1 mol–1,
(3) Kp = Q (iii) Spontaneous and respectively. Standard Gibb's energy change for
endothermic the same reaction at 298 K is [2004]
DH (a) –22.1 kJ mol–1 (b) –339.3 kJ mol–1
(4) T > (iv) Spontaneous (c) –439.3 kJ mol–1 (d) –523.2 kJ mol–1
DS
EBD_8336
64 CHEMISTRY
74. Considering entropy (S) as a thermodynamic 2Zn(s) + O2 (g) ¾¾

® 2ZnO(s) ; DG = –480 kJ
parameter, the criterion for the spontaneity of Then DG for the reaction :
any process is [2004]
2ZnS(s) + 3O2 (g) ¾¾
® 2ZnO(s) + 2SO2 (s)
(a) DSsystem + DSsurroundings > 0
will be : [2000]
(b) DSsystem - DSsurroundings > 0
(a) –357 kJ (b) –731 kJ
(c) DSsystem > 0 only (c) –773 kJ (d) –229 kJ
(d) DSsurroundings > 0 only 76. Consider the following reaction occurring in an
75. The factor of DG values is important in automobile [1994]
metallurgy. The DG values for the following
reactions at 800ºC are given as : ® 16CO 2 +18H 2 O(g)
2C8H18 (g) + 25 O 2 (g) ¾¾
® 2SO2 (g) ; DG = –544 kJ
S2 (s) + 2O 2 (g) ¾¾ the sign of D H, D S and D G would be
(a) +, –, + (b) –, +, –
2Zn(s) + S2 (s) ¾¾ ® 2ZnS(s) ; DG = –293 kJ (c) –, +, + (d) +, +, –.
ANSWER KEY
1 (d) 9 (a) 17 (d) 25 (a) 33 (c) 41 (b) 49 (d) 57 (a) 65 (a) 73 (b)
2 (c) 10 (d) 18 (c) 26 (d) 34 (a) 42 (b) 50 (c) 58 (a) 66 (d) 74 (a)
3 (a) 11 (a) 19 (b) 27 (c) 35 (a) 43 (b) 51 (d) 59 (b) 67 (d) 75 (b)
4 (a) 12 (b) 20 (a) 28 (d) 36 (a) 44 (b) 52 (a) 60 (d) 68 (b) 76 (b)
5 (b) 13 (a) 21 (b) 29 (b) 37 (c) 45 (b) 53 (b) 61 (d) 69 (d)
6 (a) 14 (d) 22 (c) 30 (c) 38 (d) 46 (c) 54 (a) 62 (a) 70 (a)
7 (c) 15 (c) 23 (d) 31 (N) 39 (c) 47 (d) 55 (d) 63 (c) 71 (c)
8 (c) 16 (a) 24 (b) 32 (d) 40 (b) 48 (c) 56 (a) 64 (b) 72 (a)
Hints & Solutions

1. (d) Free expansion of ideal gas 5. (b) The system is in isolated state.
Pex = 0 Q For an adiabatic process, q = 0
\ w = - Pex DV = 0 DU = q + w
\ DU = w
Q Adiabatic process Þ q = 0 = –pDV
DE = q + w (first law of thermodynamics) = –2.5 atm × (4.5 – 2.5) L
\ DE = 0 = –2.5 × 2 L-atm
= –5 × 101.3 J
DE = nCv dT Þ DE = 0 = –506.5 J » –505J
So, q = 0, DT = 0, w = 0. 6. (a) C + O2 ® CO2 + 393.5 kJ/mol
2. (c) W = –Pext (Vf – Vi) = –10 (10 – 10 ) = –900 J
5 –2 –3 12g 44g
44g CO2 is formed from 12g of carbon
3. (a) Since graph A to C represents adiabatic
reversible expansion, so work is done on 12 ´ 35.2
35.2g is formed from g of C
the expense of internal energy, therefore, 44
there is decrease in internal energy. So the = 9.6 g of C = 9.6/12 = 0.8 mole
temperature decreases. 1 mole release heat 393.5 kJ
i.e., TC < TA 0.8 mole release heat = 393.5 × 0.8
4. (a) W = – Pext (V2 – V1) (Irreversible isothermal = 314.8 kJ » 315 kJ
expansion) 7. (c) CH 4 + 2O 2 ¾® CO2 + 2H2O
= –2 (0.25 – 0.1) x 2x
= – 2 (0.15) = – 0.3 L Bar
C3 H8 + 5O 2 ¾® 3CO2 + 4H2O
= – 0.3 × 100 J = – 30 J (5- x ) 5(5- x )
Thermodynamics 65
2x + 5(5– x) = 16 DH = DE + DngRT Þ DE = DH – DngRT

Þ x = 3L Dng = number of gaseous moles of products
\ Heat released – number of gaseous moles of reactants
H2Ol H2O(g)
3 2
= ´ 890 + ´ 2220 = 317 Dng = 1 – 0 = 1
22.4 22.4
DE = DH – RT
8. (c) For adiabatic process DQ = 0 DE = (40.66 × 103) – (8.314 × 373)
In free expansion, external pressure is zero. = 37559 J/mol or 37.56 kJ / mol
Thus, work done W = 0 and DE = W = 0. If 17. (d) For a monoatomic gas
DE = 0, then DT = 0. 3
9. (a) Ideal gas during spontaneous expansion Cv = R
into vacuum does not do any external work. 2
10. (d) We know that q (heat) and work (w) are not 3 5
\ Cp = R + R = R
state functions but (q + w) is a state functions. 2 2
H – TS (i.e. G) is also a state function. 5
11. (a) Internal energy is dependent upon Cp 2 R 5
temperature and according to first law of = = = 1.67
thermodynamics total energy of an isolated Cv 3 R 3
system remains same, i.e., in a system of 2
constant mass, energy can neither be created
nor destroyed by any physical or chemical Cp
For monoatomic gases = 1.67
change but can be transformed from one form Cv
to another Cp
DE = q + w diatomic gases = 1.40
Cv
For closed insulated container, q = 0, so, Cp
DE = +W, as work is done on the system triatomic gases = 1.29 if degree of freedom = 7
Cv
12. (b) As volume is constant hence, work done Cp
= 1.33 if degree of freedom = 6
in this process is zero hence, heat supplied is Cv
equal to change in internal energy.
13. (a) DE =DQ – W 18. (c) Given
For adiabatic expansion, DQ = 0 4H(g) ¾¾ ® 2H 2 (g); DH = -869.6 kJ
Þ DE = –W or 2H 2 (g) ¾¾ ® 4H(g); DH = 869.6 kJ
The negative sign shows decrease in Internal
869.6
energy, which is equal to the work done by the H 2 (g) ¾¾ ® 2H(g); DH = = 434.8 kJ
system on the surroundings. 2
14. (d) Let B.E of X2, Y2 and XY are x kJ mol–1, 19. (b) Given DH
0.5 x kJ mol–1 and x kJ mol–1 respectively 1
A ¾¾ ®B + 150 ...(a)
1 1 2
X 2 + Y2 ® XY; DH = –200 kJ mol–1 3B ¾¾ ® 2C + D –125 ...(b)
2 2
DH = –200 = S (B.E)Reactants – S(B.E)Product E + A ¾¾ ® 2 D +350 ...(c)
To calculate DH operate
é1 1 ù 2 × eq. (a) + eq. (b) – eq. (c)
= ê ´ ( x) + ´ (0.5 x ) ú – [1 ´ ( x )]
ë 2 2 û DH = 300 – 125 – 350 = – 175
On solving, x = 800 kJ mol–1 20. (a) Fe2O3(s)+ CO(g) ® 2FeO(s)+ CO2(g)
15. (c) Applying Hess’s law, equation (i) can be Given
obtained by adding equations (ii) and (iii). Fe2O3(s)+ 3CO(g) ® 2Fe(s)+ 3CO2(g) ;
\x=y+z DH = – 26.8 kJ … (i)
16. (a) Dvap H° = 40.66 kJ mol–1 FeO(s) + CO(g) ® Fe(s) + CO2(g) ;
T = 100 + 273 = 373 K, DE = ? DH = –16.5 kJ … (ii)
EBD_8336
66 CHEMISTRY
\ DH for the reaction The resonance energy provides extra stability

Fe2O3(s) + CO2(g) ® 2FeO(s) + CO2(g) to the benzene molecule so it has to overcome
can be calculate as for hydrogenation to take place. So DH = – 358.5
eqn (i) — 2 × eqn (ii) – (–150.4) = –208.1 kJ
\ D H = –26.8 + 33.0 = + 6.2 kJ
Resonance reduces the energy of molecule and thus,
21. (b) Enthalpy of reaction increases the stability. Hence, the magnitude of
= SB.E(Reactant)– SB.E(Product) enthalpy of hydrogenation will be less than the
= éë B.E (C= C) + 4 B.E.(C–H) + B.E.(H - H) ùû expected value for benzene.
26. (d) We know that

- éë B.E.(C - C) + 6 B.E.(C - H) ùû DH = DE + PDV
= [606.1 + (4 × 410.5) + 431.37)] – [336.49 In the reaction, H2 + Br2 ® 2HBr this is no
+ (6 × 410.5)] change in volume or DV = 0
= –120.0 kJ mol–1 So, DH = DE for this reaction
22. (c) The reaction for formation of HCl can be
written as If the container is closed then pressure is not
H2 + Cl2 ® 2HCI constant and DH = DE + V DP
H – H + Cl – Cl ® 2 (H – Cl)
Substituting the given values, we get enthalpy 27. (c) As MgO is a oxide of weak base hence
of formation of some energy is lost to break MgO (s). Hence
DHf (HCl) = [(B.E)H–H + (B.E)Cl–Cl] – enthalpy is less than –57.33 kJ mol–1.
[2 × B.E. (H–Cl)] 28. (d) H 2 (g) + Br2 (g) ® 2HBr (g)
= 434 + 242 – 2 × (431) = –186 kJ
DH ° = (B E)reactant – (B E) product
\ Enthalpy of formation for
= (433 + 192) - (2 ´ 364)
-186
1 mol HCl = kJ = –93 kJ. = 625 – 728 = – 103 kJ
2 29. (b) W = – PDV
23. (d) This reaction shows the formation of H2O,
and the X2 represents the enthalpy of formation = -3(6 - 4) = -6 litre atmosphere
of H2O. = -6 ´101.32 = -608 J
The enthalpy of formation is the heat evolved or 30. (c) Given Cp = 75 JK–1 mol–1
absorbed when one mole of substance is formed 100
n= mole , Q = 1000 J DT = ?
from its constituent atoms. 18
Q = nCpDT
1 1
24. (b) H 2 + Cl2 ¾¾
® HCl 1000 ´ 18
2 2 Þ DT = = 2.4 K
100 ´ 75
D H HCl = å B.E. of reactant 31. (N) Change in volume from 1 mole of graphite
to 1 mole of diamond
- å B.E. of products
12 12
DV = - = -1.71 cm3
1 1 3.31 2.25
-90 = ´ 430 + ´ 240 - B.E. of HCl
2 2 = –1.71 × 10–6 m3
\ B.E. of HCl = 215 + 120 + 90 Gibb's free energy is the measure of useful work
= 425 kJ mol–1 done at constant temperature and pressure.
DG = –p.DV
25. (a) + H2 ¾ ¾
® ; DH = – 119.5 kJ -DG 1895J
Þ p= =
DV 1.71 ´ 10-6 m3
= 1.1 × 109 Pa
+ 3 H2 ¾¾
® ; DH = 3(– 119.5)
32. (d) N2(g) + O3(g) ¾¾ ® N2O3(g)
= – 358.5 kJ
Thermodynamics 67
The state of N2O3 is liquid in NTP conditions. 38. (d) For a cyclic process
Thus, this reaction is not equal to DHf° for the DE = 0, DH = 0 & DG = 0. As all depend upon
product. final state and initial state,W doesn’t depend
(d) Xe(g) + 2F2(g) ¾¾ ® XeF4(g) on path followed.
For this reaction DHr° is equal to DHf° of XeF4(g). 39. (c) As all reactant and product are liquid
33. (c) DH = DE + DnRT Dn ( g ) = 0
Dn = 3 – (1 + 5)
= 3 – 6 = –3 DH = DE - DnRT
DH - DE = (-3RT ) DH = DE (Q Dn = 0)
40. (b) For an isothermal process DE = 0
34. (a) C(s) + O2 (g) ® CO2 (g)
41. (b) Given C + O 2 = CO 2 , DH º = - x kJ ....(a)
DH = -94 kcal/mole ..(i)
1 2CO 2 = 2CO + O 2 DH º = + y kJ … (b)
H 2 (g) + O2 ® H 2 O(g)
2 or CO2 = CO + 1/ 2 O2 , DH º = + y / 2 kJ ...(c)
DH = -68 kcal/mole ..(ii) From eq. no. (a) and (c)
CH 4 + 2O2 ® CO2 + 2H 2O, 1 y - 2x
DH = -213 k cal/mole ...(iii) C + O 2 = CO, DH º = y / 2 - x = kJ
2 2
C(s) + 2H 2 ® CH 4 (g), DH = ? ...(iv) 42. (b) Hydration energy of Cl+ is very less than
Eqn. (iv) can be obtained by H+, hence it doesn’t form Cl+ (aq) ion.
eq. (i) + eq. (ii) × 2 – eq.(iii) 43. (b) Enthalpy of formation of C 2 H 4 , CO2 and
C(s) + O2 (g) ® CO 2 (g) H 2 O ar e 52, – 394 an d – 286 kJ/ mol
2H 2 (g) + O2 (g) ® 2H 2O(g) respectively. (Given)
CO2 (g) + 2H 2 O(g) ® CH 4 (g) + 2O 2 (g) The reaction is
C(s) + 2H 2 (g) ® CH 4 (g) C 2 H 4 + 3O 2 ® 2CO 2 + 2H 2O.
So, DH CH 4 = -94 + 2( -68) - ( -213) change in enthalpy,
= –94 – 136 + 213 = –17 k cal/mole
( DH ) = DH products - DH reactants
35. (a) The enthalpy of combustion is always
negative. = 2 ´ (-394) + 2 ´ (-286) - (52 + 0)
CH4 + 2O2 ¾¾ ® CO2 + 2H2O; DH1 = –x kJ = – 1412 kJ/ mol.
3 44. (b) 1 M H2SO4 = 2g eq. of HCl
CH3OH + O2 ¾¾ ® CO2 + 2H2O; D H2 = - ykJ
2 1
1 Hence y = 2x or x = y.
CH4 + O2 ¾¾ ®CH2OH; + DH = DH1- DH2 2
2
It is given that DH = is negative. 45. (b) D ng = 2 – 4 = – 2, D H = D E – 2RT.
Thus, –x –(–y) = – ve 46. (c) During isothermal expansion of ideal gas,
y – x = –ve D T = 0. Now H = E + PV
Hence, x > y.
Q DH = DE + D( PV )
36. (a) 2H 2 O 2 (l) ¾¾ ® 2H 2 O(l) + O 2 (g) DH = ?
\ D H = D E + D (nRT);
DH = [2 ´ DH f of H 2 O ( l ) + ( DH f of O 2 ) Thus, if D T = 0., DH = DE
-(2 ´ DH f of H 2O2(l) )] i.e., remain unaffected.
47. (d) As DH = DE + DngRT
= [(2 ´ ( -286)) + (0) - (2 ´ (-188))]
if np < nr; D ng = np – nr = – ve.
= [-572 + 376] = -196 kJ / mole
Hence D H < D E.
1
37. (c) SO 2 + O2 ¾
¾® SO 3
48. (c) We know that, Cl 2 (g) ¾¾ ® 2Cl (g) is
2
DH = DH fo (SO ) - DH fo (SO ) endothermic reaction because it required energy
3 2 to break bond.
= –98.2 + 298.2 = 200 kJ/Mole
EBD_8336
68 CHEMISTRY
= 2 × 2 × T × 2.303 × 1 = 9.2 T
So reverse reaction, 2Cl (g) ¾¾ ® Cl2 (g) will
be q 9.2T
Entropy change, DS = = = 9.2 cal.
exothermic, D r H < 0 . T T
q
Also, two gaseous atom combine together to 56. (a) DS =
form 1 gaseous molecule. T
q ¾¾ ® required heat per mole
49. (d) In 2H(g) ¾ ® H 2 (g), no. of moles T ¾¾ ® constant absolute temperature
decreases, therefore entropy decreases. Unit of entropy is JK–1 mol–1
Latent heat of fusion DH y
DH 1.435 ´ 103 57. (a) DS = =
50. (c) DS = = Melting point T
T 273
= 5.260 cal / mol - K 2930
51. (d) Given D H = 30 kJ mol–1 T = 273 + 27 = 300 K = J K–1 mol–1 = 9.77 J K–1 mol–1
300
58. (a) We know from the third law of
DHT 3 ´ 104
DST = = J mol–1 thermodynamics, the entropy of a perfectly
T 300 crystalline substance at absolute zero
= 100 J mol–1 K–1 temperature is taken to be zero.
1 3 59. (b) Entropy is zero for perfectly crystaline solid
52. (a) ΔS for the reaction X 2 + Y2 XY3 at absolute zero.
2 2
ΔS = 50 – (30 + 60) = – 40 J
Entropy states the randomness or disorderness of
For equilibrium D G = 0 = D H – T D S the system. At absolute zero, the movement of
H - 30000
D
molecules of the system or randomenss of the
T = = = 750 K system is zero, hence entropy is also zero.
S
D - 40
53. (b) For the reaction 60. (d) Entropy change

PCl5 (g) PCl3 (g) + Cl2 (g) DS = DSproduct - DSreactant
The reaction given is an example of
decomposition reaction and we know that = 2 (186.7) – (223 + 130.6)
decomposition reactions are endothermic in = 373.4 – 353.6
nature, i.e, D H > 0. = 19.8 JK–1 mol–1
Further 61. (d) D G is negative for a spontaneous process.
D n = (1 + 1) – 1= + 1 62. (a) Given D H 35.5 kJ mol–1
Hence more number of molecules are present in D S = 83.6 JK
–1 mol–1
products which shows more randomness i.e. Q D G = D H – TD S
D S > 0 (D S is positive) For a reaction to be spontaneous, D G = –ve
DH i.e., D H < TD S
54. (a) DS =
T DH 35.5 ´ 103 Jmol -1
\ T> =
DH per mole 6000 DS 83.6 JK -1
DS (per mole) = = So, the given reaction will be spontaneous at
T 273
T > 425 K
= 21.98 JK 1mol 1
- -
63. (c) D G = D H – T · D S
55. (d) For isothermal reversible expansion For a spontaneous reaction D G = –ve (always)
which is possible only if
v2 D H < 0 and D S > 0
w = q = nRT ´ 2.303 log
v1 \ spontaneous at all temperatures.
64. (b) Given D U = 2.1 k cal, D S = 20 cal. K– 1

20 T = 300 K
= 2 RT ´ 2.303 log
2 Q D H = D U + D ngRT
Putting the values given in the equation
Thermodynamics 69
2 When the reaction is in equilibrium, DG = 0

DH = 2.1 + 2 ´ ´ 300 DH
1000 0 = DH - T DS Þ T =
= 2.1 + 1.2 = 3.3 k cal. DS
Now, DG = DH – TDS 2 ´ 30 ´ 1000
20 T= = 285.7 K
= 3.3 - 300 ´ = - 2.7 k cal 2 ´ 105
1000 70. (a) If DGsystem = 0 the system has attained
65. (a) Since, in the first reaction more (Dn > 0) equilibrium.
gaseous products are forming from solid carbon If DG < 0, the process is spontaneous
hence, entropy will increase i.e. If DG > 0, the process does not occur in the forward
DS = +ve. direction. It may occur in the backward direction.
1 71. (c) For a spontaneous reaction
C (gr.) + O (g) ® CO(g); DS° = + ve DG(–ve), which is possible if DS = +ve,
2 2 DH = +ve
Since, DG° = DH° – TDS hence the value of DG and TDS > DH [As DG = DH – TDS]
decrease on increasing temperature. 72. (a) Measure of disorder of a system is nothing
1atm
but Entropy. For a spontaneous reaction,
66. (d) H 2 O( l ) H2O(g) DG < 0. As per Gibbs Helmholtz equation,
DH = 40630 J mol –1 DG = DH – TDS
DS = 108.8 JK–1 mol –1 Thus DG is –ve only
When DH = –ve (exothermic)
DG = DH - T DS
and DS = +ve (increasing disorder)
When DG = 0, DH - T DS = 0 73. (b) DG = DH - T DS
-1
DH 40630 J mol =-382.64 - ( -298 ´145.6 ´10-3 )
T = DS = = 373.4 K.
108.8 J mol-1 = -339.3 kJ mol -1
67. (d) When KP > Q: 74. (a) For a spontaneous process, DStotal is
Rate of forward reaction > Rate of backward always positive
reaction 75. (b) For the reaction
\ Reaction is spontaneous 2 ZnS ® 2 Zn + S2 ; DG1º = 293 kJ ..........(i)
(2) When DG° < RT ln Q 2 Zn + O2 ® 2ZnO ; DG2º = –480 kJ ..........(ii)
RT ln K < RT ln Q S2 + 2 O2 ®2 SO2 ; DG3º = –544 kJ .........(iii)
Þ K<Q DGº for the reaction
The reaction will move in backward direction 2 ZnS + 3 O2 ®2 ZnO + 2 SO2
or the reaction is non-spontaneous. can be obtained by adding eqn. (i), (ii) and (iii)
(3) When TDS > DH, Þ DGº = 293 – 480 – 544 = – 731 kJ
DG = DH – TDS 76. (b) This is combustion reaction, which is always
When DH > 0 and TDS > DH then DG < 0. exothermic hence
Hence, reaction is endothermic and spontaneous. DH = –ve
68. (b) DG = DH – TDS As the no. of gaseous molecules are increasing
At equilibrium, DG = 0 hence entropy increases
Þ 0 = (170 × 103 J ) – T (170 JK– 1) now DG = DH – TDS
Þ T = 1000 K For a spontaneous reaction
For spontaneity, DG is – ve, which is possible DG = - ve
only if T > 1000 K. Which is possible in this case as DH = –ve and
69. (d) We know that DS = +ve.
DG = DH – TDS
EBD_8336
70 CHEMISTRY
7 Equilibrium
2020 2019 2018 2017 2016

Law of mass
action,equilibrium equilibrium
2 A
constant and its constant/Kp and Kc
application
relation between K
1 A 1 D
and G
Relation between K,Q Le-chatelier
1 A
and G and factors principle
affecting equilibrium Clausius and
Clapeyron's 1 E
equation
Bronsted acid and
Theories of acid and 1 E
bases
bases,ionic product of
water and pH scale pH scale 1 E 1 D
Common ion effect,salt solubility 1 D 1 A

hydrolysis, buffer
solution and solubility Ksp 1 A 1 A 1 A
product
Topic 1: Law of Mass Action, Equilibrium The equilibrium constant (K) of the reaction :
Constant (Kc and Kp) and its Application 5 K

2NH3 + O 2 2NO + 3H2O, will be;
2
1. The equilibrium constant of the following are :
N2 + 3H2 2NH3 K1 [2017] (a) K 2 K33 / K1 (b) K2K 3/K 1
N2 + O2 2NO K2 (c) K 23 K3 / K1 (d) K1K33 / K 2
1
H 2 + O 2 ® H 2O K3
2
Equilibrium 71
2. A 20 litre container at 400 K contains CO2(g) at 7. 2NO(g),

For the reaction N2(g) + O2(g)
pressure 0.4 atm and an excess of SrO (neglect
the equilibrium constant is K1. The equilibrium
the volume of solid SrO). The volume of the
constant is K2 for the reaction [2011]
container is now decreased by moving the
movable piston fitted in the container. The 2NO (g).
2NO(g) + O2(g) 2
maximum volume of the container, when pressure What is K for the reaction
of CO2 attains its maximum value, will be :
1 N (g) + O (g) ?
NO2(g)
(Given that : SrCO3 (s) SrO (s) + CO2(g), Kp 2 2 2
= 1.6 atm) [2017]
(a) 10 litre (b) 4 litre (a) 1 / (2K1K2) (b) 1 / (4K1K2)
(c) 2 litre (d) 5 litre (c) [1 / K1K2 ]½ (d) 1 / (K1K2)
3. If the value of an equilibrium constant for a
8. In which of the following equilibrium Kc and Kp
particular reaction is 1.6 × 10 12 , then at
are not equal? [2010]
equilibrium the system will contain :- [2015]
(a) mostly reactants (a) 2 NO(g) N 2 (g) + O2 (g)
(b) mostly products
(b) SO2 (g) + NO 2 (g) SO3 (g) + NO(g)
(c) similar amounts of reactants and products
(d) all reactants (c) H 2 (g) + I 2 (g) 2HI(g)
4. If the equilibrium constant for (d) 2C(s) + O2(g) 2CO2(g)
2NO(g) is K,
N2(g) + O2(g) 9. The reaction 2A(g) + B(g) 3C(g) + D(g) is
the equilibrium constant for [2015 RS] begun with the concentrations of A and B both
1 1 at an initial value of 1.00 M. When equilibrium is
NO(g) will be:
N (g) + O2(g)
2 2 2 reached, the concentration of D is measured and
1 found to be 0.25 M. The value for the equilibrium
1 constant for this reaction is given by the
(a) K2 (b) K
2 expression [2010]
(c) K (d) K 2 (a) [(0.75)3 (0.25)] ¸ [(0.75)2 (0.25)]
5. Given that the equilibrium constant for the (b) [(0.75)3 (0.25)] ¸ [(1.00)2 (1.00)]
reaction 2SO2(g) + O2(g) 2SO (g) has a
3 (c) [(0.75)3 (0.25)] ¸ [(0.50)2 (0.75)]
value of 278 at a particular temperature. What is (d) [(0.75)3 (0.25)] ¸ [(0.50)2 (0.25)]
the value of the equilibrium constant for the
10. If the concentration of OH– ions in the reaction
following reaction at the same temperature ?
Fe(OH) (s) Fe3+ (aq) + 3OH– (aq) is
1 3
SO2 (g) + O2 (g)
SO3 (g) [2012 M] 1
2 decreased by times, then equilibrium
4
(a) 1.8 × 10–3 (b) 3.6 × 10–3 concentration of Fe3+ will increase by : [2008]
(c) 6.0 × 10 –2 (d) 1.3 × 10–5 (a) 8 times (b) 16 times
6. Given the reaction between 2 gases represented (c) 64 times (d) 4 times
by A2 and B2 to give the compound AB(g). 11. The dissociation equilibrium of a gas AB2 can
2 AB(g).
A2(g) + B2(g) be represented as : [2008]
At equilibrium, the concentration 2 AB ( g ) + B2 ( g )
2 AB2 ( g )
of A2 = 3.0 × 10–3 M The degree of dissociation is ‘x’ and is small
of B2= 4.2 × 10–3 M compared to 1. The expression relating the
of AB = 2.8 × 10–3 M degree of dissociation (x) with equilibrium
lf the reaction takes place in a sealed vessel at constant Kp and total pressure P is :
527°C, then the value of Kc will be : [2012 M] (a) (2Kp/P) (b) (2Kp/P)1/3
(a) 2.0 (b) 1.9
(c) 0.62 (d) 4.5 (c) (2Kp /P)1/2 (d) (Kp /P)
EBD_8336
72 CHEMISTRY
12. The values of Kp1 and Kp2 for the reactions 16. K1 and K2 are equilibrium constant for reactions
Y + Z
X ...(a) [2008] (i) and (ii)
2 NO (g) .............(i)
N2(g) + O2 (g)
2 B
and A ...(b)
1 1
are in the ratio of 9 : 1. If degree of dissociation
NO(g) N 2 (g) + O 2 (g) ......(ii)
2 2
of X and A be equal, then total pressure at
Then, [1989, 94, 2005]
equilibrium for (a) and (b) are in the ratio :
(a) 3 : 1 (b) 1 : 9 2
æ 1 ö
(c) 36 : 1 (d) 1 : 1 (a) K1 = ç (b) K1 = K22
è K 2 ÷ø
13. The value of equilibrium constant of the reaction
1 1 1
HI (g ) H 2 (g) + I 2 is 8.0 [2008] (c) K1 =
K2
(d) K1 = (K2)0
2 2
The equilibrium constant of the reaction 17. Value of KP in the reaction
2HI(g) will be:
H 2 (g) + I 2 (g) MgCO3 (s ) ® MgO( s) + CO2 ( g ) is [2000]
1 1 (a) KP = PCO
(a) (b) 2
16 64 P ´ PMgO
(b) K P = PCO ´ CO2
1 2 PMgCO3
(c) 16 (d)
8
14. The following equilibrium constants are given: PCO2 ´ PMgO
(c) KP =
2NH3 ; K1
N 2 + 3H 2 [2003, 2007] PMgCO3
2NO; K 2
N 2 + O 2 PMgCO3
(d) KP =
1 PCO2 ´ PMgO
H 2O; K3
H 2 + O2
2 18. For dibasic acid correct order is [2000]
The equilibrium constant for the oxidation of 2
(a) Ka1 < Ka 2 (b) K a1 > K a2
moles NH3 by oxygen to give NO is
(c) Ka1 = Ka2 (d) not certain
K 2 K32 K 22 K3
(a) (b) 19. If K1 and K2 are the respective equilibrium
K1 K1 constants for the two reactions
XeF6(g) + H2O(g) XeOF (g) + 2HF(g)
K1 K 2 K 2 K33 4
(c) (d) XeO4(g) + XeF6(g) XeOF (g) + XeO F (g)
K3 K1 4 3 2
the equilibrium constant of the reaction
15. For the reaction [2006]
XeO4(g) + 2HF(g) XeO F (g) + H O(g)
CO (g) + 2H O(l),
CH 4 (g) + 2O 2 (g) 3 2 2
2 2 will be [1998]
DrH = –170.8 k J mol–1 (a) K1/(K2)2 (b) K1 . K2
Which of the following statements is not true ? (c) K1/K2 (d) K2/K1
(a) The equilibrium constant for the reaction
20. If a is the fraction of HI dissociated at
[CO 2 ] H
is given by K p = equilibrium in the reaction, 2 HI (g) 2
[CH 4 ][O2 ]2 (g) + I2 (g), starting with 2 moles of HI, the total
(b) Addition of CH4(g) or O2(g) at equilibrium number of moles of reactants and products at
will cause a shift to the right equilibrium are [1996]
(c) The reaction is exothermic (a) 2 + 2a (b) 2
(d) At equilibrium, the concentrations of (c) 1 + a (d) 2 – a
CO2(g) and H2O(l) are not equal
Equilibrium 73
21. The rate constant for forward and backward 26. For the reversible reaction, [2014]
reaction of hydrolysis of ester are 1.1 ´ 10 -2 and
N2(g) + 3H2(g) 2NH3(g) + heat
1 .5 ´ 10 -3 per minute respectively. Equilibrium The equilibrium shifts in forward direction
constant for the reaction [1995] (a) By increasing the concentration of NH3(g)
+ (b) By decreasing the pressure
CH COOC H + H
3 2 5
(c) By decreasing concentration of N2(g) and
CH3COOH + C 2 H5OH is H2(g)
(a) 4.33 (b) 5.33 (d) By increasing pressure and decreasing
(c) 6.33 (d) 7.33 temperature.
Topic 2: Relation between K, Q and G and 27. For a given exothermic reaction, Kp and KP¢ are
Factors Effecting Equilibrium the equilibrium constants at temperatures T1 and
T2, respectively. Assuming that heat of reaction
22. Hydrolysis of sucrose is given by the following is constant in temperature range between T1 and
reaction. [2020] T2, it is readily observed that: [2014]
Sucrose + H2O Glucose + Fructose (a) Kp > K P¢ (b) Kp < K P¢
If the equilibrium constant (KC) is 2 × 1013 at
– 1
300 K, th e value of DrG at the same (c) Kp = K P¢ (d) Kp =
K ¢p
temperature will be :
28. The dissociation constants for acetic acid and
(a) 8.314 J mol–1K–1 × 300 K × ln(2 × 1013) HCN at 25°C are 1.5 × 10–5 and 4.5 × 10–10
(b) 8.314 J mol–1K–1 × 300 K × ln(3 × 1013) respectively. The equilibrium constant for the
(c) –8.314 J mol–1K–1 × 300 K × ln(4 × 1013) equilibrium [2009]
(d) –8.314 J mol–1K–1 × 300 K × ln(2 × 1013) CN– + CH3COOH HCN + CH COO–
3
23. Which one of the following conditions will favour would be:
maximum formation of the product in the (a) 3.0 × 10– 5 (b) 3.0 × 10– 4
(c) 3.0 × 10 4 (d) 3.0 × 105
reaction, [2018]
X 2 (g) D r H = – X kJ :
A2 (g) + B2 (g) 29. The reaction quotient (Q) for the reaction
2NH (g)
N2(g) + 3H2(g)
(a) Low temperature and high pressure 3
(b) Low temperature and low pressure [NH 3 ]2
is given by Q = . The reaction will
(c) High temperature and low pressure
[N 2 ][H 2 ]3
(d) High temperature and high pressure
24. Consider the following liquid - vapour proceed from right to left if [2003]
equilibrium. [2016] (a) Q = 0 (b) Q = Kc
Vapour
Liquid (c) Q < Kc (d) Q > Kc
where Kc is the equilibrium constant
Which of the following relations is correct ?
30. For the reaction
dlnG DH v dlnP DH v 2BaO(s) + O (g);
(a) = (b) = 2BaO2(s) 2
2 2 dT RT
dT RT DH = +ve. In equilibrium condition, pressure of
dlnP -DH v dlnP -DH v O2 is dependent on [2002]
(c) = (d) =
dT 2
T 2 dT RT 2 (a) mass of BaO2
(b) mass of BaO
25. Which of the following statements is correct for
(c) temperature of equilibrium
a reversible process in a state of equilibrium ?
(d) mass of BaO2 and BaO both
[2015]
31. In a two-step exothermic reaction
(a) DG = 2.30 RT log K
(b) DGº = –2.30 RT log K
A2(g) + B2(g)
3C(g)
D(g)
Step 1 Step 2
(c) DGº = 2.30 RT log K Steps 1 and 2 are favoured respectively by
(d) DG = –2.30 RT log K [1997]
EBD_8336
74 CHEMISTRY
(a) high pressure, high temperature and low 38. Conjugate base for Brönsted acids H2O and HF
pressure, low temperature are : [2019]
(b) high pressure, low temperature and low (a) OH– and H2F+, respectively
pressure, high temperature (b) H3O+ and F–, respectively
(c) low pressure, high temperature and high
(c) OH– and F–, respectively
pressure, high temperature
(d) low pressure, low temperature and high (d) H3O+ and H2F+, respectively
pressure, low temperature 39. Following solutions were prepared by mixing
32. The equilibrium constant for the reaction different volumes of NaOH and HCl of different
2A at 500 K and 700 K are 1 × 10–10
A2 concentrations : [2018]
and 1 × 10–5 respectively. The given reaction is M M
[1996] a. 60 mL HCl + 40 mL NaOH
10 10
(a) exothermic (b) slow M M
(c) endothermic (d) fast b. 55 mL HCl + 45 mL NaOH
33. Stan dar d Gibb’s free energy change for 10 10
isomerization reaction [1995] M M
c. 75 mL HCl + 25 mL NaOH
trans-2-pentene
cis-2- pentene 5 5
is – 3.67 kJ/mol at 400 K. If more trans-2-pentene M M
is added to the reaction vessel, then d. 100 mL HCl + 100 mL NaOH
10 10
(a) more cis-2-pentene is formed pH of which one of them will be equal to 1?
(b) equilibrium remains unaffected (a) b (b) a
(c) additional trans-2-pentene is formed (c) c (d) d
(d) equilibrium is shifted in forward direction 40. What is the pH of the resulting solution when
34. According to Le-chatelier’s principle, adding heat equal volumes of 0.1 M NaOH and 0.01 M HCl
liquid equilibrium will cause the
to a solid are mixed ? [2015 RS]
(a) temperature to increase [1993] (a) 12.65 (b) 2.0
(b) temperature to decrease (c) 7.0 (d) 1.04
(c) amount of liquid to decrease 41. Which of the following salts will give highest
(d) amount of solid to decrease.
pH in water ? [2014]
35. Which one of the following information can be
(a) KCl (b) NaCl
obtained on the basis of Le Chatelier principle?
(c) Na2CO3 (d) CuSO4
[1992]
42. Which of these is least likely to act as Lewis
(a) Dissociation constant of a weak acid
(b) Entropy change in a reaction base? [NEET 2013]
(c) Equilibrium constant of a chemical reaction (a) F– (b) BF3
(d) Shift in equilibrium position on changing (c) PF3 (d) CO
value of a constraint. 43. Which of the following is least likely to behave
as Lewis base ? [2011]
Topic 3: Theories of Acids and Bases, Ionic (a) H2O (b) NH3
Product of Water and pH Scale (c) BF3 (d) OH–
36. The pH of 0.01 M NaOH (aq) solution will be 44. Which one of the following molecular hydrides
[NEET Odisha 2019] acts as a Lewis acid? [2010]
(a) 9 (b) 7.01 (a) NH3 (b) H2O
(c) 2 (d) 12 (c) B2H6 (d) CH4
37. Which of the following cannot act both as 45. Which of the following molecules acts as a Lewis
Bronsted acid and as Bronsted base? acid ? [2009]
[NEET Odisha 2019] (a) (CH3)2 O (b) (CH3)3 P
(a) HSO4– (b) HCO3–
(c) (CH3)3 N (d) (CH3)3 B
(c) NH3 (d) HCl
Equilibrium 75
46. The ionization constant of ammonium hydroxide (a) RCOOH > HC º CH > HOH > ROH
is 1.77 × 10–5 at 298 K. Hydrolysis constant of (b) RCOOH > ROH > HOH > HC º CH
ammonium chloride is: [2009] (c) RCOOH > HOH > ROH > HC º CH
(a) 6.50 × 10– 12 (b) 5.65 × 10–13 (d) RCOOH > HOH > HC º CH > ROH
(c) 5.65 × 10–12 (d) 5.65 × 10–10 53. Which one of the following compounds is not a
47. Equal volumes of three acid solutions of pH 3, 4 protonic acid? [2003]
and 5 are mixed in a vessel. What will be the H+ (a) SO2 (OH)2 (b) B (OH)3
ion concentration in the mixture ? [2008] (c) PO (OH)3 (d) SO (OH)2
(a) 1.11 × 10–4 M (b) 3.7 × 10–4 M 54. In HS–, I–, RNH2 and NH3, order of proton
(c) 3.7 × 10– 3 M (d) 1.11× 10–3 M accepting tendency will be [2001]
48. Calculate the pOH of a solution at 25°C that (a) I– > NH3 > RNH2 > HS–
contains 1× 10– 10 M of hydronium ions, i.e. (b) HS– > RNH2 > NH3 > I–
H3O+. [2007] (c) RNH2 > NH3 > HS– > I–
(a) 4.000 (b) 9.0000 (d) NH3 > RNH2 > HS– > I–
(c) 1.000 (d) 7.000 55. A base when dissolved in water yields a solution
with a hydroxyl ion concentration of 0.05 mol litre–1.
49. The hydrogen ion concentration of a 10–8 M
The solution is [2000]
HCl aqueous solution at 298 K (Kw = 10–14) is
(a) basic (b) acidic
[2006] (c) neutral (d) either 'b' or 'c'
(a) 11 × 10 M–8 (b) 9.525 × 10 M –8
56. Conjugate acid of NH -2 is : [2000]
(c) 1.0 × 10–8 M (d) 1.0 × 10–6 M (a) NH4+ (b) NH3
50. What is the correct relationship between the (c) NH2 (d) NH
pHs of isomolar solutions of sodium oxide 57. Which of the following statements about pH
(pH 1 ), sodium sulph ide (pH 2 ), sodium and H+ ion concentration is incorrect? [2000]
selenide (pH3) and sodium telluride (pH4)? (a) Addition of one drop of concentrated HCl in
[2005] NH4OH solution decreases pH of the solution.
(a) pH1 > pH2 > pH3 > pH4 (b) A solution of the mixture of one equivalent of
(b) pH1 > pH2 » pH3 > pH4 each of CH3COOH and NaOH has a pH of 7
(c) pH1 < pH2 < pH3 < pH4 (c) pH of pure neutral water is not zero
(d) pH1 < pH2 < pH3 » pH4 (d) A cold and concentrated H2SO4 has lower
51. The rapid change of pH near the stoichiometric H+ ion concentration than a dilute solution
point of an acid-base titration is the basis of of H2SO4
indicator detection. pH of the solution is related 58. Among boron trifluoride, stannic chloride and
to ratio of the concentrations of the conjugate stannous chloride, Lewis acid is represented by
acid (HIn) and base (In–) forms of the indicator [1999]
by the expression [2004] (a) only stannic chloride
(b) boron trifluoride and stannic chloride
[ In - ]
(a) log = pK In - pH (c) boron trifluoride and stannous chloride
[ HIn ] (d) only boron trifluoride
[ HIn ] 59. What is the H+ ion concentration of a solution
(b) log = pK In - pH
[ In - ] prepared by dissolving 4 g of NaOH (Atomic
[ HIn ] weight of Na = 23 amu) in 1000 mL? [1999]
(c) log = pH - pK In (a) 10–10 M (b) 10–4 M
[ In - ]
(c) 10–1 M (d) 10–13 M
[ In - ]
(d) log = pH - pK In 60. The pH value of a 10 M solution of HCl is [1995]
[ HIn ] (a) less than 0 (b) equal to 0
52. Which one of the following orders of acid (c) equal to 1 (d) equal to 2
strength is correct? [2003]
EBD_8336
76 CHEMISTRY
Topic 4: Ionisation of Weak Acids and 68. The molar solubility of CaF2(Ksp = 5.3 × 10–11)
Bases and Relation between K a and K b in 0.1 M solution of NaF will be
61. At 100°C the Kw of water is 55 times its value at [NEET Odisha 2019]
–10
(a) 5.3 × 10 mol L –1
25°C. What will be the pH of neutral solution?
(log 55 = 1.74) [NEET Kar. 2013] (b) 5.3 × 10–11 mol L–1
(a) 6.13 (b) 7.00 (c) 5.3 × 10–8 mol L–1
(c) 7.87 (d) 5.13 (d) 5.3 × 10–9 mol L–1
62. Accumulation of lactic acid (HC3H5 O3 ), a 69. pH of a saturated solution of Ca(OH)2 is 9. The
monobasic acid in tissues leads to pain and a solubility product (Ksp) of Ca(OH)2 is: [2019]
feeling of fatigue. In a 0.10 M aqueous solution,
lactic acid is 3.7% dissociated. The value of (a) 0.5 10–15 (b) 0.25 10–10
(c) 0.125 10 –15 (d) 0.5 10–10
dissociation constant, Ka, for this acid will be:
[NEET Kar. 2013] 70. The solubility of BaSO4 in water is
(a) 2.8 × 10–4 (b) 1.4 × 10–5 2.42 × 10–3 gL–1 at 298 K. The value of its
(c) 1.4 × 10–4 (d) 3.7 × 10–4 solubility product (Ksp) will be
63. A weak acid, HA, has a Ka of 1.00 × 10–5. If (Given molar mass of BaSO4 = 233 g mol–1)
0.100 mol of this acid is dissolved in one litre of
(a) 1.08 × 10–10 mol2L–2 [2018]
water, the percentage of acid dissociated at –12 2 –2
equilbrium is closest to [2007] (b) 1.08 × 10 mol L
(a) 1.00% (b) 99.9% (c) 1.08 × 10–8 mol2L–2
(c) 0.100% (d) 99.0% (d) 1.08 × 10–14 mol2L–2
64. At 25°C, the dissociation constant of a base, 71. Concentration of the Ag+ ions in a saturated
BOH, is 1.0 ´ 10-12. The concentration of solution of Ag2C2O4 is 2.2 × 10–4 mol L–1.
hydroxyl ions in 0.01 M aqueous solution of Solubility product of Ag2C2O4 is :- [2017]
the base would be [2005]
(a) 2.66 × 10–12 (b) 4.5 × 10–11
(a) 1.0 ´ 10- 5 mol L-1 (b) 1.0 ´ 10-6 mol L-1
(c) 2.0 ´ 10-6 mol L-1 (d) 1.0 ´ 10-7 mol L-1 (c) 5.3 × 10–12 (d) 2.42 × 10–8
65. Ionisation constant of CH3COOH is 1.7 × 10–5. 72. MY and NY3, two nearly insoluble salts, have
If concentration of H+ ions is 3.4 × 10–4M, then the same Ksp values of 6.2 × 10–13 at room
find out initial concentration of CH3COOH temperature. Which statement would be true in
molecules [2001] regard to MY and NY3 ? [2016]
(a) 3.4 × 10–4M (b) 3.4 × 10–3M (a) The molar solubilities of MY and NY3 in
(c) 6.8 × 10–3M (d) 6.8 × 10–4M water are identical.
66. Aqueous solution of acetic acid contains (b) The molar solubility of MY in water is less
[1991]
than that of NY3
(a) CH3COO– and H+
(b) CH3COO–, H3O+ and CH3COOH (c) The salts MY and NY3 are more soluble in
(c) CH3COO–, H3O+and H+ 0.5 M KY than in pure water.
(d) CH3COOH, CH3COO– and H+ (d) The addition of the salt of KY to solution
of MY and NY3 will have no effect on their
Topic 5: Common Ion Effect, Salt Hydrolysis, solubilities.
Buffer Solutions and Solubility Product
73. Consider the nitration of benzene using mixed
67. Find out the solubility of Ni(OH)2 in 0.1 M conc of H2SO4 and HNO3. If a large amount of
NaOH. Given that the ionic product of Ni(OH)2 KHSO4 is added to the mixture, the rate of
is 2 × 10–15 [2020] nitration will be [2016]
(a) 2 × 10–8 M (b) 1 × 10–13 M (a) faster (b) slower
(c) 1 × 108 M (d) 2 × 10–13 M (c) unchanged (d) doubled
Equilibrium 77
74. The Ksp of Ag2 CrO4, AgCl, AgBr and AgI (a) BaCl2 (b) AlCl3
are respectively, 1.1 × 10 –12 , 1.8 × 10–10 , (c) LiCl (d) BeCl2
5.0 × 10–13, 8.3 × 10–17. Which one of the 82. Buffer solutions have constant acidity and
following salts will precipitate last if AgNO3 alkalinity because [2012]
solution is added to the solution containing equal (a) these give unionised acid or base on
moles of NaCl, NaBr, NaI and Na2CrO4?[2015] reaction with added acid or alkali.
(b) acids and alkalies in these solutions are
(a) AgCl (b) AgBr
shielded from attack by other ions.
(c) Ag2CrO4 (d) AgI
(c) they have large excess of H+ or OH– ions
75. Which one of the following pairs of solution is
(d) they have fixed value of pH
not an acidic buffer ? [2015 RS]
83. A buffer solution is prepared in which the
(a) HClO4 and NaClO4
concentration of NH3 is 0.30 M and the
(b) CH3COOH and CH3 COONa
concentration of NH4+ is 0.20 M. If the equilibrium
(c) H2CO3 and Na2CO3
constant, Kb for NH3 equals 1.8 × 10–5, what is
(d) H3PO4 and Na3PO4
the pH of this solution ? (log 2.7 = 0.433).
76. Using the Gibbs energy change, DG° = + 63.3kJ,
[2011]
for the following reaction, [2014]
2Ag+ (aq) + CO 2–(aq) (a) 9.08 (b) 9.43
Ag2CO3 3 (c) 11.72 (d) 8.73
the Ksp of Ag2CO3(s) in water at 25°C is:-
84. In qualitative analysis, the metals of Group I can
(R = 8.314 J K–1 mol–1) be separated from other ions by precipitating
(a) 3.2 × 10–26 (b) 8.0 × 10–12 them as chloride salts. A solution initially
(c) 2.9 × 10 –3 (d) 7.9 × 10–2 contains Ag+ and Pb2+ at a concentration of
77. Identify the correct order of solubility in aqueous 0.10 M. Aqueous HCl is added to this solution
medium: [NEET 2013] until the Cl– concentration is 0.10 M. What will
(a) ZnS > Na2S > CuS (b) Na2S > CuS > ZnS the concentrations of Ag+ and Pb2+ be at
(c) Na2S > ZnS > CuS (d) CuS > ZnS > Na2S equilibrium?
78. The values of Ksp of CaCO3 and CaC2O4 are (Ksp for AgCl = 1.8 × 10–10,
4.7 × 10–9 and 1.3 × 10–9 respectively at 25°C. If Ksp for PbCl2 = 1.7 × 10–5) [2011M]
(a) [Ag+] = 1.8 × 10–7 M ; [Pb2+] = 1.7 × 10–6 M
the mixture of these two is washed with water,
(b) [Ag+] = 1.8 × 10–11 M ; [Pb2+] = 8.5 × 10–5 M
what is the concentration of Ca 2+ ions in water? (c) [Ag+] = 1.8 × 10–9 M ; [Pb2+] = 1.7 × 10–3 M
[NEET Kar. 2013] (d) [Ag+] = 1.8 × 10–11 M ; [Pb2+] = 8.5 × 10–4 M
(a) 7.746 × 10–5 M (b) 5.831 × 10–5 M 85. If pH of a saturated solution of Ba(OH)2 is 12,
(c) 6.856 × 10–5 M (d) 3.606 × 10–5 M the value of its K(sp) is : [2010]
79. The dissociation constant of a weak acid is
1 × 10– 4. In order to prepare a buffer solution (a) 4.00 × 10–6 M3 (b) 4.00 × 10–7 M3
with a pH = 5 the [Salt]/[Acid] ratio should be (c) 5.00 × 10–6 M3 (d) 5.00 × 10–7 M3
[NEET Kar. 2013] 86. What is [H+] in mol/L of a solution that is 0.20 M
(a) 1 : 10 (b) 4 : 5 in CH3COONa and 0.10 M in CH3COOH? Ka for
(c) 10 : 1 (d) 5 : 4
CH3COOH = 1.8 × 10-5 . [2010]
80. pH of a saturated solution of Ba(OH)2 is 12.
The value of solubility product (Ksp) of Ba (OH)2 (a) 3.5 × 10–4 (b) 1.1 × 10–5
is : [2012] (c) 1.8 × 10–5 (d) 9.0 × 10–6
(a) 3.3 × 10– 7 (b) 5.0 × 10–7 87. In a buffer solution containing equal
(c) 4.0 × 10–6 (d) 5.0 × 10–6 concentration of B– and HB, the Kb for B–
is 10–10. The pH of buffer solution is : [2010]
81. Equimolar solutions of the following substances
(a) 10 (b) 7
were prepared separately. Which one of these
(c) 6 (d) 4
will record the highest pH value ? [2012]
EBD_8336
78 CHEMISTRY
88. Equimolar solutions of the following were 96. Solubility of a M2S salt is 3.5 × 10–6, then its
prepared in water separately. Which one of the solubility product will be [2001]
solutions will record the highest pH ? [2008] (a) 1.7 × 10–16 (b) 1.7 × 10–6
(a) SrCl2 (b) BaCl2 (c) 1.7 × 10–18 (d) 1.7 × 10–12
(c) MgCl2 (d) CaCl2
97. The solubility product of a sparingly soluble
89. Which of the following pairs constitutes a
salt BA2 is 4 × 10–12. The solubility of BA2 is
buffer? [2006]
[1999]
(a) NaOH and NaCl
(b) HNO3 and NH4NO3 (a) 4 × 10–4 (b) 4 × 10–12
(c) HCl and KCl (c) 4 × 10–3 (d) 1 × 10–4
(d) HNO2 and NaNO2 98. The solubility products of CuS, Ag2S and HgS
90. H2S gas when passed through a solution of are 10 –31 , 10 –44 , 10 –54 respectively. The
cations containing HCl, precipitates the solubilities of these sulphides are in the order
cati ons of secon d group of qualitative [1997]
analysis but not those belonging to the fourth (a) Ag2S > HgS > CuS (b) Ag2S > CuS > HgS
group. It is because [2005]
(c) HgS > Ag2S > CuS (d) CuS > Ag2S > HgS
(a) presence of HCl decreases the sulphide
ion concentration. 99. A physician wishes to prepare a buffer solution
(b) solubility product of group II sulphides of pH = 3.58 that efficiently resists a change in
is more than that of group IV sulphides. pH yet contains only small concentrations of
(c) presence of HCl increases the sulphide the buffering agents. Which one of the following
ion concentration. weak acids together with its sodium salt would
(d) sulphides of group IV cations are be the best to use ? [1997]
unstable in HCl. (a) m-chlorobenzoic acid (pKa = 3.98)
91. The solubility product of a sparingly soluble (b) p-chlorocinnamic acid (pKa = 4.41)
salt AX2 is 3.2 × 10–11. Its solubility ( in moles/ (c) 2, 5-dihydroxy benzoic acid (pKa = 2.97)
litre) is [2004] (d) Acetoacetic acid (pKa = 3.58)
(a) 5.6 × 10 –6 (b) 3.1 × 10 –4
100. The pH value of blood does not appreciably
(c) 2 × 10–4 (d) 4 × 10–4 change by a small addition of an acid or a base,
92. The solubility product of AgI at 25ºC is because the blood [1995]
1.0 × 10–16 mol 2 L–2 . The solubiliy of AgI in (a) is a body fluid
10–4 N solution of KI at 25ºC is approximately
(b) can be easily coagulated
(in mol L–1 ) [2003]
(c) contains iron as a part of the molecule
(a) 1.0 × 10–8 (b) 1.0 × 10–16
(d) contains serum protein which acts as buffer
(c) 1.0 × 10–12 (d) 1.0 × 10–10
101. Which of the following is most soluble ? [1994]
93. Solubility of MX2-type eletrolytes is 0.5 × 10–4
mol/lit, then find out Ksp of electrolytes [2002] (a) Bi2 S3 (Ksp = 1 × 10–17)
(a) 5 × 10–12 (b) 25 × 10–10 (b) MnS (Ksp = 7 × 10–16)
(c) 1 × 10 –13 (d) 5 × 10–13 (c) CuS (Ksp = 8 × 10–37)
94. Which has the highest value of pH? [2002] (d) Ag2 S (Ksp = 6 × 10–51).
(a) CH3COOK (b) Na2CO3 102. 0.1 M solution of which one of these substances
(c) NH4Cl (d) NaNO3 will be basic ? [1992]
(a) Sodium borate
95. Solution of 0.1 N NH4OH and 0.1 N NH4Cl has
pH 9.25. Then find out pKb of NH4OH [2002] (b) Ammonium chloride
(a) 9.25 (b) 4.75 (c) Calcium nitrate
(c) 3.75 (d) 8.25 (d) Sodium sulphate.
Equilibrium 79
103. In which of the following solvents, AgBr will 104. The compound whose aqueous solution has the
have the highest solubility ? [1992] highest pH is [1988]
(a) 10-3 M NaBr (b) 10 -3 M NH 4 OH (a) NaCl (b) NaHCO3
(c) Na2CO3 (d) NH4Cl.
(c) Pure water (d) 10 -3 M HBr
ANSWER KEY
1 (a) 12 (c) 23 (a) 34 (d) 45 (d) 56 (b) 67 (d) 78 (a) 89 (d) 100 (d)
2 (d) 13 (b) 24 (d) 35 (d) 46 (d) 57 (b) 68 (d) 79 (c) 90 (a) 101 (a)
3 (b) 14 (d) 25 (b) 36 (d) 47 (b) 58 (c) 69 (a) 80 (b) 91 (c) 102 (a)
4 (a) 15 (a) 26 (d) 37 (d) 48 (a) 59 (d) 70 (a) 81 (a) 92 (c) 103 (b)
5 (c) 16 (a) 27 (a) 38 (c) 49 (a) 60 (a) 71 (c) 82 (a) 93 (d) 104 (c)
6 (c) 17 (a) 28 (c) 39 (c) 50 (a) 61 (a) 72 (b) 83 (b) 94 (b)
7 (c) 18 (b) 29 (d) 40 (a) 51 (d) 62 (c) 73 (b) 84 (c) 95 (b)
8 (d) 19 (d) 30 (c) 41 (c) 52 (c) 63 (a) 74 (c) 85 (d) 96 (a)
9 (c) 20 (b) 31 (d) 42 (b) 53 (b) 64 (d) 75 (a) 86 (d) 97 (d)
10 (c) 21 (d) 32 (b) 43 (c) 54 (c) 65 (c) 76 (b) 87 (d) 98 (b)
11 (b) 22 (d) 33 (a) 44 (c) 55 (a) 66 (b) 77 (c) 88 (b) 99 (d)
Hints & Solutions

1. (a) Kp = PCO = 1.6 atm = maximum pressure of CO2
2
2NH3 ; K1 =
(i) N 2 + 3H 2
[ NH3 ] 2
volume of container at this stage.
[ N 2 ][ H 2 ]3 V=
nRT
…(i)
P
2NO; K 2 =
[ NO ]2 Since container is sealed and reaction was not
(ii) N 2 + O 2
[ N 2 ][ O 2 ] earlier at equilibrium.
\ n = constant.
1
(iii) H 2 + O 2 ¾¾
® H 2 O; K 3 =
[ H 2O ] PV 0.4 ´ 20
n= = …(ii)
2 [ H 2 ][ O 2 ]1/2 RT RT
Applying (II + 3 × III – I) we will get Put equation (ii) in equation (i)
5 K é 0.4 ´ 20 ù RT
2NH3 + O 2 2NO + 3H 2O; V= ê = 5L
2 ë RT úû 1.6
3. (b) Equilibrium constant for reaction:
K=
[ NO]2
´
[ H 2O ]
3
[ NH3 ]
2
[Product]
[ N2 ][ O 2 ] [ H 2 ]3 ´ [ O2 ]3 / 2 [ N 2 ][ H 2 ]3 K = 1.6 × 1012 =
[Reactant]
\ K = K2 × K33 / K1 The value of K is very high so the system will
2. (d) Max. pressure of CO2 = Pressure of CO2 at contain mostly products at equilibrium.
equilibrium 4. (a) N2(g) + O2(g) 2NO(g)
For reaction, [NO]2
K=
SrO(s) + CO2(g)
SrCO3(s) [N 2 ][O2 ]
EBD_8336
80 CHEMISTRY
1 1 9. (c) 2A(g) + B(g) 3C(g) + D(g)

N 2 + O 2 NO
2 2 Mole ratio 2 1 3 1
[NO] Molar concentration 1 1 0 0
K¢ = = K1 2
[N 2 ] [O 2 ]1 2
12 at t = 0
Molar 0.50 0.75 0.75 0.25
5. (c) 2SO3 K = 278 (given)
2SO2 + O2 concentration at equilibrium
æ 1ö
SO2 + 1 O2 K' =
SO3 [C ]3 [ D ] (0.75)3 (0.25)
2 ç K÷ Kc = =
è ø
1 [ A]2 [ B ] (0.50) 2 (0.75)
= = 6 × 10–2 10. (c) For this reaction Keq. is given by
278
2 3
2AB ; K c = [ AB] éFe3+ ù éOH - ù
K=ë ûë û
6. (c) A2 + B2
[ A2 ][ B2 ]
[ Fe(OH)3 ]
(2.8 ´ 10-3 )2 (2.8)2 = (Fe3+) (OH–)3 [\ [solid]=1].
Kc = -3 -3
= = 0.62
3 ´ 10 ´ 4.2 ´ 10 3 ´ 4.2 1
7. (c) For the reaction If (OH–) is decreased by times then for given
4
2NO(g)
N 2 (g) + O 2 (g) reaction, equilibrium constant to remain
constant, we have to increase the concentration
[NO]2 of [Fe3+] by a factor of 43 i.e. 4× 4 × 4 = 64. Thus,
K1 =
[N 2 ][O 2 ] option (c) is correct answer.
For the reaction
2NO2 (g)
2NO(g) + O2 (g) To maintain the equilibrium constant if
concentration of one of the product decreases by
2
[NO 2 ] 1
K2 = times then the concentration of another product
[NO]2 [O 2 ] n
For the reaction is increased by the factor of (n)x, where x is the
stoichiometric coeficient.
1 N 2 (g) + O2 (g)
NO2 (g) 11. (b) For the reaction
2
1 2 AB2 (g) 2 AB(g) + B2 (g)
[N 2 ] 2 [O
2]
initially 2 0 0
K= at equi 2(1- x) 2x x
[NO2 ]
The partial pressure at equilibrium are calculated
1 1 on the basis of total number of moles at
Hence, K = ´
K1 K 2 equilibrium.
1 1 1 1 Total number of moles
[N 2 ] 2 [O 2 ] 2 [NO][O2 ] 2 [N 2 ] 2 [O2 ] = 2 (1–x) + 2x + x = (2 + x)
K= ´ =
[NO] [NO2 ] [NO2 ] 2(1 - x)
\ PAB = ´ P where P is the total
8. (d) 2C(s)+O2 (g) 2 CO 2 (g)
2 (2 + x )
pressure.
Dn = 2 – 1 = + 1 2x x
\ Kc and Kp are not equal. PAB = ´ P , PB = ´P
(2 + x ) 2 (2 + x )
Since x is very small so can be neglected in
If Dn = 0, then (RT)Dn = 1 denominator
Þ Kc = Kp
Thus, we get
PAB = (1 – x) × P PAB = x × P
2
Equilibrium 81
x 1 P é KP 9ù
PB = ´P or 9 = . 1 ê\ 1 = ú
2 2 4 P2 êë KP2 1 úû
x P1 36
( PAB )2 ( PB2 ) ( x )2 ´ P 2 .P ´
2
or
P2 1
= or P1 : P2 = 36 : 1
Now, K P = =
( PAB2 ) 2 (1 - x) 2 ´ P 2 13. (b) Given : Equilibrium constant (K1) for the
reaction:
x 3 .P3
= [Q 1 – x ; 1 ] K1

1 1
2 ´ 1 ´ P2 HI(g) H 2 (g) + I 2 (g); K1 = 8; … (i)
1 2 2
x3 .P 2.K p æ 2K p ö 3 To find equilibrium constant for the following
= or x3 = or x = ç reaction:
2 P è P ÷ø
H 2 (g) + I2 (g) 2HI(g); K2 = ? .....(ii)
12. (c) Given reaction are
multiply (i) by 2, we get
Y + Z
X ..... (i)
2HI(g) H 2 (g) + I2 (g);
2B
and A ......(ii)
Let the total pressure for reaction (i) and (ii) be K1 = 82 = 64. … (iii)
P1 and P2 respectively, then Now reverse equation (iii), we get
1
KP
1 =9
H 2 (g) + I2 (g) 2HI(g); K = .....(iv)
(given) 64
KP 1 Equation (iv) is the same as the required equation
2
After dissociation, 1
(ii), thus K2 for equation (ii) is i.e. option (b)
Y + Z
X 64
(1– a) a a is correct.
At equilibrium
[Let 1 mole of X dissociate with a as degree of When the equation for an equilibrium is multiplied
by a factor, the equilibrium constant must be raised
dissociation] to the power equal to the factor.
Total number of moles = 1– a + a + a = (1+ a) For a reversible reaction, the equilibrium constant
æ1- a ö of the backward reaction is inverse of the
æ a ö
Thus PX = ç .P ;P = P; equilibrium constant for the forward reaction.
è 1 + a ÷ø 1 Y çè 1 + a ÷ø 1
14. (d) Given,
æ a ö 2NH 3 ; K1
PZ = ç .P N 2 + 3H 2 ....(i)
è 1 + a ÷ø 1
æ a ö a 2NO; K2
N2 + O2 ....(ii)
\ KP = ç .P ´ .
1 è 1 + a ÷ø 1 (1 + a ) 1
H2 + H 2 O; K 3
O 2 ....(iii)
æ1- aö 2
P1 / ç .P ....... (i)
è 1 + a ÷ø 1 We have to calculate
Similarly for A 2B 4NH 3 + 5O2 ¾¾ ® 4NO + 6H 2O; K = ?
At equilibrium (1– a) 2a 5
or 2NH 3 + O2 ¾¾ ® 2NO + 3H 2 O
We have, 2
2 [NO]2 [H 2O]3
æ 2aP2 ö æ 1 - a ö For this equation, K =
KP = ç / P ........(ii)
2 è 1 + a ÷ø çè 1 + a ÷ø 2 [NH3 ]2 [O 2 ]5 / 2
Dividing (i) by (ii), we get [NH3 ]2 [NO]2
but K1 = , K2 =
K P1 a 2 .P1 KP 1 P [N 2 ] [H 2 ]3 [N 2 ] [O2 ]
= 2 or 1 = . 1
KP 4a . P2 KP 4 P2
2 2
& K3 =
[H 2O] 3 [H 2 O]3
or K =
[H 2 ] [O2 ]½ 3
[H 2 ]3 [O 2 ]3/2
EBD_8336
82 CHEMISTRY
K 2 . K33 K=
[XeO3F2 ][H 2O]
Now operate,
K1 [XeO4 ][HF]2
[NO]2 [H 2O]3 [N ] [H 2 ]3 \ From eq. no. (a) and (b)
= ´ . 2 K = K 2 / K1
[N 2 ] [O2 ] [H 2 ]3 [O2 ]3/ 2 [NH3 ]2 20. (b) According to equation
[NO]2 [H 2 O]3 2HI H2 + I2
= =K
[NH3 ]2 [O2 ]5 / 2 At t = 0 (2 moles) 0 0
At equilibrium (2 – 2a) moles a mole a mole
K 2 . K 33 Total moles at equilibrium = 2 – 2a + a + a = 2
\ K=
K1 mole
15. (a) First option is incorrect as the value of KP 21. (d) Rate constant of forward reaction (Kf )
given is wrong. It should have been = 1.1 × 10–2 and rate constant of backward
PCO2 reaction (Kb) = 1.5 × 10–3 per minute. Equilibrium
KP = constant (Kc)
PCH4 ´ [PO2 ]2
16. (a) For reaction (i) K f 1.1 ´ 10 -2
= = = 7.33
K b 1.5 ´ 10 -3
[NO]2
K1 = 22. (d) DG = DG° + RT ln Q
[N 2 ][O2 ]
At equilibrium DG = 0, Q = Keq
and for reaction (ii)
So, DrG° = –RT ln Keq
[N 2 ]½ [O2 ]½ 1
DrG° = –8.314 J mol–1 K–1 × 300 K × ln(2 × 1013)
K2 = therefore K1 = 2
[NO] K2 23. (a) A2(g) + B2(g) X (g); DH = –X kJ
2
17. (a) MgCO3 (s) ® MgO(s) + CO 2 (g) On increasing pressure equilibrium shifts in a
MgO & MgCO3 are solid and they do not exert direction where number of moles decreases i.e.
any pressure and hence only pressure exerted forward direction.
is by CO2. Therefore KP = PCO2 On decreasing temperature, equilibrium shifts
18. (b) In polyprotic acids the loss of second in exothermic direction i.e., forward direction.
proton occurs much less readily than the first. So, high pressure and low temperature favours
Usually the Ka values for successive loss of maximum formation of product.
protons from these acids differ by at least a factor 24. (d) Clausius – Clapeyron's equation
of 10–3 i.e., K a1 > K a2 d ln P DH v
=
dT RT 2
H 2X ( 1)
H+ + HX- K a 25. (b) DG° = –2.30RT log K
because at equilibrium DG = 0
H+ + X 2- ( K a )
HX- 2 26. (d) Given reaction is exothermic reaction.
19. (d) For the reaction Hence according to Le-Chatelier's principle low
XeOF (g) + 2HF(g)
XeF6(g) + H2O(g) temperature favours the forward reaction and
4
on increasing pressure equilibrium will shift,
[XeOF4 ][HF]2
K1 = ....(a) towards lesser number of moles i.e. forward
[XeF6 ][H 2 O] direction.
and for the reaction 27. (a) In exothermic reactions on increasing
XeOF (g) + HeO F (g)
XeO4(g) + XeF6(g) temperature value of Kp decreases
4 3 2
[XeOF4 ][XeO 3 F2 ] \ Kp > Kp¢ (Assuming T1 < T2)
K2 = ....(b)
[XeO 4 ][XeF6 ]
28. (c) Given, CH3COOH CH3COO– + H+ ;
For reaction :
K a1 , = 1.5 × 10– 5 ....(i)
XeO 4 (g) + 2HF(g) ® XeO3F2(g) + H 2 O(g)
Equilibrium 83
HCN H++ CN–; K = 4.5 × 10–10 34. Liquid
(d) Solid
a2
It is an endothermic process. So when
+ –
or H + CN HCN; temperature is raised, more liquid is formed.
1 1 Hence adding heat will shift the equilbrium in
K a' 2 = = ...(ii)
Ka2 4.5 ´ 10 –10 the forward direction.
35. (d) According to Le-chatelier's principle
\ From (i) and (ii), we find that the equilibrium
whenever a constraint is applied to a system in
constant (Ka) for the reaction,
equilibrium, the system tends to readjust so as
CN– + CH3COOH CH COO– + HCN, is
3 to nullify the effect of the constraint.
K a = K a1 ´ K a' 2 36. (d) [OH–] = 0.01 M = 10–2 M
pOH = –log[OH–] = –log(10–2) = 2
1.5×10 –5 1 pH = 14 – pOH = 12
= ´ 105 = 3.33 ´ 10 4
=
4.5×10 –103 37. (d) HCl cannot accept H+ therefore cannot act
29. (d) For reaction to proceed from right to left as Bronsted base.
Q > Kc 38. (c) When a proton is removed from an acid,
æbackward ö æforward ö i.e the reaction will be fast we obtain its conjugate base.
èrate ø èrate ø H + + OH -
H 2 O
in backward direction i.e rb > rf . H + + F -
HF
When Q = Kc, the system is at equilibrium 1
39. (c) Meq. of HCl = 75 ´ ´ 1 = 15
Q < Kc, reaction shift to the right from left. 5
Q > Kc, reaction proceed from right to left. 1
Meq. of NaOH = 25 ´ ´ 1= 5
30. (c) For the reaction 5
BaO(s) + O2 (g); DH = +ve.
BaO 2 (s) Meq. of HCl in resulting solution = 10
At equilibrium K p = PO2 10 1
Molarity of [H+] in resulting mixture = =
[For solid and liquids concentration term is taken 100 10
as unity] +
é1ù
pH = –log[H ] = –log ê ú = 1.0
Hence, the value of equilibrium constant ë 10 û
depends only upon partial pressure of O2 . 40. (a) g eq of NaOH = 0.1 × V = 0.1V
Further on increasing temperature, formation of g eq of HCl = 0.01 × V = 0.01V
O2 increases as this is an endothermic reaction. g eq of NaOH > g eq. HCl
31.
(d) A2(g)+ B2(g)
3C(g)
D(g) hence, resultant solution should be basic, hence
Step 1 Step 2 from the eqn
since the steps 1 and 2 are exothermic hence M1V1 – M2V2 = MV
low temprature will favour both the reactions. In 0.1V – 0.01V = MV
step - 1, moles are increasing hence low pressure
0.09
will favour it. In step 2, moles are decreasing, M= = 0.045 = 4.5 × 10–2
hence high pressure will favour it. 2
32. (b) A2 2A Equilibrium constant is given by Now, pOH = – log [OH–]
= – log 4.5 × 10–2 = 1.34
[ A]2 Q pH + pOH = 14
Kc = \ pH = 14 – 1.34 = 12.65
[ A2 ]
41. (c) Na2CO3 is a salt of strong base (NaOH)
Since the value given is very small, hence conc.
and weak acid (H2CO3). On hydrolysis this salt
of products is less. It means the reaction is slow.
33. (a) If more trans-2-pentene is added, then its will produce strongly basic solution. i.e. pH will
concentration in right hand side will increase. be highest (pH > 7) for this sotluion. Others are
But in order to maintain the K constant, combination of
concentration of cis-2-pentene will also increase.
Therefore more cis-2-pentene will be formed.
EBD_8336
84 CHEMISTRY
KCl = Strong acid + Strong base 50. (a) The solution formed from isomolar
® neutral solution (pH » 7) solutions of sodium oxide, sodium sulphide,
NaCl = Strong acid + Strong base sodium selenide and sodium telluride are H2O,
® neutral solution (pH » 7) H2S, H2Se & H2Te respectively. As the acidic
CuSO4 = Strong acid + wake base strengh increases from H2O to H2Te thus pH
® Acidic solution (pH < 7) decreases and hence the correct order of pHs is
42. (b) BF3 acts as Lewis acid. pH1 > pH2 > pH3 > pH4.
51. (d) For an acid-base indicator
43. (c) BF3 behaves as lewis acid as it is an
H+ + In–
HIn
electron deficient species.
44. (c) Boron in B2H6 is electron deficient.
[H + ][In - ] [HIn]
45. (d) (CH3)3 B – is an electron deficient, thus \ K In = or [H + ] = K In ´
behave as a lewis acid.
[HIn] [In - ]
46. (d) Ammonium chloride is a salt of weak base [HIn]
and strong acid. In this case, hydrolysis or log H + = log K In + log
[In - ]
constant, Kh can be calculated as
Taking negative on both sides
K 1 ´ 10 -14
Kh = w = = 5.65 ´ 10 -10 [HIn]
- log[H + ] = - log K In - log -
K b 1.77 ´ 10 -5
[In ]
47. (b) [H3O]+ for a solution having pH = 3 is given [In - ]
by or we can write pH = pK In + log
[HIn ]
[H3O]+ = 1×10–3 moles/litre [\ [H3O]+ = 10–pH]
Similarly for solution having pH = 4, [In - ]
or log = pH - pK In
[H3O]+ = 1 × 10–4 moles/ litre and for pH=5 [HIn]
[H3O+] = 1×10–5 moles/ litre 52. (c) The higher is the tendency to donate
Let the volume of each solution in mixture be 1L, proton, stronger is the acid. Thus, the correct
then total volume of mixture solution order is R – COOH > HOH > R – OH > CH º CH
= (1 + 1 + 1) L =3L depending upon the rate of donation of proton.
Total [H3O]+ ion present in mixture solution
= (10–3 + 10–4 + 10–5) moles The stability order of conjugate base is
Then [H3 O]+ ion concentration of mixture RCOOQ > H - OQ > R – OQ > HC º CQ
solution
53. (b) B(OH)3 does not provide H+ ions in water
-3 -4 -5
10 + 10 + 10 0.00111 instead it accepts OH– ion and hence it is Lewis
= M= M acid
3 3
= 0.00037 M = 3.7 ×10–4 M. [B(OH) ]- + H +
B(OH )3 + H 2O 4
48. (a) Given [H3O+] = 1 × 10–10 M 54. (c) Strong base has higher tendency to accept
at 25ºC [H3O+] [OH–] = 10–14 the proton. Increasing order of base and hence
10 -14 the order of accepting tendency of proton is
\ [OH - ] = = 10-4
10 -10 I- < HS- < NH3 < RNH 2
55. (a) Given : Hydroxyl ion concentration
Now, [OH - ] = 10 - pOH = 10–4
[OH–] = 0.05 mol L–1. We know that the
\ pOH = 4
49. (a) For a solution of 10–8 M HCl, [H+] = 10–8 [H + ][OH - ] = 1´10 -14
[H+] of water = 10–7 -14
or [H + ] = 1´ 10
–1
Total [H+] = 10–7 + 10–8 = 10 × 10–8 + 10–8 = 2 ´ 10 -13 mol L
0.05
10–8 (10 + 1) = 11 × 10–8
Equilibrium 85
Since [OH–] > [H+] On taking log on both side

Therefore the solution is basic. – log [H+] = –log (55 × 10–14)1/2
56. (b) Because NH3 after losing a proton (H+)
1
gives NH2– pH = ( - log 55 + 14log10)
NH 2– + H 3O + 2
NH + H O
3 2 pH = 6.13
(Conjugate acid-base pair differ only by a proton)
57. (b) CH3COOH is weak acid while NaOH is Calculation of pOH in this question: value of pH
and pOH must be same for a neutral solution.
strong base, so one equivalent of NaOH can Thus, pOH = 6.13, also pH + pOH = –log (55 × 10–14)
not be neutralized with one equivalent of
CH3COOH. Hence the solution of one equivalent Ka Ka
of each does not have pH value as 7. Its pH will be 62. (c) a = = 0.037 = ;
c 0.10
towards basic side as NaOH is a strong base
hence conc. of OH– will be more than the conc. K a = (0.037) 2 ´ 0.10 = 1.37 ×10–4
of H+.
; 1.4 × 10–4
58. (c) Because of electron deficiency, boron
63. (a) Given Ka = 1.00×10–5, C= 0.100 mol
trifluoride and stannous chloride are lewis acid.
for a weak electrolyte,
Vacant d-orbitals are available with stannic degree of dissociation
chloride, hence it can also accept pair of electrons
and act as a lewis acid. Ka 1 ´ 10 –5
4 a= = 10-2 = 1%
59. (d) No. of moles of NaOH = = 0.1 C 0.100
40
[Molecular weight of NaOH = 40] 64. (d) Given Kb = 1.0 × 10–12
[BOH] = 0.01 M [OH] = ?
No. of moles of OH– = 0.1
a= Kb / c
0.1
Concentration of OH– = = 0.1 mol / L
1 litre 1 ´ 10-12
= = 1.0 × 10–5
0.01
As we know that, [H + ] [OH - ] = 10 -14
Now [OH–] = c.a = 0.01 × 10–5
+
\ [H ] = 10 -13 – –1 = 1 × 10–7mol L–1
(Q[OH ] = 10 )
60. (a) Molarity (M) = 10M. HCl is a strong acid 65. (c) CH3COOH CH COO– + H+
3
and it is completely dissociated in aqueous [CH3COO- ][H+ ]
solutions as : HCl (10) H+(10) + Cl–. Ka =
[CH 3COOH]
So, for every moles of HCl, there is one H+.
Given that,
Therefore [H+] = [HCl] or [H+] = 10.
pH = – log[H+] = – log [10] = – 1. [CH 3 COO - ] = [H + ] = 3.4 ´ 10 -4 M
61. (a) Kw at 25°C = 1 × 10–14 Ka for CH3COOH = 1.7 × 10–5
At 25ºC CH3COOH is weak acid, so in it [CH3COOH] is
Kw = [H+] [OH–] = 10–14 equal to initial concentration. Hence
At 100°C (given)
(3.4 ´ 10-4 )(3.4 ´10 -4 )
Kw = [H+] [OH–] = 55 × 10–14 1.7 ´10 -5 =
[CH 3COOH]
Q for a neutral solution
[H+] = [OH–] 3.4 ´ 10 -4 ´ 3.4 ´ 10 -4
[ CH 3 COOH ] =
\ [H+]2 = 55 × 10–14 1.7 ´ 10 -5
or [H+] = (55 × 10–14)1/2 = 6.8 × 10–3M
Q pH = – log [H+]
EBD_8336
86 CHEMISTRY
66. (b) An aqueous solution of acetic acid \ Ksp = (2.2 × 10–4)2 (1.1 × 10–4)
dissociates as = 5.324 × 10–12
CH3COOH + H2O CH COO– + H O+ 72. | M+ + Y–
(b) MY
3 3
67. (d) Ni(OH)2 Ni2+ + 2OH–
2
Ksp = s = 6.2 × 10–13
s s 2s
NaOH ¾¾ ® Na + OH–
s = 6.2´ 10- 13
Total [OH–] = 2s + 0.1 » 0.1 s = 7.87 × 10–7 mol L–1
| N3+ + 3Y –
NY3
Ionic product = [Ni]2+[OH]2
2 × 10–15 = s(0.1)2 Ksp = s × (3s)3 = 27s4 = 6.2 × 10–13
1/4
s = 2 × 10–13 æ 6.2 ´ 10-13 ö
Solubility of Ni(OH)2 = 2 × 10–13 M s= ç ÷
è 27 ø
68. (d) CaF2 Ca2+ + 2F– s = 3.89 × 10 mol L–1
–4
t=0 0 0 \ molar solubility of NY3 is more than MY in

At eqm. s 2s water.
NaF ¾¾
® Na+ + F– 73. (b) The presence of large amount of KHSO4
0.1 0.1 0.1 will decrease ionisation of H2SO4 that result in
Due to common ion effect of NaF, solubility of lesser ionisation of nitric acid and lesser
CaF2 is further supressed. Therefore, the formation of nitronium ion [NO2+]. Hence the
concentration of F– will be mainly due to NaF. rate of nitration will be slower.
Ksp = [Ca2+] [F–]2 74. (c) Ag2CrO4
Ksp = (s) (0.1 + 2s) 2 0.1 + 2s » 0.1 Ksp = [Ag+]2 é CrO 4–2 ù = 1.1 × 10–12
ë û
Ksp 5.3 ´ 10 –11
s= = = 5.3 × 10–9 mol L–1 1.1 ´ 10 –12
(0.1) 2
(0.1)2 [Ag + ] =
éCrO4–2 ù
69. (a) Ca(OH) 2 Ca 2 + + 2OH - ë û
AgCl
pH = 9, pOH = 14 – 9 = 5
Ksp = [Ag+] [Cl–] = 1.8 × 10–10
[OH–] = 10–5
-5 1.8 ´ 10 –10
é Ca 2 + ù = 10 [Ag+] =
ë û 2 [Cl – ]
æ 10-5 ö -5 2 AgBr
Ksp = [Ca2+] [OH–]2 = ç 2 ÷ ´ (10 ) Ksp = [Ag+] [Br–] = 5.0 × 10–13
è ø
= 0.5 × 10–15 5.3 ´ 10 –13
[Ag + ] =
70. (a) Solubility of BaSO4 = 2.42 × 10–3 gL–1 [Br – ]
2.42 ´ 10-3 AgI
\ s= = 1.038 ´ 10-5 mol L-1 Ksp = [Ag+] [I–] = 8.3 × 10–17
233
Ksp = s2 = (1.038 × 10–5)2 = 1.08 × 10–10 mol2 L–2 8.3 ´ 10–17
[Ag + ] =
71. (c) [I – ]
2Ag + ( aq ) + C 2O 42- ( aq )
Ag 2C 2 O 4 (s)
If we take éë CrO 4 ùû = [Cl ] = [Br ] = [I ] = 1
–2 – – –
2s s
Ksp = [Ag+]2 [C2O42–] then maximum [Ag+] will be required in case of
[Ag+] = 2.2 × 10–4 M Ag2CrO4.
75. (a) Among the given acids, HClO4 is a very
Given that:
strong acid, completely dissociates
\ Concentration of C2O42– ions,
-4
\ [HA] ® 0 in this case, hence cannot be used
éë C2 O24 - ùû = 2.2 ´ 10 M = 1.1 ´ 10 -4 M for acidic buffer.
2
Equilibrium 87
76. (b) DG = – 2.303 log K Ba(OH) 2 Ba 2+ + 2OH

here K = [Ag+]2 [CO2–
3 ] = Ksp
s 2s
+ 3
\ 63.3 × 10 = – 2.303 × 8.314 × 298 log Ksp [OH–] = 10–2
+3 2s = 10–2
63.3 ´ 10
\ log Ksp = - = - 11.09
10-2
5705.8
s= = 5 ´ 10-3 m , Ksp = s . (2s)2
\ Ksp = Antilog (– 11.09) = 8 × 10– 12 2
77. (c) Solubility of alkali metal is maximum among Þ Ksp = 5 × 10–7
the following. Among ZnS (1.7 × 10–5) & CuS
81. (a) (AlCl3, LiCl & BeCl2) ) all these solutions
(8 × 10–37) ZnS has higher value of Ksp.
are acidic due to cationic hydrolysis, whereas
78. (a) CaCO3 ¾® Ca 2+ + CO32- BaCl2, is salt of strong base (Ba(OH)2) and strong
x x acid (HCl), hence it will have maximum pH.
82. (a) Constant acidity and alkalinity of buffer
CaC2O4 ¾® Ca 2+ + C 2 O 24- solution is due to the unionised acid or base.
y y
Lets take an example of an acidic buffer
\ [Ca2+] = x + y CH3COOH and CH3COONa.
CH3COOH CH3COO– + H+ ;
Now, Ksp (CaCO3) = [Ca2+] [CO32-]
CH3COONa CH3COO– + Na+
or 4.7 × 10 –9 = (x + y) x
when few drops of HCl are added to this buffer,
similarly, Ksp (CaC2O4) = [Ca2+] [C2O42–] the H + of HC l immediatly combine with
CH3COO– ions to form undissociated acetic acid
or 1.3 × 10 –9 = (x + y) y molecules. Thus there will be no H + ions to
On solving, we get combine with CH 3 COO – ions to form
undissociated acetic acid molecules. Thus there
[Ca2+] = 7.746 × 10–5 M will be no appreciable change in its pH value.
79. (c) Given, Ka = 1 × 10– 4 Likewise if few drops of NaOH are added, the
OH – ions will combine with H + ions to form
\ pKa = – log (1× 10– 4) = 4 unionised water molecule. Thus pH of solution
Now from Handerson equation will remain constant.
[Salt] 83. (b) Given : [NH3] = 0.3 M, [NH4+] = 0.2 M,

pH = pKa + log
[Acid] Kb = 1.8 × 10–5 .
Putting the values [salt]
pOH = pKb + log
[base]
[Salt] [pKb = –log Kb; pKb = –log 1.8 × 10–5]
5 = 4 + log
[Acid] \ pKb = 4.74
[Salt] 0.2
log = 5–4=1 pOH = 4.74 + log
[Acid] 0.3
Taking antilog = 4.74 + 0.3010 – 0.4771 = 4.56
[Salt]/[Acid] = 10 = 10 : 1 pH = 14 – 4.56 = 9.436
80. (b) Given pH = 12 84. (c) Ksp = [Ag+] [Cl–]
or [H+] = 10–12 1.8 × 10–10 = [Ag+] [0.1]
Since, [H+] [OH–] = 10–14 [Ag+] = 1.8 × 10–9 M
Ksp = [Pb+2] [Cl–]2
10-14 1.7 × 10–5 = [Pb+2] [0.1]2
\ [OH–] = -12 = 10–2
10 [Pb+2] = 1.7 × 10–3 M
EBD_8336
88 CHEMISTRY
85. ® Ba 2+ (aq) + 2 OH - (aq)

(d) Ba (OH)2 (s) ¾ ¾ 91. (c) For AX 2 ; K sp = 4s3 \ 3.2 ´ 10-11 = 4 s3
pH = 12 or pOH = 2
3.2 ´ 10-11
[OH - ] = 10-2 M or s = 3 = 2 ´ 10-4
4
Ba(OH) 2 ¾¾® Ba 2 + + 2 OH– 92. (c) Ksp for AgI = 1 × 10–16
10-2 In solution of KI, I– would be due to the both
0.5× 10-2
AgI and KI, 10–4 solution KI would provide
[\ Concentration of Ba 2 + is half of OH - ] = 10–4 I–
K sp = [Ba 2+ ] [OH - ]2 AgI would provide, say = x I– (x is solubility of
AgI)
= [0.5 × 10-2 ] [1 × 10-2 ]2 Total I– = (10–4 + x) , Ksp of AgI = (10–4 + x) x
Þ Ksp = 10–4x + x2
= 0.5 × 10 -6 = 5 × 10-7 M3 as x is very small
é Salt ù \ x2 can be ignored
86. (d) pH = p Ka+ log ê \ 10–4 x = 10–16
ë Acid úû
10 -16
or x = = 10 -12 (mol L-1 )
log é H = log Ka – log é Salt ù
+ù
10 -4
ë û êë Acid úû (solubility)
+ é Acid ù 93. (d) Given s = 0.5 × 10–4 moles/L

log éë H ùû = log Ka + log ê M2+ + 2X]
ë Salt úû [MX2
Q For MX2, Ksp = s × (2s)2 = 4s3
é H + ù = K é Acid ù Ksp = 4 × (0.5 × 10–4)3 = 4 × 0.125 ×10–12
ë û aê
ë Salt úû = 0.5 × 10–12 = 5 × 10–13
0.1 94. (b) Na2CO3 is a salt of weak acid H2CO3 and
= 1.8 × 10 -5 ´ = 9 × 10-6 M
0.2 strong base NaOH, therefore, its aqueous
87. (d) Kb = 10-10 ; Ka = 10-4 or pKa = 4 solution will be basic hence has pH more than 7.
For the buffer solution containing equal Na 2 CO 3 + 2H 2 O ¾¾
® 2NaOH + 2H 2 CO 3
strong base weak acid
concentration of B– and HB
pH = pKa + log 1 [Salt]
95. (b) pOH = pKb + log
pH = pKa = 4 [Base]
88. (b) The highest pH will be recorded by the [salt]
most basic solution. The basic nature of or pKb = pOH–log
[Base]
hydroxides of alkaline earth metals increase as
but pOH+ pH = 14 or pOH = 14 – pH
we move from Mg to Ba and thus the solution of
BaCl2 in water will be most basic and so it will [Salt]
\ 14– pH – log = pK b
have highest pH. [Base]
89. (d) HNO2 is a weak acid and NaNO2 is salt of 0.1
that weak acid and strong base (NaOH). 14 - 9.25 - log = pK b
0.1
90. (a) IV th g r oup n eeds h i gh er S 2– i on 14 – 9.25 – 0 = pKb
concentration. pKb = 4.75
In presence of HCl, the dissociation of H 2 S
decreases hence produces less amount of sulphide 96. (a) 2 M + + S––
M 2S
2s s
ions due to common ion effect, thus HCl decreases
the solubility of H 2 S which is sufficient to Solubility product = (2s)2 (s) = 4s3
precipitate IInd group radicals. = 4 (3.5 × 10–6)3 = 1.7 × 10–16
Equilibrium 89
101. (a) For Bi2S3 . Ksp = (2s)2.(3s)3

97. (d) BA2 ® B+ 2 A
s 2s = 4s2. 27s3 = 108s5
Solubility product = [s] [2s]2 = 4s3
K sp 1 ´ 10 –17
- 12 or s = 5 = 5
3 4´ 10 108 108
4 × 10–12 = 4s3 or s =
4 For MnS. Ksp = s2
\ s = 10–4
98. (b) For Binary salts like CuS & HgS, solubilty,
or s = K sp = 7 ´ 10- 16
s = K sp for CuS s = K sp = 8 ´ 10-37

For Ag2S Ksp = 2s2. s = 4s3
Þ sCuS = 10-31 = 3.16 × 10–16,
sHgS = 10 -54 = 10–27 K sp 3 6 ´ 10 -51
or s = 3 =
4 4
+ 2
For Ag 2S ® 2 Ag + S thus Bi2S3 has maximum solubility.
2s s
K sp 10-44 The solubility of Bi2S3 will be in the order of 5th

K sp = 4s3 or sAg 2S = 3 =3 root of 10–17, thus, it is most soluble.
4 4
102. (a) Sodium borate is a salt of strong base
= 3 -45 -16 (NaOH) and weak acid (H3BO3). Hence, its
0.25 ´ 10 ´ 10 = 13.54 ´ 10
\ The order is Ag2S > CuS > HgS aqueous solution will be basic.
103. (b) AgBr has the highest solubility in 10–3 M
[Salt]
99. (d) pH = pKa + log NH4OH. AgBr is less soluble in NaBr and HBr
[Acid]
For acetoacetic acid due to presence of common ion (Br). With
[Salt] NH4OH, AgBr will react as:
3.58 = 3.58 + log AgBr(s) + 2NH4OH(aq.)
[Acid]
[Salt] ® [Ag(NH3)2]Br(aq.) + 2H2O(l)
Þ log =0
[Acid] Hence, the highest solubility with NH4 OH
solution.
[Salt] 104. (c) NaCl is a salt of strong acid and strong
Þ =1
[Acid] base hence its aqueous solution will be neutral
This is the required condition for maximum buffer i.e. pH = 7. NaHCO3 is an acidic salt hence pH <
capacity. 7. Na2CO3 is a salt of weak acid and strong base.
100. (d) The buffer system present in serum is Hence its aqueous solution will be strongly
H2CO3 + NaHCO3 and as we known that a buffer basic i.e. pH > 7.
solution resist the change in pH therefore pH NH4Cl is salt of weak base and strong acid, hence
value of blood does not change by a small its aqueous solution will be strongly acidic i.e.
addition of an acid or a base. pH < 7.
EBD_8336
90 CHEMISTRY
8 Redox Reactions
2020 2019 2018 2017 2016

Oxidation number oxidation number 1 E
disproportionation
Disproportionation 1 A 1 D
reaction
and balancing of redox
balancing of redox
reaction 1 A
reaction
Topic 1: Oxidation and Reduction Reactions (a) 0 to + 4 (b) – 4 to + 4

(c) 0 to – 4 (d) + 4 to + 4
1. Zn gives H2 gas with H2SO4 and HCl but not 5. The oxidation state of Cr in CrO6 is
with HNO3 because [2002] [NEET Odisha 2019]
(a) Zn acts as an oxidising agent when it reacts (a) +4 (b) –6
with HNO3 (c) +12 (d) +6
(b) HNO3 is weaker acid than H2SO4 and HCl
(c) In electrochemical series, Zn is above 6. Oxidation numbers of P in PO3– 2–
4 , of S in SO 4
hydrogen and that of Cr in Cr2 O 72– are respectively
(d) NO3- is reduced in preference to hydronium [2009]
ion (a) + 3, + 6 and + 5 (b) + 5, + 3 and + 6
2. Which of the following involves a redox reaction? (c) – 3, + 6 and + 6 (d) + 5, + 6 and + 6
(a) Reaction of H2SO4 with NaOH [1997] 7. The oxidation states of sulphur in the anions
(b) Production of ozone from oxygen in the SO32–, S2O42– and S2O62– follow the order[2003]
atmosphere by lightning (a) S2 O 6 2 - < S2 O 4 2- < SO 3 2-
(c) Production of nitrogen oxides from nitrogen
and oxygen in the atmosphere by lightning (b) S2 O 4 2 - < SO 3 2- < S2 O 6 2-
(d) Evaporation of water (c) SO32- < S2 O4 2- < S2O 6 2-
3. The loss of electron is termed as [1995]
(d) S2 O 4 2 - < S 2 O 6 2- < SO 3 2-
(a) oxidation (b) reduction
8. A compound contains atoms of three elements
(c) combustion (d) neutralization
A, B and C. If the oxidation number of A is +2, B
Topic 2: Oxidation Number is +5, and that of C is –2, the possible formula of
the compound is : [2000]
4. What is the change in oxidation number of
(a) A2(BC3)2 (b) A3(BC4)2
carbon in the following reaction? [2020]
CH4(g) + 4Cl2(g) ¾® CCl4(l) + 4HCl(g) (c) A3(B4C)2 (d) ABC2
Redox Reactions 91
9. The oxidation number of phosphorus in pyro- 15. A mixture of potassium chlorate, oxalic acid and
phosphoric acid is [1999] sulphuric acid is heated. During the reaction
(a) +3 (b) +1 which element undergoes maximum change in
(c) +4 (d) +5 the oxidation number ? [2012]
10. The oxidation number of chromium in potassium (a) S (b) H
dichromate is [1988, 1995] (c) Cl (d) C
(a) + 6 (b) – 5
16. When Cl2 gas reacts with hot and concentrated
(c) – 2 (d) + 2
sodium hydroxide solution, the oxidation number
11. Phosphorus has the oxidation state of + 3 in
of chlorine changes from : [2012]
(a) Phosphorous acid [1994]
(b) Orthophosphoric acid (a) zero to +1 and zero to –5
(c) Hypophosphorous acid (b) zero to –1 and zero to +5
(d) Metaphosphoric acid. (c) zero to –1 and zero to +3
Topic 3: Disproportionation and Balancing (d) zero to +1 and zero to –3
of Redox Reactions 17. The following redox reaction is balanced by
which set of coefficients ? [1999]
12. Which of the following reactions are dispro-
portionation reaction? [2019] aZn + bNO 3- + cH + ® dNH +4 + eH 2 O + fZn 2+
(a) 2Cu+ ® Cu2+ + Cu a b c d e f
(b) 3MnO42– + 4H+ ® 2MnO4– + MnO2 + 2H2O (a) 1 1 10 1 3 1
D
(b) 2 2 10 2 3 2
(c) 2KMnO4 ¾¾® K2MnO4 + MnO2 + O2 (c) 4 2 10 1 3 4
D (d) 4 1 10 1 3 4
(d) 2MnO4–+ 3Mn2+ + 2H2O ¾¾® 5MnO2 + 4H+
18. In which of the following reactions, there is no
Select the correct option from the following: change in valency ? [1994]
(a) (a) and (b) only (b) (a), (b) and (c)
(a) 4 KClO3 ¾ ¾® 3KClO4 + KCl
(c) (a), (c) and (d) (d) (a) and (d) only
13. For the redox reaction [2018] (b) SO2 + 2H2S ¾ ¾® 2H2O + 3S
+ 2+ (c) BaO2 + H2SO4 ¾ ¾® BaSO4 + H2O2
MnO4– + C2 O2–4 + H ® Mn + CO2 + H 2 O
(d) 3 BaO + O2 ¾ ¾® 2 BaO2.
The correct coefficients of the reactants for the 19. Which substance serves as a reducing agent in
balanced equation are the following reaction ? [1994]
MnO4– C2 O2–4 H+
14H+ + Cr2 O 27 - + 3Ni ® 2Cr3+ + 7H2O + 3Ni2+
(a) 16 5 2
(a) H2O (b) Ni
(b) 2 5 16
(c) 5 16 2 (c) H+ (d) Cr2 O 27-
(d) 2 16 5
14. Consider the change in oxidation state of Topic 4: Electrode Potential and Oxidising,
bromine corresponding to different emf values Reducing Agents
as shown in the diagram below : [2018] 20. The standard electrode potential (E°) values of
BrO4– 1.82 V 1.5 V Al3+/Al, Ag+/Ag, K+/K and Cr3+/Cr are –1.66 V,
¾¾¾® BrO3– ¾¾¾® HBrO
0.80 V, –2.93V and –0.74 V, respectively. The
¾¾
correct decreasing order of reducing power of

Br –¬¾¾¾ Br2 ¬¾¾¾ the metal is [NEET Odisha 2019]
1.0652 V 1.595 V
Then the species undergoing disproportion- (a) Al > K > Ag > Cr
ation is (b) Ag > Cr > Al > K
(a) BrO3– (b) BrO 4– (c) K > Al > Cr > Ag
(c) HBrO (d) Br2 (d) K > Al > Ag > Cr
EBD_8336
92 CHEMISTRY
21. Standard reduction potentials of the half The strongest oxidising and reducing agents
reactions are given below : respectively are : [2012 M]
F2(g) + 2e– ® 2F– (aq); E° = + 2.85 V (a) F2 and I– (b) Br2 and Cl–
Cl2(g) + 2e– ® 2Cl–(aq); E° = + 1.36 V (c) Cl2 and Br– (d) Cl2 and I2
22. The oxide, which cannot act as a reducing agent,
Br2(l) + 2e– ® 2Br–(aq); E° = + 1.06 V is [1995]
I2(s) + 2e– ® 2I–(aq); E° = + 0.53 V (a) NO2 (b) SO2
(c) CO2 (d) ClO2
ANSW E R K E Y
1 (d ) 4 (b ) 7 (b ) 10 (a ) 13 (b ) 16 (b ) 19 (b ) 22 (c )
2 (c ) 5 (d ) 8 (b ) 11 (a ) 14 (c ) 17 (d ) 20 (c )
3 (a ) 6 (d ) 9 (d ) 12 (a ) 15 (c ) 18 (c ) 21 (a )
Hints & Solutions

1. (d) Zinc gives H2 gas with dil H2SO4/HCl but 5. (d) +6 is the most appropriate oxidation state
not with HNO3 because in HNO3, NO3– ion is of Cr in CrO6.
reduced and give NH4NO3, N2O, NO and NO2 –1 –1
O O
[Zn + 2HNO3 ¾¾
® Zn(NO3 )3 + 2H] ´ 4
–1 +6 –1
(nearly 6%)
O Cr O
HNO3 + 8H ¾® NH3 + 3H2O
NH3 + HNO3 ¾® NH4NO 3
O O–1
4Zn+10HNO3 ¾® 4Zn(NO3)2+NH4NO3+3H2O –1
Zn is above of hydrogen in electrochemical series.
So, Zn displaces H2 from dilute H2SO4 and HCl 6. (d) PO3–
4 = x + 4 (– 2) = – 3; x – 8 = – 3; x = + 5
with liberation of H2. SO 2–
4 = x + 4 (– 2) = – 2; x – 8 = – 2; x = + 6
Zn + H2SO4 ® ZnSO4 + H2
Cr2 O72– = 2x + 7 (– 2) = – 2; 2x – 14 = – 2;
2. (c) (a) 2NaOH+H 2SO 4 ¾¾
® Na 2SO 4 +2H 2 O 2x =12; x = + 6
(neutralization)
7. (b) SO 32 - ® S is in + 4 oxidation state
0 0
(b) Light
3 O 2 ¾¾¾® 2 O 3 (not redox reaction) S2 O 24- ® S is in + 3 oxidation state
Light
S2 O 62- ® S is in + 5 oxidation state
(c) N 2 + O2 ¾¾¾® 2 N O (redox reaction)
0 0 +2 -2 The structure of S 2O 42– and S 2 O 6 2– are
here oxidation of N2 & reduction of O2 is taking symmetrical. Thus, both sulphur atoms are in same
place oxidation state. This is not the case with S2O32–
D or S4O62– ions.
(d) H 2O(l) ¾¾® H 2 O(g) (not redox reaction)
3. (a) Losing of electron is called oxidation. 8. (b) Oxidation number of a compound must be
-4 +4 0. Using the values for A, B and C in the four
4. (b) CH 4 (g) + 4Cl2 (g) ® CCl 4 (l ) + 4HCl (g)
options we find that A3(BC4)2 is the answer.
Change in oxidation state of carbon is –4 to +4. Check : (+2)3 + [(+5) + 4(–2)]2 = 6 + (5 – 8)2 = 0
Redox Reactions 93
9. (d) Pyrophosphoric acid H4P2O7 Reaction in (d) involves comproportionation or

Let oxidation state of phosphorus is x synproportionation. When two reactants, each
(4 × 1 + (– 2) × 7 + 2 x) = 0 containing the same element but with a different
\ 2x = 10 or x = +5 oxidation number, form a product in which the
10. (a) Let x = oxidation no. of Cr in K2Cr2O7. element involved reach the same oxidation number.
Oxidation
\ (2 × 1) + (2 × x) + 7 (– 2) = 0 +4
+7 2+ +
or 2 + 2x – 14 = 0 or x = + 6. 2MnO–4 + 3Mn + 2H2O 5MnO2 + 4H
11. (a) O.N. of P in H3PO3 (phosphorous acid)
Reduction
3 × 1 + x + 3 × (– 2) = 0 or x = + 3 It is opposite to disproportionation.
In orthophosphoric acid (H3PO4) O.N. of P is
+5 +6 +6
+ 5, in hypophosphorous acid (H3PO2) it is + 1 15. (c) KClO 3 + H 2C 2 O 4 + H 2SO 4 ® K 2SO 4
while in metaphosphoric acid (HPO3), it is + 5. –1
12. (a) In a disproportionation reaction, one species + KCl + CO 2 + H 2 O
undergoes both oxidation and reduction. i.e. maximum change in oxidation number is
observed in Cl (+5 to –1).
Reduction
16. (b) On reaction with hot and concentrated alkali
+ 2+ a mixture of chloride and chlorate is formed
2 Cu ¾¾¾¾® Cu + Cu°
Oxidation Hot
3Cl2 + 3 NaOH(excess) ¾¾¾ ®
Reduction -1 +5
5NaCl + NaClO3 + 3H 2O
+6 +7 +4
2– +
3MnO4 + 4H ¾® 2MnO4 + MnO2 + 2H2O
–
17. (d) Zn ® Zn +2 + 2e - ....(1)
8e - + 10H + + NO 3- ® NH +4 + 3H 2 O .....(2)
Oxidation
operate eq. (1) × 4 + eq. (2) × 1

+7 +2
13. (b) ® Mn2+; 5e– gain
Mn O 4– ¾¾ ...(i) 4Zn + 10H + + NO3- ® 4Zn 2 + + NH 4+ + 3H 2O
+2 -1 +1 +6 -2 +2 +6 -2 +1 - 1
+3 +4
- 18. (c) Ba O 2 + H 2 S O4 ¾¾ ® Ba S O4 + H 2 O2
C2O 42– ¾¾
® CO2 ; 2e loss ...(ii)
Multiplying (i) by 2 and (ii) by 5 to balance e– In this reaction, none of the elements undergoes
2+ a change in oxidation number or valency.
2 MnO 4– + 5 C 2 O 2– ® 2 Mn + 10 CO2
4 ¾¾ 19. (b) The element undergo oxidation itself and
On balancing charge; reduces others is known as reducing agent. In
+ this reaction O. N. of Ni Changes from 0 to + 2
2 MnO 4– + 5 C2 O 2–
4 + 16 H ¾¾
®
and hence Ni acts as a reducing agent.
2 Mn 2 + + 10 CO 2 + 8 H 2O 20. (c) Lesser is the reduction potential greater is
14. (c) Calculate E°cell corresponding to each the reducing power.
compound undergoing disproportionation Reducing power : K > Al > Cr > Ag
reaction. The reaction for which E°cell comes out 21. (a) F2 is the strongest oxidising agent as it
+ ve is spontaneous. has highest reduction potential while I– is the
HBrO ¾® Br2 E° = 1.595 V, SRP (cathode) strongest reducing agent since it has lowest
reduction potential.
HBrO ¾® BrO 3– E° = –1.5 V, SOP (anode)
Higher the value of reduction potential, higher will
2HBrO ¾® Br2 + BrO 3– be the oxidising power whereas the lower the value
E°cell = SRP (cathode) – SRP (anode) of reduction potential higher will be the reducing
power.
= 1.595 – 1.5
= 0.095 V 22. (c) Carbon has the maximum oxidation state
E°cell > 0 Þ DG° < 0 [spontaneous] of + 4, therefore carbon dioxide (CO2) cannot
act as a reducing agent.
EBD_8336
94 CHEMISTRY
9 Hydrogen
2020 2019 2018 2017 2016

Preparation and properties of
1 A
properties of hydrogen hydrogen
Preparation and hardness of water 1 A
properties of water
Topic 1: Preparation and Properties of 4. The hydride ion, H–, is a stronger base than the
Hydrogen hydroxide ion, OH–. Which one of the following
reactions will occur if sodium hydride (NaH) is
1. Which of the following statements about
dissolved in water? [1997]
hydrogen is incorrect ? [2016]
(a) hydrogen has three isotopes of which (a) H - (aq) + H 2 O(l) ® H 3O - (aq)
tritium is the most common. (b) H - (aq) + H 2 O(l) ® OH - (aq) + H 2 (g)
(b) Hydrogen never acts as cation in ionic salts
(c) Hydronium ion, H3 O+ exists freely in (c) H – (aq) + H 2 O(l) ®
solution OH– (aq) + 2H+ (aq) + 2e–
(d) Dihydrogen does not act as a reducing agent (d) H (aq) + H2O(l) ® reaction
–
2. When a substance A reacts with water, it 5. The ionization of hydrogen atom would give rise
produces a combustible gas B and a solution of to [1990]
substance C in water. When another substance
D reacts with this solution of C, it also produces (a) Hydride ion (b) hydronium ion
the same gas B on warming but D can produce (c) Proton (d) hydroxyl ion.
gas B on reaction with dilute sulphuric acid at Topic 2: Preparation and Properties of Water
room temperature. A imparts a deep golden yellow
colour to a smokeless flame of Bunsen burner. 6. The number of hydrogen bonded water
A, B, C and D respectively are [1998] molecules(s) associated with CuSO4·5H2O is
(a) Na , H2, NaOH, Zn [NEET 2019 Odisha]
(b) K, H2, KOH, Al (a) 5 (b) 3
(c) Ca, H2, Ca(OH)2, Sn (c) 1 (d) 2
(d) CaC2, C2H2, Ca(OH)2, Fe 7. The method used to remove temporary hardness
3. Which one of the following pairs of substances of water is: [2019]
on reaction will not evolve H2 gas? [1998] (a) Calgon’s method
(a) Iron and H2SO4 (aqueous) (b) Clark’s method
(b) Iron and steam (c) Ion-exchange method
(c) Copper and HCl (aqueous) (d) Synthetic resins method
(d) Sodium and ethyl alcohol
Hydrogen 95
8. Some statements about heavy water are given (c) Na 4 [Na 4 (PO4 )5 ]
below:
(a) Heavy water is used as a moderator in (d) Na 4 [Na 2 (PO 4 )6 ]
nuclear reactors.
(b) Heavy water is more associated than Hydrogen Peroxide
ordinary water.
(c) Heavy water is more effective solvent than 13. (i) H2O2 + O3 ® H2O + 2O2
ordinary water. (ii) H2O2 + Ag2O ® 2Ag + H2O + O2
Which of the above statements are correct? Role of hydrogen peroxide in the above reactions
(a) (a) and (c) (b) (a) and (b)[2010] is respectively - [2014]
(c) (a), (b) and (c) (d) (b) and (c)
(a) Oxidizing in (i) and reducing in (ii)
9. Which of the following groups of ions makes
the water hard ? [1994] (b) Reducing in (i) and oxidizing in (ii)
(a) Sodium and bicarbonate (c) Reducing in (i) and (ii)
(b) Magnesium and chloride (d) Oxidizing in (i) and (ii)
(c) Potassium and sulphate 14. When H2O2 is oxidised, the product is [1999]
(d) Ammonium and chloride. (a) OH– (b) O2
10. The dielectric constant of H2 O is 80. The (c) O2– (d) HO2–
electrostatic force of attraction between Na+ and
15. The volume strength of 1.5 N H2O2 solution is
Cl– will be [1994]
(a) 4.8 L (b) 5.2 L [1996]
(a) reduced to 1/40 in water than in air
(c) 8.4 L (d) 8.8 L
(b) reduced to 1/80 in water than in air
(c) will be increased to 80 in water than in air
(d) will remain unchanged. 16. The O – O – H bond angle in H2O2 is [1994]
11. At its melting point, ice is lighter than water (a) 106° (b) 109° 28'
because [1992] (c) 120° (d) 97°
(a) H2O molecules are more closely packed in 17. Which of the following is the true structure of
solid state H2O2 ? [1989]
(b) Ice crystals h ave hollow hexagonal H
arrangement of H2O molecules.
(a) H– O – O – H (b) O O
(c) On melting of ice the H2O molecule shrinks
in size H
(d) Ice froms mostly heavy water on first H H
(c) O=O (d) O O
melting. H H
12. Calgon used as a water softener is [1989] 18. The reaction of H2O2 with sulphur is an example
of ........reaction [1988]
(a) Na 2 [Na 4 (PO3 )6 ] (a) Addition (b) Oxidation
(b) Na 4 [Na 2 (PO3 )6 ] (c) Reduction (d) Redox
ANSWER KEY
1 (a, d) 3 (c) 5 (c) 7 (b) 9 (b) 11 (b) 13 (c) 15 (c) 17 (b)
2 (a) 4 (b) 6 (c) 8 (b) 10 (b) 12 (a) 14 (b) 16 (d) 18 (d)
EBD_8336
96 CHEMISTRY
Hints & Solutions

1. (a, d) Among the three isotopes of hydrogen, 8. (b) Heavy water is used for slowing down the
( ) 1
speed of neutrons and used as moderators.
Protium 1 H is most common. It is an energetic Boiling point of heavy water is more than that
reducing agent. It reduces oxides, chlorides and of ordinary water, so it is more associated. The
sulphides of certain metals and produce free dielectric constant of heavy water is slightly les
metals at ordinary temperature. than that of ordinary water. Hence, ordinary water
CuO + 2H ® Cu + H2O is more effective solvent than heavy water.
9. (b) Temporary hardness is due to presence of
2. (a) 2Na + 2H 2 O ® 2NaOH + H 2 bicarbonates of calcium and magnesium and
'A' 'C' 'B'
permanent hardness is due to the sulphates or
Zn + 2 NaOH ® Na 2 ZnO 2 + H 2 chlorides of both of calcium and magnesium.
'D ' 'C' 'B' 10. (b) Electrostatic forces of attraction are
reduced to 1/80th in water.
Zn + dil. H 2SO 4 ® ZnSO 4 + H 2
'D ' 'B'
Dielectric constant or relative permittivity is the
Na produces golden yellow colour with
factor by which the electric field between the
smokeless flame of Bunsen burner.
charges is decreased relative to vacuum (or air as
3. (c) Fe + dil. H 2SO 4 ® FeSO 4 + H 2 mentioned in this question).
3Fe + 4H 2 O ® Fe 3O 4 + 4H 2 11. (b) In liquid state, the H2O molecules are held
Steam together by intermolecular H-bonds.
Cu + dil. HCl ® No reaction
When water freezes at atmospheric pressure it
Copper does not evolve H2 from acid as it is crystalises in normal hexagonal form. In it, each
below hydrogen in electrochemical series. oxygen atom is surrounded by 4 hydrogen atoms,
2 Na + C 2 H 5 OH ® 2C 2 H 5 ONa + H 2 two by strong covalent bonds and two by weak
hydrogen bonds. Since hydrogen bonds are longer
than covalent bonds. The molecules of water are
4. (b) H - (aq)+ H 2 O(l) ¾¾
® OH - (aq) + H 2 (g) not closely packed in crystal lattice. There exists a
base 1 acid 1 base 2 acid2
number of hollow spaces in the crystal lattice,
In this reaction H–
acts as bronsted base as it which decreases the density of ice.
accepts one proton (H+) from H2O to form H2. 12. (a) The complex salt of metaphosphoric acid
5. (c) ¾® H + (g ) + e - .
H (g ) ¾ sodium hexametaphosphate (NaPO3)6, is known
6. (c) The actual structure of CuSO4· 5H2O is as calgon. It is represented as Na2[Na4(PO3)6]
[Cu(H2O)4]SO4 · H2O, so only one water molecule Reduction
is associated with the molecule via hydrogen
bond. o –2 o
13. (c) (i) H2–1O2 + O3 H2O + 2O2
7. (b) In this method Ca(OH)2 is used.
Oxidation
Hydrogen 97
Oxidation 14. (b) H 2 O 2 + [O ] ¾Oxidation

¾¾ ¾ ¾® H 2 O + O 2
15. (c) Volume strength = 5.6 × Normality
(ii) –1 –2 o
H2O2 + Ag2O 2Ag + H2O +2O2 = 5.6 × 1.5 = 8.4 L
16. (d) O – O – H bond angle in H2O2 is 97°.
Reduction
17. (b) H is the true structure of H2O2.
O O
Hence, in both the reactions, H2O2 is acting as H
an reducing agent. oxidation
18. (d)
Half equations for oxidation of H2O2. H2S + H2O2 2H2O + S
(i) In acidic medium reduction
H2O2 ¾® 2H+ + O2 + 2e–
(ii) In basic medium
In this reaction, H2S is oxidised to sulphur and
H2O2 + OH– ¾® 2H2O + O2 + 2e– H2O2 is reduced to H2O, hence this reaction show
Half equations for reduction of H2O2: oxidation-reduction both i.e., redox reaction.
(i) In acidic medium
H2O2 + 2H+ + 2e– ¾® 2H2O
(ii) In basic medium
H2O2 + 2e– ¾® 2OH–
EBD_8336
98 CHEMISTRY
10 The s -Block
Elements
2020 2019 2018 2017 2016

Preparation and
biological
properties of alkali
importance of 1 E
metals and their
alkali metals
compounds
Some important properties of
1 E
compounds of sodium sodium chloride
properties of
alkaline earth 1 A 2 A
Preparation and
metals compounds
properties of alkaline
biololgical
earth metal and their
importance of
compounds 1 E 1 E
alkaline earth
metals
Topic 1: Preparation and Properties of Alkali 4. Which one of the alkali metals, forms only, the
Metals and their Compounds normal oxide, M2O on heating in air ? [2012]
(a) Rb (b) K
1. The following metal ion activates many (c) Li (d) Na
enzymes, participates in the oxidation of glucose 5. The ease of adsorption of the hydrated alkali
to produce ATP and with Na, is responsible for metal ions on an ion-exchange resins follows the
the transmission of nerve signals. [2020] order : [2012]
(a) Copper (b) Calcium (a) Li+ < K+ < Na+ < Rb+
(c) Potassium (d) Iron (b) Rb+ < K+ <Na+ < Li+
2. Which of the alkali metal chloride (MCl) forms (c) K+ < Na+ < Rb+ < Li+
its dihydrate salt (MCl × 2H2O) easily? (d) Na+ < Li+ < K+ < Rb+
[NEET Odisha 2019 ] 6. In the replacement reaction
(a) KCl (b) LiCl CI + MF CF + MI
(c) CsCl (d) RbCl The reaction will be most favourable if M happens
to be : [2012 M]
3. The function of "Sodium pump" is a biological
(a) Na (b) K
process operating in each and every cell of all
(c) Rb (d) Li
animals. Which of the following biologically
7. The sequence of ionic mobility in aqueous
important ions is also a consituent of this
solution is : [2008]
pump : [2015]
(a) Mg2+ (b) K+ (a) K+ > Na+ > Rb+ > Cs+
(c) Fe2+ (d) Ca2+ (b) Cs+ > Rb+ > K+ > Na+
The s-Block Elements 99
(c) Rb+ > K+ > Cs+ > Na+ Topic 2: Some Important Compounds of Sodium
(d) Na+ > K+ > Rb+ > Cs+
16. HCl was passed through a solution of CaCl2,
8. The alkali metals form salt-like hydrides by the MgCl 2 and NaCl. Which of the following
direct synthesis at elevated temperature. The compound(s) crystallise(s)? [2020]
thermal stability of these hydrides decreases in
(a) Only NaCl
which of the following orders ? [2008]
(b) Only MgCl2
(a) CsH > RbH > KH > NaH > LiH
(b) KH > NaH > LiH > CsH > RbH (c) NaCl, MgCl2 and CaCl2
(c) NaH > LiH > KH > RbH > CsH (d) Both MgCl2 and CaCl2
(d) LiH > NaH > KH > RbH > CsH 17. Crude sodium chloride obtain ed by
9. The correct order of the mobility of the alkali metal crystallisation of brine solution does not contain
ions in aqueous solutions is [2006]
(a) Na+ > K+ > Rb+ > Li+ [NEET Odisha 2019]
(b) K+ > Rb+ > Na+ > Li+ (a) CaSO4 (b) MgSO4
(c) Rb+ >K+ > Na+ > Li+
(d) Li+ > Na+ > K+ > Rb+ (c) Na2SO4 (d) MgCl2
10. In crystals of which one of the following ionic 18. In Castner-Kellner cell for production of sodium
compounds would you expect maximum distance hydroxide: [NEET Kar. 2013]
between centres of cations and anions? [1998] (a) Brine is electrolyzed with Pt electrodes
(a) LiF (b) CsF (b) Brine is electrolyzed using graphite
(c) CsI (d) LiI electrodes
11. Which of the following metal ions plays an
important role in muscle contraction ? [1994] (c) Molten sodium chloride is electrolysed
(a) K+ (b) Na+ (d) Sodium amalgam is formed at mercury
(c) Mg2+ (d) Ca2+ cathode
12. Which of the following statement is false ? [1994] 19. Which of the following statements is incorrect?
(a) Strontium decomposes water readily than [2011M]
beryllium
(b) Barium carbonate melts at a higher (a) Pure sodium metal dissolves in liquid
temperature than calcium carbonate ammonia to give blue solution.
(c) Barium hydroxide is more soluble in water (b) NaOH reacts with glass to give sodium silicate
than magnesium hydroxide (c) Aluminium reacts with excess NaOH to give
(d) Beryllium hydroxide is more basic than Al(OH)3
barium hydroxide.
(d) NaHCO3 on heating gives Na2CO3
13. Which of the following has largest size ?[1993]
(a) Na (b) Na+ 20. Which of the following oxides is not expected to
(c) Na – (d) Can’t be predicted react with sodium hydroxide? [2009]
14. Compared with the alkaline earth metals, the alkali (a) CaO (b) SiO2
metals exhibit [1990] (c) BeO (d) B2O3
(a) Smaller ionic radii
(b) Highest boiling points 21. In which of the following processes, fused
(c) Greater hardness sodium hydroxide is electrolysed at a 330ºC
(d) Lower ionization energies. temperature for extraction of sodium? [2000]
15. Which one of the following properties of alkali (a) Castner's process (b) Down's process
metals increases in magnitude as the atomic (c) Cyanide process (d) Both 'b' and 'c'
number rises ? [1989] 22. Aqueous solution of sodium carbonate absorbs
(a) Ionic radius NO and NO2 to give [1996]
(b) Melting point
(a) CO2 + NaNO3 (b) CO2 + NaNO2
(c) Electronegativity
(d) First ionization energy. (c) NaNO2 + CO (d) NaNO3 + CO
EBD_8336
100 CHEMISTRY
23. Which of the following is known as fusion 32. Which of the following alkaline earth metal
mixture? [1994] sulphates has hydration enthalpy higher than
(a) Mixture of Na2CO3 + NaHCO3 the lattice enthalpy? [2010]
(b) Na2CO3.10H2O (a) CaSO 4 (b) BeSO 4
(c) Mixture of K2CO3 + Na2CO3 (c) BaSO 4 (d) SrSO 4
(d) NaHCO3 33. Property of the alkaline earth metals that increases
24. Washing soda has formula [1990] with their atomic number [2010]
(a) Na2CO3.7H2O (b) Na2CO3.10H2O (a) Solubility of their hydroxides in water
(c) Na2CO3.3H2O (d) Na2CO3 (b) Solubility of their sulphates in water
Topic 3: Preparation and Properties of Alkaline (c) Ionization energy
Earth Metals and their Compounds (d) Electronegativity
25. Which of the following is an amphoteric 34. The correct order of increasing thermal stability
hydroxide ? [2019] of K2CO3, MgCO3, CaCO3 and BeCO3 is [2007]
(a) Sr(OH)2 (b) Ca(OH)2 (a) BeCO3< MgCO3 < CaCO3 < K2CO3
(c) Mg(OH)2 (d) Be(OH)2 (b) MgCO3 < BeCO3 < CaCO3 < K2CO3
26. Enzymes that utilize ATP in phosphate transfer (c) K2CO3 < MgCO3 < CaCO3 < BeCO3
require an alkaline earth metal (M) as the cofactor.
M is: [2019] (d) BeCO3 < MgCO3 < K2CO3 < CaCO3
(a) Be (b) Mg 35. In which of the following the hydration energy is
(c) Ca (d) Sr higher than the lattice energy? [2007]
27. Which of the following oxides is most acidic in (a) MgSO4 (b) RaSO4
nature? [2018] (c) SrSO4 (d) BaSO4
(a) MgO (b) BeO 36. Calcium is obtained by the [1997]
(c) CaO (d) BaO (a) electrolysis of solution of calcium chloride
28. Among CaH2, BeH2, BaH2, the order of ionic in water
character is [2018]
(b) electrolysis of molten anhydrous calcium
(a) BeH2 < CaH2 < BaH2
chloride or fused calcium chloride
(b) CaH2 < BeH2 < BaH2
(c) roasting of limestone
(d) BaH2 < BeH2 < CaH2 (d) reduction of calcium chloride with carbon
(d) BeH2 < BaH2 < CaH2 37. For two ionic solids CaO and KI, identify the
29. Which of the following statements is false ? wrong statement amongst the following : [1997]
[2016] (a) The lattice energy of CaO is much large
(a) Mg2+ ions form a complex with ATP than that of KI
(b) Ca2+ ions are important in blood clotting (b) KI is more soluble in water
(c) Ca2+ ions are not important in maintaining (c) KI has higher melting point
the regular beating of the heart.
(d) CaO has higher melting point
(d) Mg2+ ions are important in the green parts
of plants. 38. Which one is the correct statement with reference
30. Solubility of the alkaline earth's metal sulphates to solubility of MgSO4 in water? [1996]
in water decreases in the sequence :- [2015] (a) SO 4 2– ion mainly contributes towards
(a) Ca > Sr > Ba > Mg (b) Sr > Ca > Mg > Ba hydration energy
(c) Ba > Mg > Sr > Ca (d) Mg > Ca > Sr > Ba (b) Sizes of Mg2+ and SO42– are similar
31. Which of the following compounds has the (c) Hydration energy of MgSO4 is higher in
lowest melting point ? [2011] comparison to its lattice energy
(a) CaCl2 (b) CaBr2 (d) Ionic potential (charge/radius ratio) of Mg2+
(c) CaI2 (d) CaF2 is very low
39. Sodium is made by the electrolysis of a molten List - I List - II

mixture of about 40% NaCl and 60% CaCl2 Substances Composition
because [1995] (1) Plaster of paris (i) CaSO4.2H2O
(a) Ca2+ can reduce NaCl to Na (2) Epsomite (ii) CaSO4.½ H2O
(b) Ca2+ can displace Na from NaCl (3) Kieserite (iii) MaSO4.7 H2O
(c) CaCl2 helps in conduction of electricity (4) Gypsum (iv) MgSO4. H2O
(d) this mixture has a lower melting point than NaCl (v) CaSO4
40. All the following substances react with water. Code :
The pair that gives the same gaseous product is (1) (2) (3) (4)
(a) (iii) (iv) (i) (ii)
[1994]
(b) (ii) (iii) (iv) (i)
(a) K and KO2 (b) Na and Na2O2
(c) (i) (ii) (iii) (v)
(c) Ca and CaH2 (d) Ba and BaO2 (d) (iv) (iii) (ii) (i)
41. Which one of the following has minimum value 47. The compound A on heating gives a colourless
of cation/anion ratio. [1993] gas and a residue that is dissolved in water to
(a) NaCl (b) KCl obtain B. Excess of CO2 is bubbled through
(c) MgCl2 (d) CaF2 aqueous solution of B, C is formed which is
42. Electronic configuration of calcium atom can be recovered in the solid form. Solid C on gentle
written as [1992] heating gives back A. The compound is [2010]
(a) [Ne], 4p 2 (b) [Ar], 4s 2 (a) CaSO4.2H2O (b) CaCO3
(c) [Ne], 4s2 (d) [Kr], 4p2 (c) Na2CO3 (d) K2CO3
43. Which of the following atoms will have the 48. A solid compound ‘X’ on heating gives CO2 gas
smallest size ? [1989] and a residue. The residue mixed with water forms
(a) Mg (b) Na ‘Y’. On passing an excess of CO2 through ‘Y’ in
(c) Be (d) Li water, a clear solution ‘Z’, is obtained. On boiling
Topic 4: Some Important Compounds of Calcium ‘Z’, a compound ‘X’ is reformed. The compound
‘X’ is [2004]
44. On heating which of the following releases CO2
(a) Ca(HCO3)2 (b) CaCO3
most easily ? [2015 RS]
(c) Na2CO3 (d) K2CO3
(a) K2CO3 (b) Na2CO3
49. Identify the correct statement [1995]
(c) MgCO3 (d) CaCO3 (a) gypsum is obtained by heating plaster of
45. Which one of the following is present as an active Paris
ingredient in bleaching powder for bleaching (b) plaster of Paris can be obtained by hydration
action ? [2011] of gypsum
(a) CaOCl2 (b) Ca(OCl)2 (c) plaster of paris is obtained by partial
(c) CaO2Cl (d) CaCl2 oxidation of gypsum
46. Match List – I with List –II for the compositions (d) gypsum contains a lower percentage of
of substances and select the correct answer using calcium than plaster of Paris
the code given below the lists : [2011M]
ANSWER KEY
1 (c) 6 (c) 11 (d) 16 (a) 21 (a) 26 (b) 31 (c) 36 (b) 41 (c) 46 (b)
2 (b) 7 (b) 12 (d) 17 (b) 22 (b) 27 (b) 32 (b) 37 (c) 42 (b) 47 (b)
3 (b) 8 (d) 13 (c) 18 (d) 23 (c) 28 (a) 33 (a) 38 (c) 43 (c) 48 (b)
4 (c) 9 (c) 14 (d) 19 (c) 24 (b) 29 (c) 34 (a) 39 (d) 44 (c) 49 (d)
5 (b) 10 (c) 15 (a) 20 (a) 25 (d) 30 (d) 35 (a) 40 (c) 45 (b)
EBD_8336
102 CHEMISTRY
Hints & Solutions

1. (c) Potassium (K) activates many enzymes to order Cs+ < Rb+ < K+ < Na+. However due to
participate in oxidation of glucose to produce high degree of solvation (or hydration) and
ATP and helps in the transmission of nerve because of lower size or high charge density,
signal along with Na. the hydrated ion size follows the same order
2. (b) Only LiCl forms a dihydrate, other metal Cs+ < Rb+ < K+ < Na+ and thus conductivity
order is Cs+ > Rb+ > K+ > Na+.
chlorides do not form hydrates.
8. (d) The stability of alkali metal hydrides
3. (b) In sodium pump, high concentration of
potassium ions and a low concentration of decreases from Li to Cs. It is due to the fact that
sodium ions are maintained within a cell by a M–H bonds becomes weaker with increase in
plasma membrane protein. size of alkali metals as we move down the group
4. (c) All the alkali metals when heated with from Li to Cs. Thus the order of stability of
oxygen form different types of oxides for example hydrides is
lithium forms lithium oxide (Li2O), sodium forms LiH > NaH > KH > RbH > CsH
sodium peroxide (Na2O2), while K, Rb and Cs
9. (c) Hydrated Ionic radii of alkali metals in water
form their respective superoxides.
follows the order Li+ > Na+ > K+ > Rb+ > Cs+
Li+ being smallest, combines with small anion Thus in aqueous solution due to larger ionic
O2– to form stable Li2O. radius Li+ has lowest mobility and hence the
The Na+ being relatively larger than Li+ and weaker correct order of ionic mobility is
positive field than Li+ , combines with O 22 -
(peroxide ion) to form Na2, O2. K+, Rb+ and Cs+ Li + < Na + < K + < Rb +
being relative larger than Na+ and with weaker 10. (c) As Cs+ ion has larger size than Li+ and I–
positive field than Na + combines with O2- has larger size than F–, therefore maximum
(superoxide ion) to for KO 2, RbO 2 and CsO 2 distance between centres of cations and anions
respectively. is in CsI.
5. (b) All alkali metal salts are ionic (except 11. (d) Ca2+ ions is an essential element for the
contraction of muscles.
Lithium) and soluble in water due to the fact
12. (d) Be(OH)2 is amphoteric, but the hydroxides
that cations get hydrated by water molecules.
of other alkaline earth metals are basic. The basic
The degree of hydration depends upon the size strength increases gradually.
of the cation. Smaller the size of a cation, greater is its 13. (c) A cation is always much smaller than the
hydration energy. corresponding atom, whereas an anion is always
Relative ionic radii : larger than the corresponding atom, hence the
Cs + > Rb + > K + > Na + > Li + size decreases in the order
Relative ionic radii in water or relative degree of Na - > Na > Na +
hydration: 14. (d) Because of larger size and smaller nuclear
Li + > Na + > K + > Rb + > Cs + charge, alkali metals have low ionization
potential relative to alkaline earth metals.
6. (c) Tertiary halide can show ionic reaction with
MF so, MF should be most ionic for reaction to 15. (a) Within a group, ionic radius increases with
proceed forward. Hence ‘M’ should be ‘Rb’. increase in atomic number. The melting point
decrease down the group due to weakening of
7. (b) Smaller the ion more is its ionic mobility in
metallic bond. The electronegativity and the 1st
aqueous solution. Ionic radii of the given alkali
ionization energy also decreases down the
metals is in the order Na+ < K+ < Rb+ < Cs+ and
group.
thus expected ionic mobility will be in the same
16. (a) When HCl is passed through the solution 28. (a) BeH2 < CaH2 < BaH2
Cl– ion concentration increases. Hence ionic Smaller the size of cation, more will be its
product becomes more than solubility product. polarising power. Hence, BeH2 will be least
Only NaCl is crystallised due to less solubility ionic.
than MgCl2 and CaCl2.
29. (c) Calcium regulates muscle contraction,
17. (b) Crude sodium chloride which is obtained including beating of heart muscle, so that it can
by crystallisation of brine solution contains contract and pump out blood to all our body.
Na2SO4, CaSO4, CaCl2 and MgCl2 are present
30. (d) Solubility of alkaline earth metal sulphates
as impurities in crude.
decreases down the group due to decrease in
18. (d) In castner kellner cell, sodium amalgam is hydration energy.
formed at mercury cathode.
MgSO 4 > CaSO4 > SrSO 4 > BaSO 4
Sodium is discharged from brine at a mercury
Hydration Solubility
cathode in preference to hydrogen because of the energy
high hydrogen overpotential at mercury surface.
This is the reason of using mercury cathode instead 31. (c) Melting point of metal halides decreases
of graphite or platinum in castner-kellner cell. as the size of the halogen increases. The correct
order is
19. (c) 2Al(s) + 2NaOH (aq) + 2H2O (l) ¾¾
® CaF2 > CaCl2 > CaBr2 > CaI2
2NaAlO2 + 3H2
sod. meta aluminate 32. (b) Be 2+ is very small, hence its hydration
20. (a) NaOH is a strong alkali. It combines with enthalpy is greater than its lattice enthalpy. Also,
acidic and amphoteric oxides to form salts. Since hydration energy decreases down the group.
CaO is a basic oxide hence does not react with 33. (a) The magnitude of hydration energy for the
NaOH. hydroxides of alkaline earth metals remains
21. (a) In Castner process, for production of (Na) almost same whereas lattice energy decreases
sodium metal, sodium hydroxide (NaOH) is appreciably down the group. Hence, solubility
electrolysed at 330ºC. increases down the group.
22. (b) Na 2 CO3 + NO + NO 2 ® 2 NaNO2 + CO2 34. (a) As the cation size increases down the
23. (c) Mixture of K2CO3 and Na2CO3 is called as group, the metal carbonates become more ionic
fusion mixture. in nature. Hence, the thermal stability increases
24. (b) Washing soda is Na2CO3. 10H2O. as: BeCO3 < MgCO3 < CaCO3.
25. (d) Amphoteric hydroxide means it can react The ionic character of group 1 carbonates is
with both acid and base. more than that of group 2, thus they possess
more thermal stability. Hence, the correct order
Be ( OH ) 2 + 2HCl ¾¾
® BeCl2 + 2H 2O
of thermal stability : BeCO3 < MgCO3 < CuCO3
Be ( OH ) 2 + 2NaOH ¾¾
® Na 2 éë Be ( OH ) 4 ùû < K2CO3.
26. (b) Enzyme that utilise ATP in phosphate 35. (a) The solubility and the hydration energy of
transfer require an alkaline earth metal (M) sulphates of alkaline earth metals decreases as
Mg as the cofactor. we move down the group from Be to Ba due to
27. (b) In metals, moving down the group, metallic the reason that ionic size increases down the
character increases, so basic nature group. The lattice energy remains constant
increases hence most acidic will be BeO. because sulphate ion is so large, so that small
BeO < MgO < CaO < BaO change in cationic sizes do not make any
¾¾¾¾¾¾¾¾¾¾
® difference. Thus the order will be:
increasingbasic character
BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4
EBD_8336
104 CHEMISTRY
36. (b) Calcium is obtained by electrolysis of a 44. (c) Carbonates becomes more thermally stable
fused mass consisting six parts calcium chloride down the group, therefore MgCO3 will leave
and one part calcium fluoride at about 700°C in CO2 easily.
an electrolytic cell. 45. (b) Active ingredient in bleaching powder for
37. (c) CaO has higher lattice energy because bleaching action is Ca (OCl)2.
of higher charge on Ca 2+ and O2– , which
Bleaching powder is a mixture of calcium
results in higher attraction. KI is more soluble
hypochlorite Ca (OCl) 2 , dibasic calcium
in water because of low lattice energy and
hypochlorite Ca (OCl)2. 2 Ca (OH)2 and dibasic
higher hydration energy. Clearly (c) is wrong
calcium chloride CaCl2 . 2Ca(OH)2.
because CaO has higher melting point as
compared to KI. 1
46. (b) (A) Plaster of paris = CaSO4. H2O
38. (c) MgSO4 is the only alkaline earth metal 2
sulphate which is soluble in water and for (B) Epsomite = MgSO4.7H2O
solubility hydration energy should be greater (C) Kieserite = MgSO4.H2O
than lattice energy. (D) Gypsum = CaSO4.2H2O
39. (d) Sodium is obtained by electrolytic
reduction of its chloride. Melting point of Plaster of paris can be more accurately written as
(CaSO4)2 . H2O
chloride of sodium is high (803°C) so in order
D
to lower its melting point(600°C), calcium 47. (b) CaCO3 (s) ¾¾® CO2 (g) + CaO(s)
chloride is added to it. (A) colourless residue
40. (c) Ca and CaH2 both react with water to form
H2 gas, ® Ca (OH )2
CaO(s) + H 2 O ¾ ¾
(B)
Ca + 2 H 2 O ¾
¾® Ca ( OH ) 2 + H 2
Ca (OH )2 + 2CO2 + H2O ¾ ¾ ® Ca (HCO3 )2
CaH 2 + 2H 2 O ¾¾® Ca (OH ) 2 + 2 H 2 (C)
whereas Ñ
Ca (HCO3 )2(s) ¾¾
® CaCO3(s) + CO2(g) + H2 O
K gives H2 while KO2 gives O2 and H2O2 (A)
(C)
2K + 2 H2O ¾
¾® 2KOH + H2
48. (b) heat
X CO2 + Residue
2KO2 + 2H 2 O ¾¾
® 2KOH + O2 + H 2 O2 Solid
H2 O
2KO 2 + 2H 2 O ¾¾ ® 2KOH + O 2 + H 2 O 2 boil
¬¾ ¾ ¾¾2¾ Y
excess CO
Similarly, Na gives H2 while Na2O2 gives H2O2 Z
Clear solution
2Na + 2H 2O ¾¾ ® 2NaOH + H 2
The given properties coincide with CaCO3
Na 2 O 2 + 2H 2 O ¾
¾® 2 NaOH + H 2 O 2
Also, Ba gives H2 while BaO2 gives H2O2 heat
CaCO3 ¾ ¾ ¾® CO 2 + CaO
Ba + 2 H2O ¾ ¾® Ba (OH)2 + H2
heat ' X '
Residue
BaO2 + 2H2O ¾ ¾® Ba (OH)2 + H2 O2
H 2O
41. (c) Atomic size of K+ > Ca2+ > Mg2+ and that
of Cl– > F–. Therefore, Mg2+/Cl– ratio has the excess
Ca(HCO3 )2 ¬¾ ¾¾ Ca(OH)2
minimum value. 'Z ' CO2
'Y '
42. (b) 20Ca = 1s22s22p63s23p64s2 = [Ar] 4s2
43. (c) Within a period, the atomic size decreases 49. (d) Gypsum is CaSO4. 2H2O and plaster of
from left to right.Further atomic size increases Paris is (CaSO 4 ) 2 .H 2O. Therefore, gypsum
down the group. Hence the correct order is contains a lower percentage of calcium than
i.e. Na > Mg > Li > Be. plaster of Paris.
The p-Block Elements (Group 13 & 14) 105
11 The p-Block Elements

(Group 13 & 14)
2020 2019 2018 2017 2016

multiple concept
1 A
(structure,formulae)
Boron family physical/chemical
properties of 1 E
elements of gp 13
oxides of carbon 1 A
multiple concept
(zeolites, allotropes, 1 A
Carbon family oxides of carbon)
inert pair effect 1 A
properties of halides
2 A
of gp 14
Topic 1: Boron Family 2. Aluminium chloride in acidified aqueous

solution forms a complex ‘A’, in which
1. Match the following and identify the correct hybridisation state of Al is ‘B’. What are ‘A’ and
option. [2020] ‘B’, respectively? [NEET Odisha 2019]
(A) CO(g) + H2(g) (i) Mg(HCO3)2 + (a) [Al(H2O)6]3+, d2sp3
Ca(HCO3)2
(b) [Al(H2O)6]3+, sp3d 2
(B) Temporary (ii) An electron
(c) [Al(H2O)4]3+, sp3
hardness of deficient
water hydride (d) [Al(H2O)4]3+, dsp2
(C) B2H6 (iii) Synthesis gas 3. Which one of the following elements is unable
(D) H2O2 (iv) Non-planar to form ion? [2018]
structure (a) Ga (b) Al
(A) (B) (C) (D) (c) In (d) B
(a) (iii) (ii) (i) (iv) 4. The stability of +1 oxidation state among Al, Ga,
(b) (iii) (iv) (ii) (i) In and Tl increases in the sequence :[2015 RS]
(c) (i) (iii) (ii) (iv) (a) Ga < In < Al < Tl (b) Al < Ga < In < Tl
(d) (iii) (i) (ii) (iv) (c) Tl < In < Ga < Al (d) In < Tl < Ga < Al
EBD_8336
106 CHEMISTRY
5. Which of the following structure is similar to Topic 2: Carbon Family

graphite? [NEET 2013] 13. Which of the following is not correct about
(a) B (b) B4C carbon monoxide ? [2020]
(c) B2H6 (d) BN
(a) It reduces oxygen carrying ability of blood.
6. Aluminium is extracted from alumina (Al2O3 )
by electrolysis of a molten mixture of : [2012] (b) The carboxyhaemoglobin (haemoglobin
(a) Al2O3 + HF + NaAlF4 bound to CO) is less stable than
oxyhaemoglobin.
(b) Al2O3 + CaF2 + NaAlF4
(c) It is produced due to incomplete
(c) Al2O3 + Na3AlF6 + CaF2
combustion.
(d) Al2O3 + KF + Na3AlF6
(d) It forms carboxyhaemoglobin
7. The tendency of BF3, BCl3 and BBr3 to behave
as Lewis acid decreases in the sequence: [2010] 14. Identify the correct statements from the
(a) BCl3 > BF3 > BBr3 following : [2020]
(b) BBr3 > BCl3 > BF3 (A) CO2(g) is used as refrigerant for ice-cream
and frozen food.
(c) BBr3 > BF3 > BCl3
(B) The structure of C60 contains twelve six
(d) BF3 > BCl3 > BBr3 carbon rings and twenty five carbon rings.
8. Al2O3 can be converted to anhydrous AlCl3 by (C) ZSM-5, a type of zeolite, is used to convert
heating [2006] alcohols into gasoline.
(a) Al2O3 with NaCl in solid state (D) CO is colorless and odourless gas.
(b) a mixture of Al2O3 and carbon in dry Cl2 gas (a) (A) and (C) only
(c) Al2O3 with Cl2 gas (b) (B) and (C) only
(d) Al2O3 with HCl gas (c) (C) and (D) only
9. In borax bead test which compound is formed? (d) (A), (B) and (C) only
[2002] 15. Which of the following compounds is used in
(a) Ortho-borate (b) Meta-borate cosmetic surgery? [NEET Odisha 2019]
(c) Double oxide (d) Tetra-borate (a) Zeolites (b) Silica
10. Which of the following statements about H3BO3 (c) Silicates (d) Silicones
is not correct ? [1994] 16. Which of the following is incorrect statement?
(a) It is a strong tribasic acid (a) PbF4 is covalent in nature [2019]
(b) It is prepared by acidifying an aqueous (b) SiCl4 is easily hydrolysed
solution of borax (c) GeX4 (X = F, Cl, Br, I) is more stable than GeX2
(c) It has a layer structure in which planar BO3 (d) SnF4 is ionic in nature
units are joined by hydrogen bonds 17. Which of the following species is not stable ?
(d) It does not act as proton donor but acts as [2019]
a Lewis acid by accepting a lone pair of (a) [SiF6]2– (b) [GeCl6]2–
electrons (c) [Sn(OH)6]2– (d) [SiCl6]2–
11. Which of the following elements is extracted 18. It is because of inability of ns2 electrons of the
commercially by the electrolysis of an aqueous valence shell to participate in bonding that:-
solution of its compound ? [1993] [2017]
(a) Cl (b) Br 2+ 4+
(a) Sn is oxidising while Pb is reducing
(c) Al (d) Na (b) Sn 2+ and Pb2+ are both oxidising and
12. An example of a double salt is [1989] reducing
(a) Bleaching powder (b) K4[Fe(CN)6] (c) Sn4+ is reducing while Pb4+ is oxidising
(c) Hypo (d) Potash Alum (d) Sn2+ is reducing while Pb4+ is oxidising
19. Which of these is not a monomer for a high (c) Zeolites are aluminosilicates having three
molecular mass silicone polymer?[NEET 2013] dimensional network
(a) Me2SiCl2 (b) Me3SiCl (d) Some of the SiO44- units are replaced by
(c) PhSiCl3 (d) MeSiCl3 AlO 54- and AlO 96- ions in zeolites
20. The basic structural unit of silicates is : 25. Glass reacts with HF to produce [2000]
[NEET 2013] (a) SiF4 (b) H2SiF6
(a) SiO4 4– (b) SiO32– (c) H2SiO3 (d) Na3AlF6
(c) SiO4 2– (d) SiO 26. In graphite, electrons are [1993, 1994]
21. Which statement is wrong? [NEET Kar. 2013] (a) Localised on every third C-atom
(a) Feldspars are not aluminosilicates (b) Present in anti-bonding orbital
(b) Beryl is an example of cyclic silicate (c) Localised on each C-atom
(c) Mg2SiO4 is orthosilicate (d) Spread out between the structure
(d) Basic structural unit in silicates is the SiO4
27. Which of the following types of forces bind
tetrahedron
together the carbon atoms in diamond ?[1992]
22. Name the type of the structure of silicate in which
one oxygen atom of [SiO4]4– is shared ?[2011] (a) Ionic (b) Covalent
(a) Linear chain silicate (c) Dipolar (d) van der Waals.
(b) Sheet silicate 28. Water gas is produced by [1992]
(c) Pyrosilicate (a) Passing steam through a red hot coke bed
(d) Three dimensional (b) Saturating hydrogen with moisture
23. The straight chain polymer is formed by [2009] (c) Mixing oxygen and hydrogen in the ratio
(a) hydrolysis of CH3 SiCl 3 followed by of 1 : 2
condensation polymerisation (d) Heating a mixture of CO2 and CH4 in
(b) hydrolysis of (CH 3 ) 4 Si by addition petroleum refineries.
polymerisation 29. Glass is a [1991]
(c) hydrolysis of (CH3)2SiCl 2 followed by (a) Liquid
condensation polymerisation (b) Solid
(d) hydrolysis of (CH3 )3 SiCl followed by (c) Supercooled liquid
condensation polymerisation (d) Transparent organic polymer
24. Which one of the following statements about 30. The substance used as a smoke screen in
the zeolites is false ? [2004] warfare is [1989]
(a) They are used as cation exchangers (a) SiCl4 (b) PH3
(b) They have open structure which enables (c) PCl5 (d) Acetylene
them to take up small molecules
ANSWER KEY
1 (d) 4 (b) 7 (b) 10 (a) 13 (b) 16 (a) 19 (b) 22 (c) 25 (b) 28 (a)
2 (b) 5 (d) 8 (b) 11 (a) 14 (c) 17 (d) 20 (a) 23 (c) 26 (d) 29 (c)
3 (d) 6 (c) 9 (b) 12 (d) 15 (d) 18 (d) 21 (a) 24 (c) 27 (b) 30 (a)
EBD_8336
108 CHEMISTRY
Hints & Solutions

1. (d) D
9. (b) Na2B4O7. 10 H2O ¾¾¾¾
-10H O
®
A. Mixture of CO and H2 gases is known as 2
water gas or synthesis gas.
B. Temporary hardness of water is due to D
Na 2 B4O7 ¾¾
® 2 NaBO2 + B2 O3
bicarbonates of calcium and magnesium. anhydrous sod.metaborate Boric anhydride
C. Diborane (B2H6) is an electron deficient
hydride. CuO + B2 O3 ¾¾
® Cu(BO 2 )2
cupric meta borate(Blue beed)
D. H2O2 is non-planar molecule having open
10. (a) H3BO3 is a weak monobasic acid.
book like structure.
Acidified aq. sol.
11. (a) On a commercial scale, chlorine is prepared
2. (b) AlCl3 ¾¾¾¾¾¾ ® [Al (H2O)6]3+ by electrolysis of an aqueous solution of sodium
sp 3 d 2 chloride (brine solution). Cl2 is evolved at the
3. (d) MF63– anode.
Boron belongs to 2nd period and it does not (b) Br2 is prepared by passing Cl2 gas through
have vacant d-orbital. sea water containing NaBr, kBr etc.
4. (b) Lower oxidation state become more stable (c) Al is extracted by electrolysis of fused
on moving down the group mixture of alumina, cryolite and fluorspar.
Al < Ga < ln < Tl Products of electrolysis depend on the
concentration of electrolyte, overvoltage factor and
5. (d) Boron nitride (BN) is known as inorganic the electrodes used. Also, the commercial viability
graphite. The most stable form is hexagonal one. is an important factor.
It has layered structure similar to graphite. 12. (d) Potash Alum, K2SO4. Al2(SO4). 24H2O is a
6. (c) Fused alumina (Al2O3) is a bad conductor double salt.
of electricity. Therefore, cryolite (Na 3AlF6) and 13. (b) The carboxyhaemoglobin (haemoglobin
fluorspar (CaF2) are added to purified alumina bound to CO), is about 300 times more stable
which not only make alumina a good conductor than oxygaemoglobin.
of electricity but also reduce the melting point 14. (c)
of the mixture to around 1140 K. A. Dry ice, CO2(s), is used as refrigerant
7. (b) In BF3, p-p overlap between B and F is B. C60 contains 20 six membered rings, 12 five
maximum due to identical size and energy of membered rings
p-orbitals, so electron deficiency in boron of BF3
is neutralized partially to the maximum extent by Zeolites are crystalline, 3D aluminosilicates. ZSM-
back donation. Also, the tendency to back 5 contain two sets of perpendicular, intersecting
donate decreases from F to I. So the order will be: channel, one is 10 membered another is 8
BF3 < BCl3 < BBr3. membered.
8. (b) Al2O3 can be converted to anhydrous AlCl3 15. (d) Silicones are used in cosmetic surgery.
by heating a mixture of Al2O3 and carbon in dry 16. (a) PbF 4 is ionic in nature due to high
Cl2 gas. electronegativity difference.
1000°C
Al2O3 + 3C + 3Cl2 2AlCl3 + 3CO 17. (d) [SiCl6]2– does not exist because six large
vapours
Solid anhydrous chloride ions cannot be accommodated around
cooled
aluminium
chloride Si4+, due to its small size.
18. (d) Due to inert pair effect, Pb(II) is more stable CH3 CH3
than Pb(IV)
Sn(IV) is more stable than Sn(II) HO — Si — OH + H O —Si — OH ¾ ®
\ Pb(IV) is easily reduced to Pb(II) and can
CH3 CH3
acts as an oxidising agent whereas Sn(II) is easily
oxidised to Sn(IV) and can acts as a reducing CH3 CH3
agent.
HO — Si — O — Si — OH
Inertness of ns2 electrons of the valence shell to
participate in bonding on moving down the group CH3 CH3
in heavier p-block elements is called inert pair effect.
It occurs due to poor shielding of the ns2 electrons 24. (c) Zeolites are crystaline solid structures
of the valence shell by the intervening d and f made up of silicon, aluminium and oxygen making
electrons. a framework with cavities.
19. (b) Since Me3SiCl contains only one Cl, Zeolites have SiO4– 5–
4 and AlO4 tetrahedrons linked
therefore it can’t form high molecular mass together in a 3-D open structure in which 4 or 6
silicon polymer. It can form only dimer. membered rings predominate. Due to open
structure they have cavities and can take up water
20. (a) SiO44– is basic structural unit of silicates.
and other small molecules.
21. (a) Feldspars are 3-dimensional alumino-
silicates. 25. (b) 6 HF + SiO 2 ® H 2SiF6 + 2 H 2 O
26. (d) In graphite, each carbon is sp2 -hybridized
22. (c) O– O– and the single occupied unh ybridized
p-orbital of C-atoms overlap side ways to give
p -electron cloud which is delocalized and thus
Si Si
– the electrons are spread out between the
O O O– structure.
O
– O– 27. (b) In diamond, each carbon atom is sp 3
hybridized and thus, forms covalent bonds with
Pyrosilicate (Si 2 O 7 ) 6–
four other carbon atoms lying at the corners of a
23. (c) Hydrolysis of substituted chlorosilanes regular tetrahedron.
yield corresponding silanols which undergo 28. (a) Water gas is made by blowing steam
polymerisation. through the layer of incandescent coal.
Cl H OH – 2HCl H 2O + C ¾¾
® H 2 + CO
CH3 Steam Red hot water gas
Si + ¾¾®
CH3 Cl H OH 29. (c) Glass is a super cooled liquid.
CH3 OH Supercooling is the process of lowering the

Si temperature of a liquid or gas below its freezing
CH3 OH point without becoming a solid.
Dimethylsilanol
30. (a) SiCl4 gets hydrolysed in moist air and gives
Polymerisation of dimethylsilanol yields linear white fumes which are used as a smoke screen
thermoplastic polymer. in warfare.
EBD_8336
110 CHEMISTRY
12 Organic Chemistry -
Some Basic Principles
and Techniques
2020 2019 2018 2017 2016

Classification and
IUPAC
nomenclature of 1 E
nomenclature
organic compounds
stability of
carbocation/ 1 A 1 D 1 A
carbanion
Concept of reaction chromatography/
1 E 1 A
mechnism in organic distillation
compounds electrophillic
substitution 1 A 1 A
reactions
inductive effect 1 A
Topic 1: Classification and Nomenclature of OH

Organic Compounds COOH
(b)
1. The IUPAC name of the compound is : [2017]
O O
H–C COOH
(c)
OH
(a) 5-formylhex-2-en-3-one OH
(b) 5-methyl-4-oxohex-2-en-5-al
(c) 3-keto-2-methylhex-5-enal COOH
(d)
(d) 3-keto-2-methylhex-4-enal
2. Structure of the compound whose IUPAC name
is 3-ethyl-2-hydroxy-4-methylhex-3-en-5-ynoic 3. The structure of isobutyl group in an organic
acid is : [NEET 2013] compound is : [NEET 2013]
OH
(a) CH3 - CH - CH 2 - CH3
½
COOH
(a) (b) CH3 - CH 2 - CH2 - CH 2 -
Organic Chemistry - Some Basic Principles and Techniques 111
CH3 7. The state of hybridization of C2, C3, C5 and C6

| of the hydrocarbon, [2009]
(c) CH3 - C- CH3
| CH3
CH3 | |
CH3 C CH = CH CH C º CH
7 6| 5 4 3 2 1
CH 3
CH3
(d) CH - CH 2 -
CH 3 is in the following sequence:
(a) sp3, sp2, sp2 and sp
4. Which nomenclature is not according to IUPAC (b) sp, sp2, sp2 and sp3
system? [2012]
(c) sp, sp2, sp3 and sp2
(a) Br — CH2 — CH == CH2, (d) sp, sp3, sp2 and sp3
1-Bromo-prop-2-ene 8. In the hydrocarbon
CH3 CH3 – CH = CH – CH2 – C º CH
(b) CH3 6 5 4 3 2 1
CH2 C CH2 CHCH3
The state of hybrization of carbons 1, 3 and 5
CH3 are in the following sequence : [2008]
Br
(a) sp2, sp, sp3 (b) sp, sp3, sp2
4-Bromo-2, 4-dimethylhexane
(c) sp, sp2, sp3 (d) sp3, sp2, sp
(c) CH3 CH CH CH2 CH3, 9. The general molecular formula, which represents
the homologous series of alkanols is [2006]
CH3 (a) CnH2nO (b) CnH2n + 1O
2-Methyl-3-phenylpentane (c) CnH2n + 2O (d) CnH2n O2
(d) CH3 C CH2 CH2 CH2 COOH
Cl
O 10. The IUPAC name of is
5-oxohexanoic acid O
5. The correct IUPAC name of the compound [2006]
[2011] (a) 1- chloro -1-oxo - 2, 3- dimethyl pentane
(b) 2-ethyl -3- methylbutanoyl chloride
(c) 2, 3-dimethylpentanoyl chloride
is (d) 3, 4-dimethyl pentanoyl chloride
11. The correct order regarding the electronegativity
(a) 4-Ethyl-3-propyl hex-1-ene of hybrid orbitals of carbon is [2006]
(b) 3-Ethyl-4-ethenyl heptane (a) sp > sp2 > sp3 (b) sp < sp2 > sp3
(c) 3-Ethyl-4-propyl hex-1-ene (c) sp < sp2 < sp3 (d) sp > sp2 < sp3
(d) 3-(1-ethylpropyl) hex-1-ene 12. Names of some compounds are given. Which
6. The IUPAC name of the following compound is one is not correct in IUPAC system? [2005]
[1998, 2011 M]
CH3
Cl CH2CH3 |
(a) CH3 - CH 2 - CH 2 - CH - CH - CH2CH3
|
CH2CH3
H3C I 3-Methyl-4-ethylheptane
(a) trans-2-chloro-3-iodo-2-pentene
(b) cis-3-iodo-4-chloro-3-pentene (b) CH3 - CH - CH - CH3
| |
(c) trans-3-iodo-4-chloro-3-pentene OH CH3
(d) cis-2-chloro-3-iodo-2-pentene 3-Methyl- 2 -butanol
EBD_8336
112 CHEMISTRY
18. Huckel's rule states that a monocyclic

(c) CH3 - CH 2 - C - CH - CH 3 conjugated compound will be aromatic if it
|| |
CH2 CH3 contains [1996]
2 - Ethyl-3-methyl -but -1-ene (a) (4n + 2p) electrons
(b) (4p + 2n) electrons
(d) CH3 - C º C - CH - (CH3 ) 2 (c) 4p electrons
4- Methyl- 2 - pentyne (d) (4n + 2)p electrons
13. Name of the compound given below is [2003] 19. The first organic compound, synthesized in the
CH3 laboratory, was [1995]
H3C (a) alcohol (b) acetic acid
CH3 (c) urea (d) none of these
20. Which of the following IUPAC names is correct
for the compound? [1994]
CH3
(a) 5-ethyl-6-methyloctane H3C - C H - CH - CH 2 - CH3
| |
(b) 4-ethyl-3-methyloctane CH3 CH2CH3
(c) 3-methyl-4-ethyloctane
(d) 2, 3-diethylheptane (a) 2-Methyl-3-ethylpentane
14. IUPAC name of the following is [2002] (b) 3-Ethyl-2-methylpentane
(c) 2-Ethyl-3-methylpentane
CH 2 = CH - CH 2 - CH 2 - C º CH
(d) 3-Methyl-2-ethylpentane
(a) 1, 5-hexenyne (b) 1-hexene- 5-yne 21. Which is the correct symbol relating the two
(c) 1-hexyne- 5-ene (d) 1, 5-hexynene
Kekule structures of benzene ? [1993]
15. The incorrect IUPAC name is [2001]
(a) (b)
(a) CH 3 - C - C H - CH 3 (c) º (d)
|| |
O CH3 22. When the hybridization state of carbon atom
2-Methyl-3-butanone
changes from sp3 to sp2 and finally to sp, the
angle between the hybridized orbitals [1993]
(b) CH 3 - CH - C H - CH 3 (a) decreases gradually
| |
CH3 CH2CH3 (b) decreases considerably
2,3-Dimethylpentane (c) is not affected
(c) CH 3 C H - C H - CH 3
(d) increases progressively.
| | 23. The IUPAC name of [1992]
Cl Br CH3 - CH - CH = C - CHO
2-Bromo-3-chlorobutane | |
(d) CH 3 - C º CCH(CH 3 ) 2 OH CH3
4-Methyl-2 -pentyne (a) 4-Hydroxy-1-methylpentanal
16. The structural formula of a compound is (b) 4-Hydroxy-2-methylpent-2-en-1-al
CH3 – CH = C = CH2. The types of hybridization (c) 2-Hydroxy-4-methylpent-3-en-5-al
at the four carbons from left to right are (d) 2-Hydroxy-3-methylpent-2-en-5-al
(a) sp2, sp2, sp2, sp3 (b) sp2, sp3, sp2, sp2
24. 2-Methyl-2-butene will be represented as [1992]
(c) sp3, sp2, sp, sp2 (d) sp3, sp2, sp2, sp2
17. The IUPAC name of [1996] CH3
H 3C — C H — CH — CH 2 —CH 2— C H — CH 3 |
| | |
CH3 CH3 CH3 (a) CH3 - CH - CH 2CH3
is
(a) 1, 3-isopropyl-3-methylpropane (b) CH3 - C = CH - CH3
(b) 2, 3, 6-trimethylheptane |
(c) 2, 5, 6-trimethylheptane CH3
(d) 2, 6, 3-trimethylheptane
(c) CH 3 - CH 2 - C = CH 2 (a) 120° and 120° (b) 90° and 109.5°

| (c) 109.5° and 90° (d) 120° and 109.5°
CH 3
Topic 2: Isomerism in Organic Compounds
(d) CH3 - CH - CH = CH 2 32. Given
|
CH3 CH3 CH3 CH3
25. A straight chain hydrocarbon has the molecular CH3 CH3
formula C8H10. The hybridization of the carbon CH3
atoms from one end of the chain to the other are O O O
respectively sp3, sp2, sp2, sp3, sp2, sp2, sp and (I) (II) (III)
sp. The structural formula of the hydrocarbon
would be : [1991] Which of the given compounds can exhibit
tautomerism? [2015]
(a) CH3C º CCH2 – CH = CHCH = CH2 (a) I and III (b) II and III
(b) CH3CH2 – CH = CHCH = CHC º CH (c) I, II and III (d) I and II
(c) CH3CH = CHCH2 – C º CCH = CH2 33. Which one of the following pairs represents
(d) CH3CH = CHCH2 – CH = CH – C º CH. stereoisomerism? [2005]
(a) Structural isomerism and Geometrical
26. An sp3 hybrid orbital contains [1991] isomerism
(a) 1/4 s-character (b) 1/2 s-character (b) Optical isomerism and Geometrical
(c) 1/3 s-character (d) 2/3 s-character. isomerism
27. The shortest C – C bond distance is found in (c) Chain isomerism and Rotational isomerism.
[1991] (d) Linkage isomerism and Geometrical
(a) Diamond (b) Ethane isomerism
(c) Benzene (d) Acetylene ..
28. An organic compound X (molecular formula 34. C H 2 - C - CH 3 and CH 2 = C - CH 3 are
|| |
C6H7O2N) has six carbon atoms in a ring system, O :O
two double bonds an d a nitr o group as . .: [2002]
substituent, X is [1990] (a) Resonating structures
(a) Homocyclic but not aromatic (b) Tautomers
(b) Aromatic but not homocyclic (c) Geometrical isomers
(c) Homocyclic and aromatic (d) Optical isomers
(d) Heterocyclic and aromatic 35. Tautomerism will be exhibited by [1997]
29. Which of the following possesses a sp-carbon (a) (CH3)2NH (b) (CH3)3CNO
in its structure ? [1989]
(c) R3CNO2 (d) RCH2NO2
(a) CH2 = CCl – CH = CH2
36. The number of possible isomers of the compound
(b) CCl2 = CCl2
with molecular formula C7H8O is [1995]
(c) CH2 = C = CH2 (a) 3 (b) 5
(d) CH2 = CH – CH = CH2 (c) 7 (d) 9
30. Cyclic hydrocarbon ‘A’ has all the carbon and 37. Isomers of a substance must have the same
hydrogen atoms in a single plane. All the carbon [1991]
carbon bonds have the same length, less than (a) Structural formula
1.54 Å, but more than 1.34 Å. The C – C – C (b) Physical properties
bond angle will be [1989] (c) Chemical properties
(a) 109°28' (b) 100° (d) Molecular formula
(c) 180° (d) 120° 38. How many chain isomers could be obtained from
31. The Cl – C – Cl angle in 1,1,2,2- tetrachloroethene the alkane C6H14? [1988]
and tetrachloromethane respectively will be (a) Four (b) Five
about [1988] (c) Six (d) Seven
EBD_8336
114 CHEMISTRY
Topic 3: Concept of Reaction Mechanism in 43. Which of the following carbocations is expected
Organic Compounds to be most stable? [2018]
NO2 NO2
39. A tertiary butyl carbocation is more stable than
a secondary butyl carbocation because of which Å
of the following ? [2020] (a) Å

(b)
(a) + R effect of – CH3 groups Y H Y H
(b) – R effect of – CH3 groups NO2
NO2
(c) Hyperconjugation
H
(d) – I effect of – CH3 groups Å
(c) Y (d) H
40. Paper chromatography is an example of Y Å
[2020]
44. Which of the following is correct with respect
(a) Partition chromatography to – I effect of the substituents? (R = alkyl)
(b) Thin layer chromatography [2018]
(a) – NH2 < – OR < – F
(c) Column chromatography (b) – NR2 < – OR < – F
(d) Adsorption chromatography (c) – NR2 > – OR > – F
(d) – NH2 > – OR > – F
41. The most stable car bocation, among the 45. The most suitable method of separation of 1 : 1
following, is [NEET Odisha, 2019] mixture of ortho and para-nitrophenols is :
Å [1994, 2017]
(a) CH3 – CH2 – CH (a) Chromatography (b) Crystallisation
Å (c) Steam distillation (d) Sublimation
(b) (CH3)3 C – CH – CH3
46. The correct statement regarding electrophile is:-
Å
(c) CH3 – CH2 – CH – CH2 – CH3 [2017]
Å (a) Electrophile is a negatively charged species
(d) CH3 – CH – CH2 – CH2 – CH3 and can form a bond by accepting a pair of
42. Among the following, the reaction that proceeds electrons from another electrophile
through an electrophilic substitution, is: [2019] (b) Electrophiles are generally neutral species
and can form a bond by accepting a pair of
(a)
+ Cu Cl
2 2
N 2Cl– ¾¾® Cl + N 2 electrons from a nucleophile
(c) Electrophile can be either neutral or
positively charged species and can form a
AlCl3 bond by accepting a pair of electrons from
(b) + Cl2 ¾¾® Cl + HCl a nucleophile
(d) Electrophile is a negatively charged species
and can form a bond by accepting a pair of
Cl Cl
electrons from a nucleophile
UV light 47. The pair of electron in the given carbanion,
(c) + Cl2 ¾¾® Cl Cl CH3C º C- , is present in which of the following
orbitals ? [2016]
Cl Cl (a) 2p (b) sp3
(c) sp2 (d) sp
48. Which of the following statements is not correct
Heat for a nucleophile? [2015 RS]
(d) CH2OH + HCl ¾®
(a) Nucleophile is a Lewis acid
(b) Ammonia is a nucleophile
CH2Cl + H2O (c) Nucleophiles attack on less e– density sites
(d) Nucleophiles are not electron seeking.
49. Consider the following compounds [2015] 54. Homolytic fission of the following alkanes forms
CH3 Ph free radicals CH3 – CH3, CH3 – CH2 – CH3,
(CH3)2 CH – CH3, CH3 – CH2 – CH (CH3)2.
CH3—C—CH— Ph—C—PH
CH3 Increasing order of stability of the radicals is
CH3 [NEET Kar. 2013]
g g
(I) (II) (III) (a) (CH3)3 C < (CH3)2 C – CH2CH3 <
g g
Hyperconjugation occurs in : CH3 – C H – CH3 < CH3 – C H2
(a) II only (b) III only g g
(b) (CH3)2 C – CH2CH3 < CH3 – C H – CH3 <
(c) I and III (d) I only g g
CH3 – C H2 < (CH3)3 C
50. Which of the following is the most correct g g
electron displacement for a nucleophilic reaction (c) CH3 – C H2 < CH3 – C H – CH3 <
g g
to take place? [2015] (CH3)2 C – CH2 – CH3 < (CH3)3 C
g g
H H2 (d) CH3 – C H2 < CH3 – C H – CH3 < (CH3)3
(a) g g
H3C—C = C – C – Cl C < (CH3)2 C – CH2CH3
H
H H2 55. What is the hybridisation state of benzyl
(b) H 3C—C = C – C – Cl +
H carbonium ion CH2?
H H2
(c) H 3C—C = C – C – Cl [NEET Kar. 2013]
H (a) sp3 (b) sp2
H H2 (c) spd2 (d) sp2 d
(d) H 3C—C = C – C – Cl 56. Nitrogen detection in an organic compound is
H
carried out by Lassaigne’s test. The blue colour
51. In Duma's method for estimation of nitrogen,
formed corresponds to which of the following
0.25 g of an organic compound gave 40 mL of
formulae? [NEET Kar. 2013]
nitrogen collected at 300 K temperature and 725
(a) Fe3[Fe(CN)6]3 (b) Fe3[Fe(CN)6]2
mm pressure. If the aqueous tension at 300 K is
(c) Fe4[Fe(CN)6]3 (d) Fe4[Fe(CN)6]2
25 mm, the percentage of nitrogen in the
57. The correct order of increasing bond length of
compound is : [2015]
C – H, C – O, C – C and C = C is : [2011]
(a) 18.20 (b) 16.76 (a) C – H < C = C < C – O < C – C
(c) 15.76 (d) 17.36 (b) C – C < C = C < C – O < C – H
52. In the Kjeldahl’s method for estimation of (c) C – O < C – H < C – C < C = C
nitrogen present in a soil sample, ammonia (d) C – H < C – O < C – C < C = C
evolved from 0.75 g of sample neutralized 10 mL 58. In Duma's method of estimation of nitrogen
of 1 M H2SO4. The percentage of nitrogen in 0.35 g of an organic compound gave 55 mL of
the soil is : [2014] nitrogen collected at 300 K temperature and
(a) 37.33 (b) 45.33 715 mm pressure. The percentage composition
(c) 35.33 (d) 43.33 of nitrogen in the compound would be :
53. Arrange the following in increasing order of (Aqueous tension at 300 K = 15 mm) [2011]
stability [NEET Kar. 2013] (a) 15.45 (b) 16.45
Å Å (c) 17.45 (d) 14.45
(A) (CH3 )2 C - CH2CH3 (B) (CH3 )3 - C
59. The Lassaigne’s extract is boiled with conc.
Å Å
(C) (CH3 )2 - CH (D) CH3 - CH 2 HNO3 while testing for halogens. By doing so it
[2011]
Å
(E) CH 3 (a) decomposes Na2S and NaCN, if formed.
(b) helps in the precipitation of AgCl.
(a) E < D < C < B < A (b) E < D < C < A < B (c) increases the solubility product of AgCl.
(c) D < E < C < A < B (d) A < E < D < C < B (d) increases the concentration of NO3– ions.
EBD_8336
116 CHEMISTRY
60. The stability of carbanions in the following : 65. Which one of the following is a technique most
suitable for purification of cyclohexanone from
(a) RC º C (b) a mixture containing benzoic acid, isoamyl
alcohol, cyclohexane and cyclohexanone? [1997]
(a) Crystallization
(c) R 2C = CH (d) R 3C - CH 2 (b) Sublimation
is in the order of : [2008] (c) IR spectroscopy
(a) (a) > (b) > (c) > (d) (b) (b) > (c) > (d) > (a) (d) Gas chromatography
(c) (d) > (b) > (c) > (a) (d) (a) > (c) > (b) > (d) 66. Lassaigne’s test for the detection of nitrogen
61. Which amongst the following is the most stable fails in [1994]
carbocation? [2005] (a) NH2CONHNH2.HCl (b) NH2NH2.HCl
Å Å (c) NH2CONH2 (d) C6H5NHNH2.HCl
(a) CH3 (b) CH3 CH 2 67. A is a lighter phenol and B is an aromatic
carboxylic acid. Separation of a mixture of A and
CH3 B can be carried out easily by using a solution
|
Å
(c) CH3- CH (d) CH3 C Å of [1992]

| | (a) Sodium hydroxide (b) Sodium sulphate
CH3 (c) calcium chloride (d) Sodium bicarbonate
CH3
62. The best method for the separati on of 68. Which of the following is the most stable
naphthalene and benzoic acid from their carbocation (carbonium ion) ? [1991]
+ +
mixture is [2005] (a) CH3 C H2 (b) ( CH 3 ) 2 C H
(a) distillation (b) sublimation + +
(c) chromatography (d) crystallisation (c) ( CH 3 ) 3 C (d) C 6 H 5 C H 2
63. In steam distillation of toluene, the pressure for 69. In sodium fusion test of organic compounds,
toluene in vapour is [2001] the nitrogen of the organic compound is
(a) Equal to pressure of barometer converted into [1991]
(b) Less than pressure of barometer (a) Sodamide (b) Sodium cyanide
(c) Equal to vapour pressure of toluene in (c) Sodium nitrite (d) Sodium nitrate
simple distillation 70. Kjeldahl’s method is used in the estimation of
(d) More than vapour pressure of toluene in [1990]
simple distillation (a) Nitrogen (b) Halogens
64. Which one of the following order is correct (c) Sulphur (d) Oxygen
regarding the – I effect of the substituents ? 71. Lassaigne’s test is used in qualitative analysis
[1998] to detect [1989]
(a) –NR2 < – OR > –F (b) –NR2 > –OR > –F (a) Nitrogen (b) Sulphur
(c) –NR2 < –OR < –F (d) –NR2 > –OR < –F (c) Chlorine (d) All of these
ANSWER KEY
1 (d) 9 (c) 17 (b ) 25 (d) 33 (b) 41 (d) 49 (b) 57 (a) 65 (c)
2 (a) 10 (c) 18 (d) 26 (a) 34 (a) 42 (b) 50 (b) 58 (b ) 66 (b)
3 (d) 11 (a) 19 (c) 27 (d) 35 (d) 43 (d) 51 (b) 59 (a) 67 (d)
4 (a) 12 (a) 20 (b) 28 (a) 36 (b) 44 (a) 52 (a) 60 (a) 68 (c)
5 (a) 13 (b) 21 (d) 29 (c) 37 (d) 45 (c) 53 (b) 61 (d ) 69 (b)
6 (a) 14 (b) 22 (d) 30 (d) 38 (b) 46 (c) 54 (c) 62 (b ) 70 (a)
7 (d) 15 (a) 23 (b) 31 (d) 39 (c) 47 (d) 55 (b) 63 (b ) 71 (d)
8 (b) 16 (c) 24 (b) 32 (c) 40 (a) 48 (a) 56 (c) 64 (c)
Hints & Solutions

O O C – 5 is sp2 hybridized (C = C)
2
Thus the correct sequence is sp, sp3, sp2.
1. (d) H C 3 4 9. (c) General molecular formula of alkanols is
1
5 CnH2n + 2O , (CnH2n + 1OH)
6
3-keto-2-methylhex-4-enal
Aldehydes get higher priority over ketone and 4
alkene in numbering of principal carbon chain. 3 2 1 Cl
OH
10. (c) 5
C
||
3 2
1 O
H3C COOH
2. (a) 4 It is 2, 3-dimethylpentanoyl chloride.
6
5 CH 3 11. (a) Among the three given hybrid orbitals, sp
IUPAC name of the structure is hybrid orbital is most electronegative.
3-ethyl-2-hydroxy-4-methylhex-3-en-5-ynoic acid
CH 3 Contribution of s in sp hybrid orbital is maximum
3. (d) CH - CH 2 - (isobutyl group) (50%) so this orbital is closer to nucleus. It will
CH 3 have greater tendency to pull electron towards it.
4. (a) Br CH2 CH CH 2 Hence it becomes more electronegative and sp 3
3 2 1 becomes least electronegative as it has only 25%
The correct name is 3-Bromoprop-1-ene. s-character.
5. (a) The given compound is
12. (a) Correct IUPAC name of
2 1
CH = CH2 CH3
|
CH3 — CH2 — CH2 — C — C — CH2 — CH3 CH 3CH 2 CH 2 - C H - C H - CH 2 CH 3
|
3 4
CH 2CH3
CH2 – CH3
5 6 is 4-Ethyl-3-methylheptane
4 ethyl-3-propylhex-1-ene
13. (b) CH3 CH3
4 5 1 3 5 7
6. (a) CH2CH3 4
Cl 2 8 CH3
C=C 6
2 3
CH3 I CH3
1
Correct IUPAC name of above compound is 4–ethyl-3¢–methyloctane
trans-2-chloro-3-iodo-2-pentene 14. (b) The IUPAC name of

1 2 3 4 5 6
CH3 CH3 C H2 = C H — C H2 — C H2 — C º C H
sp 3 |
sp 2 sp3 | sp
7. (d) CH3 C CH = CH CH — C º C H is Hex-1-en-5-yne or 1-hexene-5-yne
7 6| 5 4 3 2 1
CH3
The lowest number is given to the C = C double
bond.
8. (b) C – 1 is sp hybridized (C º C)
C – 3 is sp3 hybridized (C– C)
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118 CHEMISTRY
1 2 3 4 The vital force theory suffered first death blow in

15. (a) CH3 C CH CH3 1828 when Wohler synthesized the Ist organic
compound urea in the laboratory from inorganic
O CH3 compounds reported below :
3 Methyl-2- butanone to isomeric charge
1 2 3 NH 4 CNO ¾¾ ¾ ¾ ¾ ¾ ¾¾® NH 2 CONH2
rearrangement leading
CH3 CH CH CH3 Urea
4 5 Later on a further blow to vital force theory was
CH3 CH2 CH3 given by Kolbe (1845) who prepared acetic acid,
the first organic compound, in laboratory from its
2, 3 dimethyl pentane elements.
4 3 2 1 1
CH3 CH CH CH3 20. (b) CH3 - 2CH - 3CH - 4 CH 2 - 5CH3
| |
Cl Br CH3 CH 2 CH3
2 Bromo-3-chlorobutane
3-Ethyl-2-methylpentane
5CH 21. (d) Resonance structures are separated by a
3
1 2 3 4 double headed arrow ( ¬¾® )
CH3 C C CH 22. (d) Angle increases progressively
CH3 sp3 ( 109°28' ), sp2 (120°), sp (180°)
4-Methyl-2-pentyne 23. (b) 5 CH - 4 CH - 3CH = 2C - 1CHO
3
sp3 sp 2 sp sp 2 | |
16. (c) CH 3 - CH = C = CH 2 OH CH3
4-Hydroxy-2-methylpent-2-en-1-al
1 2 3 4 5 6 7
17. (b) C H 3 – C H – C H – C H 2 – C H 2 – C H – C H 3 CH3
| | | |
CH3 CH3 CH 3 24. (b) 1
C H 3 - 2 C = 3 C H - 4 CH 3
2-Methyl-2-butene
2, 3, 6 – trimethylheptane
sp3 sp2 sp 2 sp3 sp2 sp 2 sp sp
When many substituents are present, the 25. (d) CH3 – CH = CH – CH2 - CH = CH– C º CH
numbering is done from the end where the first
point of difference is the lowest number. 26. (a) sp3 orbital has 1/4(25%) s-character & 75%
7
p-character.
CH 3 – 6 CH – 5 CH – 4 CH 2 – 3 CH 2 – 2 CH – 1CH3
| | | 27. (d) Shortest C – C distance (1.20 Å) is in
CH3 CH 3 CH 3 acetylene, as acetylene has sp hybridisation.
The bond length increases in the order
Set of locants = 2, 5, 6
1
CH3 – 2 CH – 3 CH – 4 CH 2 – 5 CH 2 – 6 CH – 7 CH 3 Cº C < C= C < C-C
| | |
sp (1.20Å) sp 2 (1.34Å) sp (1.54Å)
CH3 CH 3 CH 3
Set of locants = 2, 3, 6 NO 2
The first point of difference 3 is lower than the NO 2
number 5 of first set. Thus, the correct name is 2,
3, 6-trimethylheptane. 28. (a) or
18. (d) Huckel’s rule states that for aromaticity Hence it is homocyclic (as the ring system is made
there must be (4n + 2) p electrons present in a of one type of atoms, i.e. carbon) but not aromatic.
compound, where n is an integer. As it does not follow (4n +2)p electron rule of
aromaticity.
19. (c) Urea is the first organic compound
synthesized in the laboratory by wohler.
sp 2 sp sp 2 35. (d) As option (d) has a-hydrogen atom.

29. (c) CH 2 = C = CH 2 Therefore it shows tautomerism whereas other
30. (d) All the properties mentioned in the question structures do not.
suggest that it is a benzene molecule. Since in O OH
benzene all carbons are sp2–hybridized, therefore, R CH2 N R CH N
C – C – C angle is 120° Nitroform O Aciform O
Tautomerism is exhibited by the oscillation of
H H hydrogen atom between two polyvalent atoms
1.09Å 1.40Å present in the molecule.
C C
120°
H C 120° C 36. (b) The possible isomers of the compound with
H
molecular formula C 7 H8 O is 5. These are
C C C6H5OCH3, C6H5CH2OH and
(Anisole) benzyl alcohol
H H
CH3 CH3 CH3
31. (d) Tetrachloroethene being an alkene has sp2 - OH
hybridized C– atoms and hence the angle
Cl – C – Cl is 120° while in tetrachloromethane,
carbon is sp3 hybridized, therefore the angle Cl – o- cresol
OH
C – Cl is 109.5°. OH
p-cresol m-cresol
32. (c) All of these compounds show tautomerism
37. (d) Organic compounds having same molecular
H3C CH3 H3C CH3 formula but differ from each other in physical or
chemical properties or structural formula are
known as isomers.
38. (b) Five chain isomers are possible which are –
H (i) CH 3 - CH 2 - CH 2 - CH 2 - CH 2 - CH 3
O OH n-hexane
CH3 CH3 (ii) CH3 - CH - CH 2 - CH 2 - CH3
CH3 CH3 |
CH3
H 2-methyl pentane
O
O OH
OH
H
H CH3
|
(iii) CH3 - C - CH 2 - CH3
CH3 CH3 |
CH3
CH3 CH3
2, 2-dimethyl butane
O OH
(iv) CH3 - CH - CH - CH 3
33. (b) Optical and geometrical isomerism pair up | |
to exhibit stereoisomerism. This is because the CH3 CH3
isomers differ only in their orientation in space.
2, 3-dimethyl butane
–
34. (a) CH2 — C — CH3 CH2 = C — CH3 (v) CH3 - CH 2 - CH - CH 2 - CH3
|
O O CH3
–
3-methyl pentane
I II
both are resonating structures.
EBD_8336
120 CHEMISTRY
39. (c) 48. (a) nucleophiles are usually lewis bases.

CH3
Å
Nucleophile is a species that provide electron while
H3C – C – CH3 H3C – CH – CH2 – CH3 species which are deficient of electrons are termed
Å as lewis acid.
Tertiary butyl carbocation Secondary butyl carbocation
(9 a-H atoms) (5 a-H atom) 49. (b) Only structure (III) has H in conjugation with
t-Butyl carbocation is more stable due to hyper- free radical.
conjugation. So, hyperconjugation is possible in III only.
–
40. (a) Paper chromatography is a type of partition 50. (b) p bond is transferred after leaving Cl
Å
chromatography. CH 3 – CH=CH.CH2 —Cl CH3 – CH=CH—CH2
41. (d) Stability of carbocation µ No. of a-H Å
Among the given carbocations, CH 3—CH—CH=CH 2
a -H Å a -H
CH3 – CH– CH 2 – CH 2 – CH3 is the most
Hyperinflation results from the interaction of s
stable carbocation (5 a-H) bond electrons with an adjacent empty or partially
42. (b) (i) AlCl3 + Cl – Cl ® [AlCl4]– + Cl+ filled p-orbital or a orbital to give an extended
Electrophile molecular othital that increase the stability.
Cl
51. (b) Wt. of organic substance = 0.25 g
+ V1 = 40 mL, T1 = 300 K
(ii) + Cl ¾®
P1 = 725 – 25 = 700 mm of Hg
43. (d) –NO2 group is meta-directing group P2 = 760 mm of Hg (at STP)
NO2 NO2 T2 = 273 K
+ PV
1 1 = P2V2
¬¾® T1 T2
+
H H V2 (Volume of nitrogen at STP)
Y Y
(Less stable due to more e– withdrawing effect of –NO2) 273 ´ 700 ´ 40
NO2 = = 33.52 mL
NO2 NO2 300 ´ 760
+ + Percentage of nitrogen
¬¾® ¬¾®
H H H 28× volume of N 2 at STP ×100
Y + Y Y = 22400 × wt. of organic substance
–
(More stable due to less e withdrawing effect of –
NO 2) greater no. of resonating structures.
28 ´ 33.52 ´ 100
44. (a) –I effect increases on increasing = = 16.76%
electronegativity of atom. So, correct order of 22400 ´ 0.25
–I effect is –NH2 < – OR < – F. 52. (a) 10 mL, 1 M H2SO4 = 20 mL, 1 M NH3
45. (c) The o-isomer is steam volatile due to intra- Q wt of N in one mole NH3 = 14
molecular H-bonding. The p-isomer is not steam
volatile due to intermolecular H-bonding or \ 20 × 10– 3 mol NH3 ¾®
association of molecules. Thus, both can be 20 × 10– 3 × 14 nitrogen
separated by steam distillation. \ 0.75 g of sample contains
46. (c) Electrophite is a electron deficient species
and can accpet pair of electrons from nucleophite 14 ´ 20 ´ 10 - 3
= ´ 100 = 37.33%
47. (d) CH3—C º C 0.75
No.of s bp - 1 ù
53. (b) Greater the number of e– donating alkyl
lp –1 û 2 & hybridisation is sp groups (+I effect), greater will be the stability of
carbocations.
61. (d) More the number of alkyl groups, greater

54. (c) Stability depends on number of will be the dispersal of positive charge and
hyperconjugative structure. therefore more the stability of carbocation.
55. (b) In the carbonium ion the carbon atom
CH3
carrying the positive charge is sp2 hybridized. |
56. (c) The prussian blue colour is of Fe4 [Fe(CN)6]3 Thus CH3 –C + is most stable
|
ferric ferrocyanide CH3
57. (a) Bond length order is 62. (b) Among the given compounds naphthalene
is volatile but benzoic acid is non-volatile (it
C-H < C =C < C-O < C-C
1.10A ° 1.34A ° 1.40A ° 1.54A ° forms a dimer). So, the best method for their
separation is sublimation
58. (b) Given wt of compound taken (w) = 0.35 g
Volume of nitrogen collected (V) = 55 mL Sublimation method is applicable to compounds
which can be converted directly into the vapour
Room temperature (t K) = 300 K phase from its solid state on heating and back to
the solid state on cooling.
Atmospheric pressure (P) = 715 mm
Aq. tension (r) = 15 mm 63. (b) The principle of steam distillation is based
on Dalton's law of partial pressures. Suppose p1
Calculation - and p2 be the vapour pressures of water vapour
( P - ρ) ´ V 273 and the toluene at the distillation temperature.
Volume of N2 at NTP = ´ mL Toluene boils when total pressure is equal to
t 760 atmospheric pressure p i.e p = p1 + p2
or p2 = p – p1
(715 - 15) ´ 55 273
= ´ = 46.098 mL As a result, when toluene boil in the presence of
300 760
steam its partial pressure p 2 is less than
% of nitrogen atmospheric pressure.
28 ´ vol.of N 2 at NTP ´ 100 64. (c) As electronegativity of N, O & F follow the
= order N < O < F hence based upon
22400 ´ wt of organic compound
electronegative character order of-I effect is
28 ´ 46.098 ´ 100 – NR2 < – OR < – F.
= = 16.46%
22400 ´ 0.35 The atom or group which has more power to attract
59. (a) Conc. HNO3 decomposes NaCN and Na2S electrons in comparision to hydrogen is said to
to avoid their interference. have -I effect. Thus higher the electronegativity of
atom, stronger will be the -I effect.
NaCN + HNO 3 ¾¾
® NaNO 3 + HCN
65. (c) IR spectroscopy is used for the purification of
Na 2S + 2HNO3 ¾¾
® 2NaNO 3 + H 2S cyclohexanone from a mixture of benzoic
acid, isoamyl alcohol, cyclohexane and
60. (a) As 's' character increases, stability of cyclohexanone. Because in this method, each
carbanion increases. Also, electron donating functional group appear at a certain peak. So,
groups decreases the stability of carbanion. cyclohexanone can be identified by carbonyl
Hence, the correct stability, order: peak.
sp 2
An amyl alcohol is any one of 8 alcohols with the
C > > R2 C=CH formula C5H12O (alkanol with 5 carbons).
sp sp2
66. (b) Hydrazine (NH2 NH2 ) does not contain

R3 C CH2 carbon and hence on fusion with Na metal, it
+1 cannot form NaCN; so it does not show
Lassaigne’s test for nitrogen.
EBD_8336
122 CHEMISTRY
This test fails in case of diazo compounds, dinitro is basically used for estimating nitrogen in food
compounds and compounds containing nitrogen fertilizers and agricultural products.
in the ring.
Kjeldahl's method is not used in case of nitro, azo
67. (d) Carboxylic acids dissolve in NaHCO 3 and and azoxy compound.
evolve CO2 gas but phenols do not.
NaHCO 71. (d) Nitrogen, sulphur and halogens are tested
RCOOH ¾¾¾¾ 3
® RCOONa + H 2O + CO2
in an organic compound by Lassaigne's test.
68. (c) Higher the +I effect greater is stability of the
species. Thus,
+ + + The organic compound is fused with sodium metal
(CH3 )3 C + > (CH3 )2 C H > C6 H 5 C H 2 > CH 3 C H 2 as to convert these elements into ionisable inorganic
substances,
Also, primary benzyl carbocation have almost
the same stability as 2°-alkyl carbocations. Na + C + N ¾¾
® NaCN
69. (b) Sodium cyanide (Na + C + N ® NaCN). 2Na + S ¾¾
® Na 2S
(Lassaigne's test) 2Na + X 2 ¾¾
® 2NaX
70. (a) Kjeldahl's method is suitable for estimating The cyanide, sulphide or halide ions can be
nitrogen in those compounds in which nitrogen confirmed in aqueous solution by usual test.
is linked to carbon and hydrogen. This method
13 Hydrocarbons
2020 2019 2018 2017 2016

conversion
(substitution/ wurtz 1 E
Alkanes reaction)
conformations of
1 A 1 E
ethane
Alkenes ozonolysis 1 A 1 A
reduction of alkyne 1 E
order of
Alkyne acidity/acidic 1 E 1 A
character
hydration reaction 1 A
Topic 1: Alkanes (c) Both bond angles and bond length remains
same
1. The alkane that gives only one mono-chloro (d) Bond angle remains same but bond length
product on chlorination with Cl2 in presence of changes
diffused sunlight is [NEET Odisha 2019] 4. The correct statement regarding the comparison
(a) Isopentane of staggered and eclipsed conformation of
ethane, is [2016]
(b) 2, 2-dimethylbutane
(a) The staggered conformation of ethane is
(c) neopentane
less stable than eclipsed conformation,
(d) n-pentane because staggered conformation has
2. Hydrocarbon (A) reacts with bromine by torsional strain
substitution to form an alkyl bromide which by (b) The eclipsed conformation of ethane is
Wurtz r eaction is converted to gaseous more stable than staggered conformation,
hydrocarbon containing less than four carbon because eclipsed conformation has no
atoms. (A) is [2018] torsional strain
(a) CH º CH (b) CH2 = CH2 (c) The eclipsed conformation of ethane is
(c) CH4 (d) CH3 – CH3 more stable than staggered conformation
3. With respect to the conformers of ethane, which even though the eclipsed conformation has
of the following statements is true ? [2017] torsional strain
(a) Bond angle changes but bond length (d) The staggered conformation of ethane is
remains same more stable than eclipsed conformation,
because staggered conformation has no
(b) Both bond angle and bond length change
torsional strain.
EBD_8336
124 CHEMISTRY
5. Given OH
OH
Br Br H
H Br (c)
CH3 H
CH3 and H
H CH3 CH3
H H H
Br
OH
I II H
I and II are [NEET Kar. 2013] (d)
(a) A pair of optical isomers
(b) Identical HO
(c) A pair of conformers H H H
(d) A pair of geometrical isomers 8. Liquid hydrocarbons can be converted to a
6. In the following the most stable conformation mixture of gaseous hydrocarbons by : [2010]
of n-butane is: [2010] (a) Oxidation
CH3 CH3 (b) Cracking
H CH3 H H (c) Distillation under reduced pressure
(d) Hydrolysis
(a) (b) 9. A compound of molecular formula of C7H16
shows optical isomerism, compound will be
H H H H
(a) 2, 3-Dimethylpentane [2001]
H CH3 (b) 2,2-Dimethylbutane
CH3 CH3 (c) 2-Methylhexane
CH3 H (d) None of the above
10. The reaction of ethyl magnesium bromide with
(c) (d) water would give [1999]
H H (a) Ethane (b) Ethyl alcohol
H H H
HH H3C (c) Ethyl bromide (d) Ethyl ether
7. Which of the following conformers for ethylene 11. In commercial gasolines the type of
glycol is most stable? [2010] hydrocarbons which are more desirable, is
(a) branched hydrocarbons [1997]
OH (b) straight-chain hydrocarbons
H OH (c) aromatic hydrocarbons such as toluene
(d) linear unsaturated hydrocarbons
(a) 12. The most stable conformation of n-butane is
[1997]
(a) skew boat (b) gauche
H H (c) staggered-anti (d) eclipsed
H 13. Which one of the following reactions is
expected to readily give a hydrocarbon product
OH in good yields ? [1997]
H H Electrolyt ic
(a) RCOOK ¾¾ ¾ ¾¾®
oxidation
(b) (b) - + Br2
RCOO Ag ¾¾
¾®
Cl
H H (c) CH 3 CH 3 ¾¾
¾2®
hu
OH C 2 H 5OH
(d) (CH 3 ) 3 CCl ¾¾ ¾ ¾®
Hydrocarbons 125
14. In the free radical chlorination of methane, the CH3
–
chain initiating step involves the formation of (a) Cl – CH2 – CH2 – CH
–
(a) Chlorine free radical [1994] CH3
(b) Hydrogen chloride
CH2Cl
(c) Methyl radical
–
(b) H3C – CH2 – CH – CH3
(d) Chloromethyl radical.
15. Reactivity of hydrogen atoms attached to
CH3
different carbon atoms in alkanes has the order
–
(c) H3C – CH2 – C – CH3
[1993]
–
(a) Tertiary > Primary > Secondary Cl
(b) Primary > Secondary > Tertiary CH3
–
(c) Both (a) and (b) (d) H3C – CH – CH
–
(d) Tertiary > Secondary > Primary Cl CH3
18. 2,3-Dimethyl-2-butene can be prepared by
Topic 2: Alkenes
heating which of the following compounds with
16. An alkene on ozonolysis gives methanal as one a strong acid ? [2015 RS]
of the product. Its structure is [2020] (a) (CH3)2 CH – CH – CH = CH2
|
CH3
(b) (CH3)3 C – CH = CH2
(c) (CH3)2C = CH – CH2 – CH3
(a) (d) (CH3)2CH – CH2 – CH = CH2
19. In the reaction with HCl, an alkene reacts in
accordance with the Markovnikov's rule, to give
a product 1-chloro-1-methylcyclohexane. The
possible alkene is : [2015 RS]
CH2 CH3
(b)
(a) (b)
CH3
(c)
(c) (a) and (b) (d)
20. A single compound of the structure : [2015]

CH3 CH3
OHC C C
(d) C H C O
H2 H2
is obtainable from ozonolysis of which of the
17. An alkene “A” on reaction with O3 and Zn –
following cyclic compounds ?
H2O gives propanone and ethanal in equimolar
H3C
ratio. Addition of HCl to alkene “A” gives “B”
as the major product. The structure of product (a)
“B” is: [2019] H3C
EBD_8336
126 CHEMISTRY
CH3 The major product is : [2012]

H3C
(b) CH3
(a) C CH CH3
CH3
OH CH3
(c)
CH3 CH3
H3C (b) C CH2 CH3

(d) CH3
OH CH3
21. The total number of p-bond electrons in the
CH3
following structure is : [2015]
H H H (c) C CH CH3
H3C
H3C CH3 CH3 OH
CH3
H2C CH3 H
(a) 8 (b) 12 (d) C CH2 CH2
(c) 16 (d) 4
CH3 OH
22. The reaction of C6H5CH = CHCH3 with HBr
produces: [2015] 24. In the following reactions, [2011]
(a) C6 H5CH 2CHCH3
| CH3
Br (i) CH3–CH–CH–CH3
H + /Heat
A + B
Major Minor
(b) C6 H5CH 2CH 2CH 2Br OH products products
HBr,dark
CH=CHCH3 (ii) A ¾¾¾¾¾¾¾¾® C + D
in absenceof peroxide
A ¾¾¾¾¾¾¾¾® C + D
(c) in absenceof peroxide æMajor ö æMinor ö
èproduct ø èproduct ø
the major products (A) and (C) are respectively:

Br
CH3
(d) C 6 H 5 C HCH 2 CH3
| (a) CH2 = C – CH2– CH3 2 2 3
Br CH3
23. In the following reaction :
CH3 2 2 3 and CH2– CH– CH2– CH3
+ Br
H 2O/H CH3
C CH —
— CH2
(b) CH3– C = CH–CH3
CH3 CH3
A B 3 3 and CH 3– C – CH2– CH3
Minor Product + Major Product Br
Hydrocarbons 127
CH3 R R R H
(c) CH3– C = CH – CH3 (a) (b)
H H R H
CH 3 R R R R
3 3 and CH3 – CH – CH – CH 3 (c) (d)
R H R R
Br 30. Reaction of HBr with propene in the presence of
CH3
peroxide gives [2004]
(d) CH2 = C – CH2 – CH3 3 2 3 (a) isopropyl bromide (b) 3-bromo propane
CH3 (c) allyl bromide (d) n-propyl bromide
2 2 3 and CH3– C – CH2 – CH3
CH 3
Br |
25. The IUPAC name of the compound having the 31. The compound CH 3— C = CH — CH 3
formula CH º C – CH = CH2 is : [2009] on reaction with NaIO4 in the presence of
(a) 1-butyn-3-ene (b) but-1-yne-3-ene KMnO4 gives [2003]
(c) 1-butene-3-yne (d) 3-butene-1-yne (a) CH3CHO + CO2
26. Which of the following compounds will exhibit (b) CH3COCH3
cis-trans (geometrical) isomerism? [2009] (c) CH3COCH3 + CH3COOH
(d) CH3COCH3 + CH3CHO
(a) Butanol (b) 2-Butyne
32. Geometrical isomers differ in [2002]
(c) 2-Butenol (d) 2-Butene (a) position of functional group
27. H 3C - CH - CH = CH 2 + HBr ® A (b) position of atoms
|
(c) spatial arrangement of atoms
CH 3
(d) length of carbon chain
A (predominantly) is : [2008] 33. Which alkene on ozonolysis gives CH3CH2CHO
(a) CH 3 - CH - CH 2 - CH 2 Br and CH3CCH3 [2001]
|
||
CH 3 O
Br
| CH3
(b) CH3 - C- CH 2 - CH3 (a) CH3CH2CH = C
| CH3
CH3 (b) CH3CH2CH = CHCH2CH3
(c) CH3 - CH- CH - CH 3 (c) CH3 CH2 CH = CH CH3
| | (d) CH 3 - C = CHCH 3
Br CH3 |
CH3
(d) CH 3 - CH - CH - CH 3
| | 34. In preparation of alkene from alcohol using Al2O3
CH 3 Br which is effective factor? [2001]
28. Which of the compounds with molecular formula (a) Temperature
C5H10 yields acetone on ozonolysis? (b) Concentration
[2007] (c) Surface area of Al2O3
(a) 3-methyl-1-butene (b) cyclopentane (d) Porosity of Al2O3
(c) 2-methyl-1-butene (d) 2-methyl-2-butene. 35. Which of the following reagents convert
propene to 1-propanol? [2000]
29. Which one of the following alkenes will react (a) H2O, H2SO4
faster with H2 under catalytic hydrogenation (b) aqueous KOH
conditions? [2005] (c) MgSO4, NaBH4/H2O
(R = Alkyl Substituent) (d) B2H6, H2O2, OH–
EBD_8336
128 CHEMISTRY
36. Correct order of stability is : [2000] 42. When 3, 3-dimethyl –2-butanol is heated with
(a) cis -2- butene > 1-butene > trans -2-butene H2SO4, the major product obtained is [1995]
(b) trans-2-butene > cis-2-butene > 1-butene (a) 2, 3-dimethyl –2-butene
(c) 1-butene > cis-2-butene > trans-2- butene
(b) 3, 3-dimethyl –1- butene
(d) cis-2-butene > trans-2-butene > 1-butene
37. The correct structure of trans-2 hexenal is [1999] (c) 2, 3-dimethyl –1- butene
CHO (d) cis & trans isomers of 2, 3-dimethyl – 2-butene
(a) 43. The alkene R – CH = CH2 reacts readily with
(b) CHO B2H6 and formed the product B which on
(c) CHO (d)
CHO oxidation with alkaline hydrogen peroxides
38. A hydrocarbon ‘A’ on chlorination gives ‘B’ produces [1995]
which on heating with alcoholic potassium (a) R – CH2 – CHO (b) R– CH2 – CH2 – OH
hydroxide changes into another hydrocarbon
‘C’. The latter decolourises Baeyer's reagent and (c) R-C =O (d) R - CH - C H 2
on ozonolysis forms formaldehyde only. ‘A’ is | | |
(a) Ethane (b) Butane [1998] CH3 OH OH
(c) Methane (d) Ethene
39. In reaction sequence [1997] 44. Which of the following compounds has the
lowest boiling point ? [1994]
CH2OH
Hypochlorous R
CH 2 = CH 2 ¾¾ ¾¾¾ ¾® M ¾¾® | (a) CH3CH2CH2CH2CH3
acid CH2OH (b) CH3CH = CHCH2CH3
molecule 'M' and reagent 'R' respectively are
(c) CH3CH = CH – CH = CH2
(a) CH3CH2Cl and NaOH
(d) CH3CH2CH2CH3
(b) CH3CH2OH and H2SO4
(c) CH2Cl – CH2OH and aqueous NaHCO3 45. When hydrochloric acid gas is treated with
propene in presence of benzoyl peroxide, it gives
(d) CH2 — CH2 and heat
[1993]
O (a) 2-Chloropropane (b) Allyl chloride
40. In the presence of platinum catalyst,
hydrocarbon A adds hydrogen to form n-hexane. (c) No reaction (d) n-Propyl chloride.
When hydrogen bromide is added to A instead 46. The restricted rotation about carbon carbon
of hydrogen, only a single bromo compound is double bond in 2-butene is due to [1993]
formed. Which of the following is A? [1996] 2
(a) Overlap of one s- and sp - hybridized
(a) CH 3 — CH 2 — CH = CH — CH 2 — CH 3 orbitals
(b) CH 3 — CH 2 — CH 2 — CH = CH — CH 3 (b) Overlap of two sp2 - hybridized orbitals
(c) CH 3 — CH = CH — CH 2 — CH 2 — CH 3 (c) Overlap of one p- and one sp2 - hybridized
(d) CH 2 = CH — CH 2 — CH 2 — CH 2 — CH 3 orbitals
41. Which of the following will not show cis-trans (d) Sideways overlap of two p- orbitals.
isomerism? [1996]
47. Which one of the following can exhibit cis-trans
(a) CH 3 — CH = CH — CH 3 isomerism ? [1989]
(b) CH 3 — CH 2 — CH = CH — CH 2 — CH 3 (a) CH 3 - CHCl - COOH
(c) CH — CH = CH — CH — CH
3 2 3
| (b) H - C º C - Cl
CH3
(c) ClCH = CHCl
(d) CH 3— C H — CH = CH — CH 2 — CH 3
| (d) ClCH 2 - CH 2Cl
CH 3
Hydrocarbons 129
Topic 3: Alkynes 52. In the reaction

(1)NaNH 2 /liq.NH 3
48. In the following reaction, [NEET Odisha 2019] H - C º CH X
(2)CH 3CH 2Br
Red hot
iron tube
H3C – C º CH ¾¾¾¾
873 K
® A, the (1)NaNH 2 /liq.NH 3
Y
(2)CH3CH 2Br
number of sigma (s) bonds present in the product
A, is X and Y are [2016]
(a) 18 (b) 21 (a) X = 1-Butyne ; Y = 3-Hexyne
(c) 9 (d) 24 (b) X = 2-Butyne ; Y = 3-Hexyne
49. The most suitable reagent for the following (c) X = 2-Butyne ; Y = 2-Hexyne
conversion, is: [2019] (d) X = 1-Butyne ; Y = 2-Hexyne
H3C CH3 53. Which of the following organic compounds has
H3C – C C – CH3 same hybridization as its combustion product
H H (CO2)? [2014]
(a) Ethane (b) Ethyne
cis-2-butene
(c) Ethene (d) Ethanol
(a) Na/liquid NH3 (b) H2, Pd/C, quinoline
54. In the following reaction :
(c) Zn/HCl (d) Hg2+/H+, H2O
H SO
50. Which one is the correct order of acidity ? [2017] HC º CH ¾¾¾¾
2
2+
4 ® 'P'
Hg
(a) CH º CH > CH3 – C º CH > CH2
= CH2 > CH3 – CH3 Product ‘P’ will not give [NEET Kar. 2013]
(b) CH º CH > CH2 = CH2 > CH3 – C º CH > (a) Iodoform test
CH3 – CH3 (b) Tollen’s reagent test
(c) CH3 – CH3 > CH2 = CH2 > CH3 – C º CH> (c) Brady’s reagent test
CH º CH
(d) Victor Meyer test
(d) CH2 = CH2 > CH3 – CH = CH2 > CH3 – C º
CH > CH º CH 55. Which of the following reagents will be able to
51. Predict the correct intermediate and product in distinguish between 1-butyne and 2-butyne?
the following reaction : [2017] (a) NaNH2 (b) HCl [2012 M]
H O, H SO (c) O2 (d) Br2
H3C - C º CH ¾¾¾¾¾¾
2 2 4 ® Intermediate ® product
HgSO4 (A) (B) 56. The IUPAC name of the compound
(a) A : H3C – C = CH , B : H3C – C = CH2 CH3CH = CHC º CH is [2010]
| | (a) Pent-l-yn-3-ene (b) Pent-4-yn-2-ene
OH SO4
(c) Pent-3-en-1-yne (d) Pent-2-en-4-yne
(b) A : H3C – C = CH3, B : H3C – C º CH 57. Base strength of : [2008]
||
O
– –
(A) H 3C – CH 2 (B) H 2 C = CH and
(c) A : H3C – C = CH2 , B : H3C – C = CH3 –
| || (C) H - C º C
OH O
is in the order of :
(d) A : H3C – C = CH2 , B : H3C - C - CH3 (a) (B) > (A) > (C) (b) (C) > (B) > (A)
| ||
SO4 O (c) (A) > (C) > (B) (d) (A) > (B) > (C)
EBD_8336
130 CHEMISTRY
58. Predict the product C obtained in the following (a) Bromine in carbon tetrachloride
reaction of butyne-1. [2007] (b) Bromine in acetic acid
HI (c) Alk. KMnO4
CH 3CH 2 - C º CH + HCl ¾¾
® B ¾¾® C
I (d) Ammoniacal silver nitrate.
| 64. Acetylenic hydrogens are acidic because [1989]
(a) CH3 - CH 2 - CH 2 - C - H (a) Sigma electron density of C – H bond in
| acetylene is nearer to carbon, which has
Cl
50% s-character
I
| (b) Acetylene has only open hydrogen in each
(b) CH 3 - CH 2 - CH - CH 2 Cl carbon
I (c) Acetylene contains least number of
| hydrogens among the possible
(c) CH3CH 2 - C - CH3
| hydrocarbons having two carbons
Cl (d) Acetylene belongs to the class of alkynes
(d) CH3 - CH - CH 2CH 2 I with molecular formula, CnH2n – 2.
|
Cl Topic 4: Aromatic Hydrocarbons
59. Products of the following reaction: [2005]
65. Given:
(1) O CH3 H3C CH2 H2C
CH3CºC·CH2 CH3 ¾¾¾¾¾¾3
(2) Hydrolysis
® ...... are: H3C CH2
(a) CH3COOH + CO2

(b) CH3COOH + HOOC ×CH2CH3 CH3 CH3 CH2
(c) CH3CHO + CH3CH2CHO (III)
(I) (II)
(d) CH3COOH + CH3COCH3 The enthalpy of the hydrogenation of these
60. A compound is treated with NaNH2 to give compounds will be in the order as : [2015]
sodium salt. Identify the compound [1993] (a) III > II > I (b) II > III > I
(a) C2H2 (b) C6H6 (c) II > I > III (d) I > II > III
(c) C2H6 (d) C2H4. 66. The oxidation of benzene by V2O5 in presence
61. Reduction of 2-butyne with sodium in liquid of air produces : [2015 RS]
ammonia gives predominantly [1993] (a) benzoic anhydride (b) maleic anhydride
(a) cis-2-butene (b) No reaction (c) benzoic acid (d) benzaldehyde
(c) trans-2-butene (d) n-butane. .
67. The radical, CH2 is aromatic because
Re agent
62. R - CH2 - CCl2 - R ¾¾¾¾® R - C º C - R
it has : [NEET 2013]
The reagent is [1993] (a) 7 p-orbitals and 6 unpaired electrons
(a) Na (b) HCl in H2O (b) 7 p-orbitals and 7 unpaired electrons
(c) KOH in C2H5OH (d) Zn in alcohol. (c) 6 p-orbitals and 7 unpaired electrons
63. Which is the most suitable reagent among the (d) 6 p-orbitals and 6 unpaired electrons
following to distinguish compound (3) from rest 68. Which of the following chemical system is non
of the compounds ? [1989] aromatic? [NEET Kar. 2013]
1. CH 3 - C º C - CH 3
(a) (b)
2. CH 3 - CH 2 - CH 2 - CH 3
3. CH 3 - CH 2C º CH
(c) (d)
4. CH 3 - CH = CH 2. S
Hydrocarbons 131
69. Some meta-directing substituents in aromatic 75. Which of the following species is not
substitution are given. Which one is most electrophilic in nature? [2010]
deactivating? [NEET 2013] Å Å
(a) –SO3H (b) –COOH (a) NO 2 (b) Cl
(c) –NO2 (d) –C º N Å
70. Which of the following compounds will not (c) BH3 (d) H3O
undergo Friedal-Craft’s reaction easily : 76. Which one of the following is most reactive
[NEET 2013] towards electrophilic attack ? [2008]
(a) Xylene (b) Nitrobenzene NO2
CH2OH
(c) Toluene (d) Cumene
71. Among the following compounds the one that (a) (b)
is most reactive towards electrophilic nitration is:
[2012] Cl
(a) Benzoic acid (b) Nitrobenzene
(c) Toluene (d) Benzene OH
72. Which one of the following is most reactive (c) (d)
towards electrophilic reagent ? [2011]
CH3 77. The order of decreasing reactivity towards an
(a) electrophilic reagent, for the following would be
OCH3 [2007]
CH3 (i) benzene (ii) toluene
(b) (iii) chlorobenzene (iv) phenol
(a) (ii) > (iv) > (i) > (iii) (b) (iv) > (iii) > (ii) > (i)
OH
(c) (iv) > (ii) > (i) > (iii) (d) (i) > (ii) > (iii) > (iv)
CH3
78. Using anhydrous AlCl3 as catalyst, which one
(c) of the following reactions produces
NHCOCH3 ethylbenzene (PhEt)? [2004]
CH3
(a) H 3 C - CH 2 OH + C 6 H 6
(d)
CH2OH (b) CH 3 - CH = CH 2 + C6 H 6
73. In the following reaction, C 6 H 5 CH 2 Br
1.Mg, Ether
(c) H 2 C = CH 2 + C 6 H 6
¾¾¾¾¾
+
® X, the product ‘X’ is [2010]
2.H 3O (d) H 3C - CH 3 + C 6 H 6
(a) C6H5CH2CH2C6H5
79. Which one of the following is a free-radical
(b) C6H5CH2OCH2C6H5 substitution reaction? [2003]
(c) C6H5CH2OH
(d) C6H5CH3 (a) CH 3CHO + HCN ¾
¾® CH 3CH ( OH ) CN
74. Which one is most reactive towards electrophilic CH3 CH2Cl
Boiling
reagent? [2010] (b) +Cl2 ¾¾®
CH3 CH3
CH 3
OH CH2OH (c) Anh. AlCl
+CH 3Cl ¾¾¾®
3
(a) (b)
CH2Cl
CH3 CH3 (d) + AgNO2
NHCOCH3 OCH3 CH2NO2
(c) (d) ¾¾®
EBD_8336
132 CHEMISTRY
80. The correct order of reactivity towards the

OCH3 NO2
electrophilic substitution of the compounds
aniline (I), benzene (II) and nitrobenzene (III) is
[2003]
(a) I > II > III (b) III > II > I I II III
(c) II > III > I (d) I < II > III
(a) II > III > I (b) III > II > I
81. For the formation of toluene by Friedal Craft
(c) II > I > III (d) I > II > III
reaction, reactants used in presence of
86. When CH3Cl and AlCl3 are used in Friedel-Crafts
anhydrous AlCl3 are [2000]
reaction, the electrophile is [1994]
(a) C2H2 and CCl4 (b) CH4 and CaCN2 + –
(a) Cl (b) AlCl4
(c) C6H6 and CH3Cl (d) C2H5 OH and Zn
(c) CH3+ (d) AlCl2+
82. Which of the following compounds reacts
87. An example of electrophilic substitution reaction
slower in electrophilic substitution? [2000]
is [1994]
(a) C6H5NO2 (b) C6H5OH
(a) Chlorination of methane
(c) C6H5CH3 (d) C6H5NH2
(b) Conversion of methyl chloride to methyl alcohol
83. Which one of the following compounds will be
(c) Nitration of benzene
most easily attacked by an electrophile?[1998]
(d) Formation of ethylene from ethyl alcohol.
Cl
88. Select the true statement about benzene amongst
(a) (b) the following [1992]
(a) Because of unsaturation benzene easily
CH3 OH
undergoes addition
(c) (d)
(b) There are two types of C – C bonds in
84. Which one of these is not compatible with benzene molecule
arenes? [1997] (c) There is cyclic delocalisation of pi-electrons
(a) Greater stability in benzene
(b) Delocalisation of p-electrons (d) Monosubstitution of benzene gives three
(c) Electrophilic additions isomeric products.
(d) Resonance 89. The most reactive compound for electrophilic
85. Among the following compounds (I-III), the nitration is [1992]
ease of their reaction with electrophiles is, (a) Benzene (b) Nitrobenzene
[1997] (c) Benzoic acid (d) Toluene.
ANSWER KEY
1 (c) 10 (a) 19 (c) 28 (d) 37 (a) 46 (d) 55 (a) 64 (a) 73 (d) 82 (a)
2 (c) 11 (a) 20 (d) 29 (a) 38 (a) 47 (c) 56 (c) 65 (a) 74 (d) 83 (d)
3 (c) 12 (c) 21 (a) 30 (d) 39 (c) 48 (b) 57 (d) 66 (b) 75 (d) 84 (c)
4 (d) 13 (a) 22 (d) 31 (c) 40 (a) 49 (b) 58 (c) 67 (d) 76 (c) 85 (d)
5 (c) 14 (a) 23 (a) 32 (c) 41 (c) 50 (a) 59 (b) 68 (a) 77 (c) 86 (c)
6 (b) 15 (d) 24 (b) 33 (a) 42 (a) 51 (c) 60 (a) 69 (c) 78 (c) 87 (c)
7 (a) 16 (b) 25 (c) 34 (a) 43 (b) 52 (a) 61 (c) 70 (b) 79 (b) 88 (c)
8 (b) 17 (c) 26 (d) 35 (d) 44 (d) 53 (b) 62 (c) 71 (c) 80 (a) 89 (d)
9 (a) 18 (b) 27 (b) 36 (b) 45 (a) 54 (d) 63 (d) 72 (b) 81 (c)
Hydrocarbons 133
Hints & Solutions

1. (c) Chlorination of neopentane with Cl2 in the 6. (b) The bulky methyl groups are maximum away
presence of diffused sunlight gives only one from each other.
mono-chloro compound
Eclipsed conformation is the highest energy
CH3 conformation because of unfavorable interactions
| between the electrons in the front and back C – H
UV light bonds. The energy of eclipsed conformation is
CH3 — C — CH 3 + Cl 2 ¾¾¾¾ ®
| approx. 3 kcal/mol higher than stagged
CH3 conformation.
7. (a) Due to hydrogen bonding between the two
CH3 OH groups, gauche conformation of ethylene
| glycol (a) is the most stable conformation.
CH3 — C — CH 2Cl + HCl
| H
O
CH3
H O
1-chloro-2, 2-dimethyl propane
H
All the hydrogen atoms are similar hence only
one mono-chloro compound is formed.
H H
Br Na
2. (c) 2 ® CH – Br ¾¾¾
CH 4 ¾¾¾ 3 ® H
hv ether
8. (b) During cracking, higher hydrocarbons
CH 3 – CH 3 (liquid) are converted to lower gaseous
(less than four 'C') hydrocarbons.
3. (c) There is no change in bond angles and bond 9. (a) A compound is said to exhibit optical
lengths in the conformations of ethane. isomerism if it atleast contains one chiral carbon
4. (d) In staggered conformation any two atom, which is an atom bonded to 4 different
hydrogen atoms on adjacent carbon atoms are atoms or groups.
as far apart as possible, thereby minimising CH3
repulsion between the electron clouds of s- |
bonds of two non-bonded H-atoms (torsional (CH 3 ) 2 CH - C* - CH 2 CH 3
|
strain) H
H HH Br
H H 10. ¾® C 2 H 6 + Mg
(a) C2 H 5 MgBr + H 2 O ¾
OH
H 11. (a) Gasoline (petrol) is a mixture of alkanes,
H H H H alkenes and aromatic hydrocarbons. The quality
H
H of a gasoline is determined by the amount of
Staggered form Eclipsed form branched chain hydrocarbons (2,2,4-
No torsional strain trimethylpentane, commonly known as iso-
5. (c) Conformers are form of stereoisomers in octane) present in it.
which isomers can be interconverted by rotation 12. (c) Order of stability : staggered (anti) > gauche
about single bonds. I and II are staggered and > skew boat > eclipsed.
eclipsed conformers respectively.
EBD_8336
134 CHEMISTRY
Newman projection of n-butane is given as

17. (c)
CH3 CH3 CH3
H H H3C H
H
H3C
H H H H H
H H
CH3 H
staggered (Anti) Eclipsed Skew or gauche
The staggered conformation is most stable in which

methyl groups are as far as possible, due to
minimum repulsion between methyl groups and is 18. (b) CH 3C = C - CH 3
| |
also called anti conformation. CH 3 CH3
13. (a) Electrolysis of a concentrated aqueous
solution of either sodium or potassium salts of 2,3-Dimethyl-2-butene
saturated carboxylic acids yields higher alkane
at anode. (a) (CH3)2CH – CH – CH = CH2 contain 7
|
Kolbe's Method carbon atoms CH3
(b)
2RCOOK ¾¾¾¾¾® 2RCOO - + 2K +
Electrolytic
CH3 CH3
Oxidation Anode Cathode
CH3 – C – CH = CH2+ H ¾® CH3 – C – CH – CH3
At anode 2RCOO- ® 2RCOO + 2e – ¾¾
®
CH3 CH3
R — R + 2CO 2 Rearrangement
At Cathode 2K + + 2e – ® 2K CH3
CH3 CH3 CH3
2K + H 2O ® 2KOH + H 2 C=C ¾® CH3 – C – C
CH3 CH3 CH3
hv H
14. (a) Cl2 ¾¾¾¾¾¾¾¾ ® 2 Cl• 2, 3 - dimethyl – 2 - butene (Stable 3° carbocation)
Chain initiation step
15. (d) The reactivity of H-atoms depends upon
The driving force of the reaction is the stability of
the stability of free radicals, follows the order the carbocation. Tertiary carbocation is more stable
Tertiary > secondary > primary. than secondary carbocation which is achieved by
Therefore, reactivity of H-atoms follows the 1, 2-rearrangement
same order, i.e., tertiary > secondary > primary. 19. (c) 1-chloro-1-methylcyclohexane.
R R H H CH3
| | | | Cl
R – C• > R - C • > R - C • > H - C •
| | | |
R H H H
Tertiary Secondary primary free methyl
free radical free radical radical free radical CH2 CH3 CH3
16. (b) Cl
–
+ H – Cl + Cl
O
CH2 – CH = CH2 CH2 – C – H
CH3 CH3 CH3
O
(i) O 3 Cl
+ H H
(ii) Zn.H 2O H–C–H
+ H – Cl + Cl
Methanal
Hydrocarbons 135
20. (d) CH3 CH3

H3C
CH3— C = CH — CH 3 + CH3— CH — CH = CH2
H3C
O3 O=C 2-methyl-but-2-ene 3-methyl
¾¾¾®
CH3 Zn CH3 butene-1 (20%)
+ H 2O (80%)
OHC (B)
(A)
21. (a) No. of double bonds = 4 In this case, dehydration is governed by
No. of p bond electrons Saytzeff’s rule, according to which hydrogen is
= 2 × no. of double bond preferentially eliminated from the carbon atom
=2× 4=8 with fewer number of hydrogen atoms i.e., poor
becomes poorer. Thus, 2-methyl but-2-ene is the
major product.
22. (d) C6H5—CH=CH—CH3 + HBr CH3
¾®
HBr, dark
Å (ii) CH3— C = CH — CH 3 ¾¾¾®
in absence
C6H5—CH—CH2—CH3 (A) of peroxide
(Benzyl carbocation)
(CH3) 2— CH — CH — CH 3 +
¾®
–
Br
Br
C6H5—CH—CH2—CH3 (Minor)
CH 3
Br
CH3 — C — CH2 – CH3
CH3
H
+
Br
23. (a) C CH CH2 (Major)
This reaction is governed by Markownikoff’s
CH3 rule according to which when an unsymmetrical
CH3 CH3 reagent e.g. HBr adds to an unsymmetrical
OH
– alkene, then the negative part of the reagent is
C CH CH3 ¾¾® C CH CH3 added to that carbon atom of the double bond
Å
which bears the least number of hydrogen atom.
CH3 H3C OH Thus, in above case 2-methyl-2-bromobutane
¾¾®
1,2-methyl shift (Minor) will be the major product.

(A)
Peroxide effect is shown by HBr only because
OH CH3 H–Cl bond is stronger than H-Br and is not cleaved
OH–
by the free radicals, whereas H–I bond is weaker
C CH CH3 C CH CH3 and Iodine free radical combine to form iodine
molecule.
CH3 CH3 CH3
3° cabocation (Major)
25. (c) So the IUPAC name of the compound is 1-
(more stable) B butene-3-yne.
If both the double and triple bonds are present in
Tertiary carbocation is more stable hence gives
the compound, it is regarded as derivative of
major product. alkyne. Further if double and triple bonds are at
equidistance from either side, the preference is given
to double bond.
CH3
24. H/ Heat
(b) (i) CH3— CH — CH — CH3 ¾¾®
+
26. (d) Alkenes with double bonds cannot undergo
free rotation and can have different geometrical
OH shapes with two different groups on each end of
the double bond.
EBD_8336
136 CHEMISTRY
H3C CH3 H 28. (d)

C=C C=C H3C — C = CH — CH3
H H H CH3
CH3
cis-But-2-ene trans-But-2-ene
27. (b) The formed 2° carbocation will rearrange H3C O H
O
to a more stable 3° carbocation as: 3
¾® C C
H3C CH3
CH3 O O
CH — CH — CH 3 ¾® O O
H2O
CH ¾¾® CH3 – C – CH3 + CH3 – C – H
–H2O2 acetone acetaldehyde
CH3 29. (a) Option (a) and (b) are more stable due to
more hyperconjugated (6a – H) hydrogen atoms
Br
C — CH 2 — CH3 ¾® cis-2-butene (option a) is less hindered that 2-
methyl propene (option b).
CH3 Thus, hydrogenation will be fastest for cis-2-
butene.
CH3
H3C — C — CH2 – CH3 As catalytic hydrogenation happens on the surface
of catalysis on the some side of molecule therefore
Br the rate of catalytic hydrogenation depends on
stability of alkene and steric hindrance on the
2-Bromo-2-methyl butane molecule.
(Major product)
H3C 30. (d) In presence of peroxide, HBr adds on

| CH – CH = CH2
|
alkenes according to anti–markownikoff’s rule.

H3C 3– methyl-1-butene
Peroxide
H3CCH = CH 2 + HBr ¾¾¾¾® H3C CH 2CH 2Br
CH3 +
CH – CH2 – CH2 Propene n - propyl bromide
| (1°)
|
+ CH3 Kharasch observed that the addition of HBr to

+H
CH3 + unsymmetrical alkene in the presence of organic
| CH – CH – CH3 peroxides follows an opposite course to that
|
CH3 (2°)
suggested by Markownikoff. This is termed
Of the two possibilities, 2° carbocation is more anti-Markownikoff or peroxide effect.
stable so the product of the reaction is expected CH3
to be predominantly formed by 2° carbocation |
4® NaIO
31. (c) CH3 - C = CH - CH3 ¾¾¾
i.e. CH 3 - CH - CH - CH 3 KMnO4
| | O
CH 3 Br ||
CH 3 - C - CH 3 + CH 3COOH
i.e. 2– Bromo-3-Methylbutane 32. (c) Geometrical isomers differ in spatial
arrangement of atoms.
Some electrophilic addition reaction form products 33. (a)
that are clearly not the result of the addition of
electrophile to the sp 2 carbon bonded with the H CH3 H O CH3
| | O
most hydrogen and the addition of a nucleophile 3
to the other sp2 carbon. CH 3 – CH2– C = C CH3 – CH2– C C
The unexpected product resu lts from a | | |
rearrangement of carbocation intermediate. Please CH3 O–O CH3
O
note that all carbocation do not rearrange. ||
CH3– C – CH3+ CH3 CH2CHO
(–H 2O)
Hydrocarbons 137
34. (a) Reaction conditions for alcohol in 40. (a)

preparation of alkenes are : H2
Al2O3
CH3 - CH2 - CH = CH - CH2 - CH3 Platinum
®
R — CH 2 — CH 2OH ¾¾¾¾ (A )
350º -380ºC
CH3 - CH2 - CH 2 - CH2 - CH2
HBr
R — CH = CH 2 + H 2O n-hexane |
CH3
At 220º – 250ºC it forms ether. CH3 - CH 2 - CH - CH2 - CH2 - CH3
|
Br
35. (d) We know that 41. (c) CH3
B H CH CH CH2 CH3
6CH3 - CH = CH 2 ¾¾¾®
2 6
Propene ether, 0°C

CH3
H2O2
2(CH3CH2CH2 )3 B ¾¾¾® Due to presence of two similar methyl groups at
OH- same carbon atom, above compound doesn’t
6CH3CH 2 CH 2 OH + 2H 3 BO3 show geometrical isomerism.
Propanol 42. (a) When 3, 3 dimethyl – 2-butanol is heated
with H2SO4 the major product obtained is 2, 3-
36. (b) dimethyl – 2-butene.
H H3C H3C CH3 CH3
C=C C=C |
> Conc.H SO
H3C H H H CH3 - CH - C - CH3 ¾¾¾¾¾¾
2 4®
| |
> CH2 = CH – CH2 – CH3 OH CH3
Due to more hyper-conjugation in cis-2-butene 3,3-dimethyl - 2-butanol
(6a - H atoms) than in 1-butene (2a - H atoms), CH3 CH3
the former is more stable. +
In trans-2-butene, the two methyl groups are for CH3 – CH – C – CH3 ¾® CH3 – CH – C – CH3 ¾®
apart. Hence, it is most stable. + OH2 CH3 CH3
37. (a) When similar atoms are on the opposite side,
the compound is in trans-form. CH 3 CH3
+
H CHO CH3– CH – C – CH 3 ¾® CH3 – C = C – CH3
C C CH3 CH3
C3H7 H 2, 3-dimethyl-2-butene
B2 H6
38. (a) Since hydrocarbon C gives only CH2O, on 43. (b) 6 R - CH = CH 2 ¾¾¾® 2(RCH 2CH 2 )3 B
ozonolysis, C should be CH2 = CH2, Hence going Ether,0°C ( B)
backward, A should be ethane. Thus, the H O
reactions are ¾¾¾®
2 2 6RCH 2 CH 2OH + 2H 3BO3 .
NaOH
Cl2 /hn alc.
CH3CH3 ¾¾¾¾ ® CH3CH 2Cl ¾¾®
KOH 44. (d) Of all the options listed CH3CH2CH2CH3
(A) (B) has the least number of C-atoms and hence has
CH 2=CH 2 ¾O¾3 /¾ the lowest b.p.
¾® HCHO
H2O
(C) D ( D) 45. (a) Addition of HCl to propene even in the
39. (c) We know that presence of benzoyl peroxide occurs according
NaHCO to Markovnikov’s rule :
CH2 = CH 2 + HOCl ® CH 2 OH ¾¾¾® 3
CH2 OH
| | HCl
CH2 Cl CH2 OH CH3 - CH = CH 2 ¾¾¾¾¾¾®
(C6 H5CO)2 O 2
M = CH 2 OH - CH 2 Cl and R = NaHCO3
CH 3 - CHCl - CH 3
EBD_8336
138 CHEMISTRY
52. (a)
Peroxide effect is observed only in case of NaNH
Å
HBr. HC º CH ¾¾¾¾
2 ® HC º CNa
liq. NH 3
46. (d) Restricted rotation about carbon carbon H C–CH · Br

¾¾¾¾¾¾
3 2 ® HC º C – CH 2 – CH3
double bond in 2-butene is due to sideways (X)
overlap of two p-orbital. 1-Butyne NaNH 2 liq. NH3
Å
Rotation around p bond is not possible. If any H C -CH – Br
¬¾¾¾¾¾
3 2 ¾ H3C – CH 2 – C º C N a
attempt is made to rotate one of the carbon atoms,
the lobes of p-orbital will no longer remain H3C – CH 2 – C º C – CH 2 – CH3
coplanar i.e no parallel overlap will be possible 3-Hexyne (Y)
and thus p-bond will break . This is known as
concept of restricted rotation. In other words 53. (b) The combustion reaction of ethylene is
the presence of p-bonds fix the position of two
5
carbon atoms. C 2 H 2 + O2 ® 2CO2 + H 2 O
2
47. (c) Such isomers, which possess the same
Both HC CH and CO2 have sp hybridization.
molecular and structural formula but differ in
the arrangement of atoms around the double O
bonded carbon atoms are known as geometrical P
Hg +2 / H2SO 4
isomers. 54. (d) CH º CH ¾¾¾¾¾¾
® CH3 - C - H
H - C - Cl H - C - Cl CH3CHO does not give Victor Meyer test.
|| || 55. (a) 1-Butyne and 2-butyne are distinguished
H - C - Cl Cl - C - H by NaNH2 because 1-Butyne react with NaNH2
(cis) (trans) due to presence of terminal hydrogen.
48. (b) CH3 CH2 C CH + NaNH2
1– Butyne
3 h CH3CH 2 C CNa + NH 3
3
i 56. (c) When double and triple, both bonds are
¾¾¾®
present, then ‘lowest set of locants’ rule will
decide the IUPAC name.
3 1 2 3 4 5 (incorrect)
C H3 - C H = C H - C º C H
Number of s 5 4 3 2 1 (correct)
bonds = 21
49. (b) Alkynes can be reduced to cis-alkenes Hence, the correct name will be pent-3-en-1-yne.
with the use of Lindlar’s catalyst 57. (d) The amount of s-character in various hybrid
50. (a) Correct order is orbitals is as follows.
H - C º C - H > H 3C - C º C - H > H 2 C sp = 50%, sp2 = 33% and sp3 = 25%
( Two acidic
hydrogens ) ( One acidic
hydrogen ) Therefore s-character of the C – H bond in
acetylene (sp) is greater than that of the
C – H bond in alkene (sp2 hybridized) which in
= CH 2 > CH3 - CH3
turn has greater s-character of the C – H bond in
51. (c) Hydration of alkynes give ketones. alkanes. Thus, owing to a high s-character of the
C – H bond in alkynes, the electrons constituting
OH this bond are more strongly held by the carbon
H3 C - C º CH ¾¾
® H3C - C = CH 2 nucleus with the result the hydrogen present on
(A) such a carbon atom can be easily removed as
O
proton. The acidic nature of three types of C – H
Tautomerism
H3 C - C - CH3
¾¾¾¾® bonds follows the following order
(B) º C - H > = C - H > - C - H.
Hydrocarbons 139
Further, as we know that conjugate base of a 62. (c) On heating ethylene chloride (1, 1 dichloro
strong acid is a weak base, hence the correct ethane) with alcoholic KOH followed by
order of basicity is sodamide, alkyne is obtained
(- ) (- ) (-) R - CH 2 - CCl 2 - R
H - C º C < CH 2 = CH < CH 2 - CH3
alc.KOH
¾¾¾¾® R - CH = CCl - R
58. (c) CH3 - CH 2 - C º CH + HCl
NaNH
¾¾¾¾ 2®R - C º C - R
® CH3 - CH 2 - C = CH 2
¾¾ 63. (d) Br2 in CCl4 (a), Br2 in CH3 COOH (b) and
|
Cl alk. KMnO4 (c) will react with all unsaturated
compounds, i.e., 1, 3 and 4 while ammoniacal
I AgNO3 (d) reacts only with terminal alkynes,
| i.e., 3 and h ence compound 3 can be
HI
¾¾® CH3 - CH 2 - C - CH3
| distinguished from 1, 2 and 4 by. ammoniacal
Cl AgNO3 (d).
64. (a) The acidity of acetylene or 1–alkynes can
According to Markownikoff’s rule which states be explained on the basis of molecular orbital
that when an unsymmetrical alkene undergo concept according to which formation of
hydrohalogenation, the negative part goes to C–H bond in acetylene involves sp-hybridised
the C-atom which contain lesser no. of H-atom. carbon atom.
O
59. (b) CH 3 - C º C - CH 2 - CH 3 ¾¾3 ® s electrons are closer to the nucleus than p electrons,
the electrons present in a bond having more s-
O character will be correspondingly more closer to
2H O the nucleus.
CH3– C – C – CH2 – CH3 ¾®
2
Thus, owing to high s character of the C—H bond
O O in alkynes (s = 50%), the electrons constituting this
bond are more strongly held by the carbon nucleus
(i.e., the acetylenic carbon atom) or the sp orbital
(O ) acts as more electronegative species than the sp2
CH 3 - C O + H 2O2 ¾¾
¾®
| and sp 3 with the result the hydrogen present on
CH3CH 2CO such a carbon atom (º C—H) can be easily removed
Methylethy lglyoxal
as a proton.
65. (a) Enthalpy of hydrogenation
CH3COOH + CH3CH 2COOH
Acetic acid Propionic acid 1
µ
The glyoxal formed as an intermediate is stability of alkene
oxidised by H2O2 to give the acids.` \ III > II > I
60. (a) Only C2H2 (acetylene) has acidic H-atoms 66. (b) 2C6 H 6 (g) + 9O 2 (g) ¾¾¾®
2 5 VO
and hence reacts with NaNH2 to form sodium 410°C
salt, i.e., O
HC º CH + NaNH2 ¾ ¾® HC º CNa + NH3. CH—C
61. (c) Reduction of alkynes with Na/liq. NH3 2 O + 4CO2(g) + 4H2O(g)
gives trans-alkenes. This reaction is called Birch CH—C
reduction
CH 3 - C º C - CH 3 + H 2 O
Maleic anhydride
H3C H 67. (d) Presence of 6 p orbitals, each containing
Na / liq. NH
¾¾¾¾¾¾
3® C=C one unpaired electron, in a six membered cyclic
H CH3 structure is in accordance with Huckel rule of
trans-Butene or trans-2-Butene aromaticity.
EBD_8336
140 CHEMISTRY
68. (a) Huckel rule is not obeyed. It has only four 76. (c) Out of the given compounds the most
electrons. Further it does not have continous reactive towards nucleophilic attack is
conjugation. OH
In thiophene, one lone pair of electrons are involved
in delocalisation.
S Phenoxide ion is stable due to resonance.

Thus, the effective number of p-electrons become 77. (c) Electrophiles have high affinity for electrons.
6 which is of the form (4n + 2). Also the ring is
planar, hence this is an aromatic compound. They attack at the site where electron-density is
highest. Electron donating groups increases the
69. (c) Decreasing order of deactivating effect of electron density. The electron donating tendency
the given m-directing group is decreases in the order :
> NO2 > – CN > – SO3H > – COOH –OH > –CH3 > –H > –Cl
—NO2 group is most deactivating group due Therefore, the correct order of reactivity towards
to strong – E, – I and – M effects. electrophile is
70. (b) –NO2 is a powerful electron withdrawing C6H5OH > C6H5CH3 > C6H6 > C6H5Cl
group. Its presence on ring makes the ring less
active. AlCl
78. (c) C6H6 + CH2 = CH2 ¾¾¾
3®C H CH CH
6 5 2 3
71. (c) Electrophilic rate order
79. (b) In the presence of UV rays or energy O2 by
CH3 COOH NO2 boiling, free radical is generated which attack the
methyl carbon atom of toluene.
CH3 CH2
> > > D
¾® +H
Toluene Benzene Benzoic acid Nitrobenzene
Since nitration is an electrophilic substitution benzyl free
radical
hence presence of electron releasing group like
hn
CH3 in the nucleus facilitates nitration. Cl2 ¾¾® 2Cl•
72. (b) Due to + M effect of – OH group and •CH
hyperconjugation of – CH3 group. 2 CH2Cl
•
ether + Cl ¾®
73. (d) C6H5CH2Br + Mg ¾¾¾®
80. (a) Amino group is ring activating while nitro
+
H2O/H
C6H5CH2MgBr ¾¾¾¾ ® C6H5CH3 + Mg Br(OH) group is deactivating. Hence, correct order is
aniline > benzene > nitrobenzene.
CH3 I > II > III
OCH3 NH2 NO2
74. (d)
Among –OH, –CH2OH, –NHCOCH3 and –OCH3,

methoxy group has the highest +M effect. I II III
H –NO2 is an electron attracting group hence

75. (d) H3O + H – O+– H has a lone pair of decrease the electron density on ring, whereas –
gg NH2 group is electron releasing group hence
electrons on oxygen atom, thus it is not an increase electron density on ring. Benzene is also
electrophile. Also the octet is complete. e– rich due to delocalization of electrons.
Hydrocarbons 141
81. (c) 85. (d) –OCH3 activates the benzene ring. –NO2
CH3 deactivates the ring. Hence, the reaction of the
given compounds with electrophiles is in the
anhydrous AlCl
+ CH3Cl ¾¾¾¾¾®
3
+ HCl order, I > II > III.
Å
82. (a) CH3 and NH2 and OH are electron donating 86. ¾® CH ·3 + AlCl4–
(c) CH3Cl + AlCl3 ¾
groups, whereas NO2 is an electron withdrawing
Electrophile
group and leaves the benzene ring deactivated.
Due to stronger electron attracting (–I effect) 87. (c) Chlorination of methane proceeds via free
effect of NO2 group, C6 H5NO2 shows least radical mechanism. Conversion of methyl
reactivity towards electrophilic substitution. chloride to methyl alcohol proceeds via
83. (d) –Cl atom shows o/p-directive influence nucleophilic substitution. Formation of ethylene
but deactivate the benzene ring, while from ethyl alcohol proceeds via dehydration
[–OH/–CH3] groups show o/p influence and reaction. Nitration of benzene is electrophilic
activate the benzene ring but –OH group is more substitution reaction.
activating than –CH3. 88. (c) Benzene do not show addition reaction like
Hence order of electrophilic substitution other un saturated hydrocarbons. Due to
resonance all the C – C bonds have the same
OH CH3 Cl nature, which is possible because of the cyclic
delocalisation of p-electrons in benzene.
Monosubstitution will give only a single product.
89. (d) Due to + I-effect of the CH3-group, toluene
84. (c) In arenes, p electrons are delocalised, hence has much higher electron density in the ring than
arenes do not undergo addition reactions easily. benzene, Nitrobenzene and benzoic acid.
Aromatic compounds (Arenes) are highly stable Nitro and carboxylic group show- I-effect and
and show resonance eg. Benzene is the simplest hence deactivate the ring towards electrophillic
example. substutution .
EBD_8336
142 CHEMISTRY
14 Environmental
Chemistry
2020 2019 2018 2017 2016

green house effect 1 E
Air pollution
air pollution 1 E
Water and soil
soil pollution 1 E
pollution
Topic 1: Air Pollution 5. The greenhouse effect is because of the

1. Among the following, the one that is not a green (a) presence of gases, which in general are
house gas is: [2019] strong infrared absorbers, in the atmosphere
(a) nitrous oxide (b) methane (b) presence of CO2 only in the atmosphere
(c) ozone (d) sulphur dioxide (c) pressure of O3 and CH4 in the atmosphere
2. Which oxide of nitrogen is not a common (d) N2O and chlorofluorohydrocarbons in the
pollutant introduced into the atmosphere both atmosphere [1996]
due to natural and human activity? [2018] 6. Which of the following is/are the hazardous
(a) N2O5 (b) NO2 pollutant(s) present in automobile exhaust gases?
(c) NO (d) N2O (i) N2 (ii) CO
3. Which of the following is not a common
(iii) CH4 (iv) Oxides of nitrogen
component of Photochemical Smog? [2014]
(a) (ii) and (iii) (b) (i) and (ii) [1996]
(a) Ozone
(b) Acrolein (c) (ii) and (iv) (d) (i) and (iii)
(c) Peroxyacetyl nitrate
Topic 2: Water and Soil Pollution
(d) Chlorofluorocarbons
4. Which one of the following statements regarding 7. The liquified gas that is used in dry cleaning
photochemical smog is not correct? [2012] along with a suitable detergent is
(a) Carbon monoxide does not play any role in [NEET Odisha 2019]
photochemical smog formation. (a) CO2 (b) Water gas
(b) Photochemical smog is an oxidising agent in (c) Petroleum gas (d) NO2
character.
8. Which of the following is a sink for CO? [2017]
(c) Photochemical smog is formed through
(a) Microorganism present in the soil
photochemical reaction involving solar energy.
(b) Oceans
(d) Photochemical smog does not cause
(c) Plants
irritation in eyes and throat.
(d) Haemoglobin
Environmental Chemistry 143
(a) CO2 (b) Water gas (c) Fluoride deficiency in drinking water is
(c) Petroleum gas (d) NO2 harmful. Soluble fluoride is often used to
8. Which of the following is a sink for CO? [2017] bring its concentration upto 1 ppm.
(a) Microorganism present in the soil (d) When the pH of rain water is higher than 6.5,
it is called acid rain.
(b) Oceans
11. Which one of the following statement is not
(c) Plants
true ? [2011]
(d) Haemoglobin
(a) pH of drinking water should be between
9. Roasting of sulphides give the gas X as a by 5.5 – 9.5.
product. This is colorless gas with choking smell
(b) Concentration of DO below 6 ppm is good
of burnt sulphur and caused great damage to
for the growth of fish.
respiratory organs as a result of acid rain. Its
aqueous solution is acidic, acts as a reducing (c) Clean water would have a BOD value of less
agent and its acid has never been isolated. The than 5 ppm.
gas X is : [NEET 2013] (d) Oxides of sulphur, nitrogen and carbon are
(a) SO2 (b) CO2 the most widespread air pollutant.
(c) SO3 (d) H2S 12. Green chemistry means such reactions which
10. Which one of the following statements is not (a) produce colour during reactions [2008]
true? [NEET Kar. 2013]
(b) reduce the use and production of hazardous
(a) Dissolved oxygen (DO) in cold water can chemicals
reach a concentration upto 10 ppm.
(c) are related to the depletion of ozone layer
(b) Clean water would have a BOD value of 5
(d) study the reactions in plants
ppm.
ANSWER KEY
1 (d) 2 (a) 3 (d) 4 (d) 5 (a) 6 (c) 7 (a) 8 (a) 9 (a) 10 (d)
11 (b) 12 (b)
Hints & Solutions

1. (d) Sulphur dioxide is not a green house gas. Hydrocarbons + O 2 , NO 2 , NO, O, O 3 ®
2. (a) Nitrous oxide (N2O) occurs naturally in Peroxides, formaldehyde, peroxyacetyl-nitrate
environment. (PAN), acrolein etc. Hence, chlorofluoro carbons
In automobile engine, when fuel is burnt are not common component of photochemical
dinitrogen and dioxygen combine to yield NO smog.
and NO2. 4. (d) The oxidised hydrocarbons and ozone in
Thus, N2O5 is the answer. presence of humidity cause photochemical
3. (d) The oxidised hydrocarbons and ozone in smog.
presence of humidity cause photochemical Hydrocarbons + O 2 , NO 2 , NO, O, O 3
smong. ® Peroxides, formaldehyde, peroxyacetylnitrate
(PAN), acrolein etc.
EBD_8336
144 CHEMISTRY
It is oxidising in nature and causes irritation to
Microorganism present in soil convert CO to CO2,
eyes, lungs, nose, asthamatic attack and damage thus it's sink.
plants.
5. (a) Green house gases such as CO2, ozone, 9. (a) Based on the features given, gas must be SO2.
methane, the chlorofluoro carbon compounds 10. (d) Acid rain is the rain water containing
and water vapour form a thick cover around the sulphuric acid and nitric acid which are formed
earth which prevents the IR rays emitted by the from the oxides of sulphur and nitrogen present
earth to escape. It gradually leads to increase in in the air as pollutants. Rain water has a pH
temperature of atmosphere. below 5.6.
11. (b) The growth of fishes get hindered if the
Water vapour is the largest contributor to the earth's concentration of D.O. is below 6 ppm.
greenhouse effect. However water vapour does not 12. (b) Green chemistry are the reaction, which
control the Earth's temperature. reduces the use of hazardous chemicals.
6. (c) CO and oxides of Nitrogen are poisonous Green chemistry is the programme of developing
gases present in automobile exhaust gases. new chemical products and chemical processes or
7. (a) Liquified CO2 (carbon dioxide) with a making improvements in the already existing
compounds and processes so as to make them less
suitable detergent is used in dry cleaning.
harmful to human health and environment. This
8. (a) Microorganisms present in the soil is a sink means the same as to reduce the use and production
for CO. of hazardous chemicals.
The Solid State 145
15 The Solid State

2020 2019 2018 2017 2016

relation between r
1 A
and a
formula of
Cubic system and
compound and 1 A
Bragg's equation
voids
density ratio and
1 D
structure
Topic 1: Properties and Types of Solids Topic 2: Crystal Structure of Solids

1. A solid with high electrical and thermal 5. A solid compound XY has NaCl structure. If the
conductivity from the following is [1994] radius of the cation is 100 pm, the radius of the
(a) Si (b) Li anion (Y –) will be : [2011 M]
(c) NaCl (d) Ice (a) 275.1 pm (b) 322.5 pm
2. The pure crystalline substance on being heated (c) 241.5 pm (d) 165.7 pm
gradually first forms a turbid liquid at constant 6. The pyknometric density of sodium chloride
temperature and still at higher temperature crystal is 2.165 × 103 kg m–3 while its X-ray
turbidity completely disappears. The behaviour density is 2.178 × 103 kg m–3. The fraction of
is a characteristic of substance forming [1993] unoccupied sites in sodium chloride crystal is
(a) Allotropic crystals [2003]
(b) Liquid crystals (a) 5.96 × 10 –3 (b) 5.96
(c) Isomeric crystals (c) 5.96 × 10–2 (d) 5.96 × 10–1
(d) Isomorphous crystals. 7. When molten zinc is converted into solid state,
3. Most crystals show good cleavage because their it acquires hcp structure. The number of nearest
atoms, ions or molecules are [1991] neighbours will be [2001]
(a) weakly bonded together (a) 6 (b) 12
(b) strongly bonded together (c) 8 (d) 4
(c) spherically symmetrical 8. In the solid state, MgO has the same structure
(d) arranged in planes. as that of sodium chloride. The number of
4. The ability of a substances to assume two or oxygens surrounding each magnesium in MgO
more crystalline structures is called [1990] is [1999]
(a) Isomerism (b) Polymorphism (a) 6 (b) 1
(c) Isomorphism (d) Amorphism (c) 2 (d) 4
EBD_8336
146 CHEMISTRY
9. For orthorhombic system, axial ratios are is 2.72 g cm–3. The molar mass of the metal is :
a ¹ b ¹ c and the axial angles are [1991] (NA, Avogadro’s constant = 6.02 × 1023 mol-1)
(a) a = b = g ¹ 90° [NEET 2013]
(b) a = b = g = 90° (a) 30 g mol–1 (b) 27 g mol–1
(c) a = g = 90°, b ¹ 90° (c) 20 g mol–1 (d) 40 g mol–1
(d) a ¹ b ¹ g = 90° 16. Structure of a mixed oxide is cubic close-packed
(c.c.p). The cubic unit cell of mixed oxide is
Topic 3: Cubic System and Bragg's Equation composed of oxide ions. One fourth of the
10. An element has a body centered cubic (bcc) tetrahedral voids are occupied by divalent metal
A and the octahedral voids are occupied by a
structure with a cell edge of 288 pm. The atomic
monovalent metal B. The formula of the oxide is :
radius is: [2020]
[2012 M]
2 4 (a) ABO2 (b) A2BO2
(a) ´ 288pm (b) ´ 288pm
4 3 (c) A2B3O4 (d) AB2O2
4 17. The number of octahedral void(s) per atom
´ 288pm 3 present in a cubic close-packed structure is :
(c) (d) ´ 288pm
2 4 [2012]
11. A compound is formed by cation C and anion A. (a) 1 (b) 3
The anions form hexagonal close packed (hcp) (c) 2 (d) 4
lattice and the cations occupy 75% of octahedral 18. A metal crystallizes with a face-centered cubic
voids. The formula of the compound is: lattice. The edge length of the unit cell is 408
[2019] pm. The diameter of the metal atom is : [2012]
(a) C2A 3 (b) C3A 2 (a) 288 pm (b) 408 pm
(c) C3A 4 (d) C4A 3 (c) 144 pm (d) 204 pm
12. Iron exhibits bcc structure at room temperature. 19. AB crystallizes in a body centred cubic lattice
Above 900°C, it transforms to fcc structure. The with edge length ‘a’ equal to 387 pm. The
ratio of density of iron at room temperature to distance between two oppositely charged ions
that at 900°C (assuming molar mass and atomic in the lattice is : [2010]
radii of iron remains constant with temperature) (a) 335 pm (b) 250 pm
is [2018] (c) 200 pm (d) 300 pm
20. Copper crystallises in a face-centred cubic lattice
3 4 3 with a unit cell length of 361 pm. What is the
(a) (b)
2 3 2 radius of copper atom in pm?[2009]
1 3 3 (a) 157 (b) 181
(c) (d) (c) 108 (d) 128
2 4 2 21. Lithium metal crystallises in a body centred cubic
13. Which of the following statements about the crystal. If the length of the side of the unit cell of
interstitial compounds is incorrect ? lithium is 351 pm, the atomic radius of the lithium
[NEET 2013] will be: [2009]
(a) They are chemically reactive. (a) 151.8 pm (b) 75.5 pm
(b) They are much harder then the pure metal. (c) 300.5 pm (d) 240.8 pm
(c) They have higher melting points than the 22. Percentage of free space in a body centred cubic
pure metal. unit cell is : [2008]
(d) They retain metallic conductivity. (a) 30% (b) 32%
14. The number of carbon atoms per unit cell of (c) 34% (d) 28%
diamond unit cell is : [NEET 2013] 23. If ‘a’ stands for the edge length of the cubic
(a) 8 (b) 6 systems : simple cubic, body centred cubic and
(c) 1 (d) 4 face centred cubic, then the ratio of radii of the
15. A metal has an fcc lattice. The edge length of spheres in these systems will be respectively,
the unit cell is 404 pm. The density of the metal [2008]
The Solid State 147
1 1 (a) Simple cubic [1997]

1 3 1
(a) a: a: a (b) a : 3a : a (b) Face-centred cubic
2 4 2 2 2 2 (c) Body-centred cubic
1 3 3 (d) None
(c) a: a: a (d) a : 3a : 2a 31. The edge length of a face centred unit cubic cell
2 2 2
24. The fraction of total volume occupied by the is 508 pm. If the radius of the cation is 100 pm,
atoms present in a simple cube is [2007] the radius of the anion is [1996]
(a) 288 pm (b) 398 pm
p p (c) 154 pm (d) 618 pm
(a) (b)
3 2 4 2 32. In the fluorite structure, the coordination number
p p of Ca2+ ion is : [1993]
(c) (d) (a) 4 (b) 6
4 6
25. CsBr crystallises in a body centered cubic lattice. (c) 8 (d) 3
The unit cell length is 436.6 pm. Given that the 33. The number of atoms contained in an fcc unit
atomic mass of Cs = 133 and that of Br = 80 amu cell of a monoatomic substance is [1993]
and Avogadro number being 6.02 × 1023 mol–1, (a) 1 (b) 2
(c) 4 (d) 6
the density of CsBr is [2006]
(a) 0.425 g/cm3 (b) 8.25 g/cm3 Topic 4: Imperfection in Solids
(c) 4.25 g/cm 3 (d) 42.5 g/cm3 34. Formula of nickel oxide with metal deficiency
26. In face-centred cubic lattice, a unit cell is defect in its crystal is Ni 0.98 O. The crystal
shared equally by how many unit cells? [2005] contains Ni2+ and Ni3+ ions. The fraction of
(a) 2 (b) 4 nickel existing as Ni2+ ions in the crystal is
(c) 6 (d) 8 [NEET Odisha 2019]
27. A compound formed by elements X and Y (a) 0.31 (b) 0.96
crystallizes in a cubic structure in which the X (c) 0.04 (d) 0.50
atoms are at the corners of a cube and the Y 35. With which one of the following elements silicon
atoms are at the face-centres. The formula of the should be doped so as to give p-type
compound is [2004] semiconductor ? [2008]
(a) XY3 (b) X3Y (a) Germanium (b) Arsenic
(c) XY (d) XY2 (c) Selenium (d) Boron
28. A compound is formed by elements A and B. 36. If NaCl is doped with 10– 4 mol % of SrCl2, the
The crystalline cubic structure has the A atoms concentration of cation vacancies will be
at the corners of the cube and B atoms at the (NA = 6.02 × 1023 mol–1) [2007]
body centre. The simplest formula of the (a) 6.02 × 1016 mol–1 (b) 6.02 × 1017 mol–1
compound is [2000] (c) 6.02 × 1014 mol–1 (d) 6.02 × 1015 mol–1
(a) AB (b) A6 B 37. The appearance of colour in solid alkali metal
(c) AB6 (d) A8 B4 halides is generally due to [2006]
29. The second order Bragg diffraction of X-rays (a) Schottky defect (b) Frenkel defect
with l = 1.00 Å from a set of parallel planes in a (c) Interstitial positions (d) F-centres
metal occurs at an angle 60º. The distance 38. Schottky defect in crystals is observed when
between the scattering planes in the crystal is [1998]
[1998] (a) an ion leaves its normal site and occupies
(a) 0.575 Å (b) 1.00 Å an interstitial site
(c) 2.00 Å (d) 1.15 Å (b) unequal number of cations and anions are
30. The intermetallic compound LiAg crystallizes in missing from the lattice
a cubic lattice in which both lithium and silver (c) density of the crystal is increased
atoms have coordination number of eight. To (d) equal number of cations and anions are
what crystal class does the unit cell belong ? missing from the lattice
EBD_8336
148 CHEMISTRY
39. When electrons are trapped into the crystal in 40. On doping Ge metal with a little of In or Ga, one
anion vacancy, the defect is known as [1994] gets [1993]
(a) Schottky defect (a) p-type semi conductor
(b) Frenkel defect (b) n-type semi conductor
(c) Stoichiometric defect (c) insulator
(d) F-centres (d) rectifier
ANS WER KEY

1 (b ) 5 (c) 9 (b) 13 (a) 17 (a) 21 (a) 25 (c) 29 (d) 33 (c) 37 (d )
2 (b ) 6 (a) 10 (d) 14 (a) 18 (a) 22 (b) 26 (c) 30 (c) 34 (b) 38 (d )
3 (d ) 7 (b) 11 (c) 15 (b ) 19 (a) 23 (a) 27 (a) 31 (c) 35 (d) 39 (d )
4 (b ) 8 (a) 12 (d) 16 (d ) 20 (d) 24 (d) 28 (a) 32 (c) 36 (b) 40 (a)
Hints & Solutions

1. (b) Out of the given substances, only Li has 9. (b) For orthorhombic system a = b = g = 90°
high electrical and thermal conductivity.
2. (b) Liquid crystals on heating first become 3a
10. (d) For bcc, 3a = 4r Þ r =
turbid and on further heating they become clear. 4
3. (d) Crystals show good cleavage because their Given, a = 288 pm
constituent particles are arranged in planes.
4. (b) The phenomenon of occurrence of a 3
r= ´ 288 pm
substance in two or more crystalline structures 4
is called polymorphism. 11. (c) Oh void (C) : HCP (A)
5. (c) Radius ratio of NaCl like crystal
75
r+ No. of ions Þ 6 ×
100
: 6
= - = 0.414
r 3
100 : 1
r- = = 241.5 pm (r + = 100) 4
0.414 3 : 4 C3 A4
6. (a) Fraction of unoccupied sites in NaCl crystal
4r
x-ray density–pyknometric density 12. (d) For bcc lattice : Z = 2, a =
= 3
x-ray density
2.178 ´ 103 - 2.165 ´ 10 3 0.013 ´ 103
For fcc lattice : Z = 4, a = 2 2r
= =
2.178 ´ 103 2.178 ´ 103 æ ZM ö
= 5.96 × 10–3 d25 °C çè N a3 ÷ø
A bcc
Pyknometric density is nearest to true density \ =
d900 °C æ ZM ö
calculated from the molecular mass and crystalline çè N a3 ÷ø
lattice of the product. A fcc
7. (b) hcp is a closed packed arrangement in 3
which the unit cell is hexagonal and coordination 2 æ 2 2r ö 3 3
number is 12. = ç ÷ =
4 4 r 4 2
8. (a) Since MgO has a rock salt structure. In this ç ÷
è 3 ø
structure each cation is surrounded by six anions
and vice versa.
The Solid State 149
13. (a) Interstitial compounds are chemically inert. a
charged ions = 3
In interstitial compounds small atoms like H, B &
2
387 ´ 1.732
C enter into the void sites between the packed = ; 335pm
atoms of crystalline metal. They retain metallic 2
conductivity and are chemically inert. 20. (d) Since Cu metal crystallises in a face centred
cubic lattice
14. (a) Diamond is like ZnS. In diamond cubic unit a
cell, there are eight corner atoms, six face \ r=
centered atoms and four more atoms inside the 2 2
361
structure (tetrahedral voids). r= = 127.6 ; 128pm
Total no. of atoms present per unit cell 2 2
1 1 21. (a) Since lithium metal crystallises in a body
= 8´ + 6´ + 4 = 8 centred cubic crystal
8 2
(corners) (face (inside a 3 351 ´ 1.732
centered) body) \ r= = =151.98 pm
4 4
15. (b) Density is given by 22. (b) Percentage of occupied space in a bcc is 68%.
Z ´M \ Percentage of free space in a bcc is
d= ; where Z = number of formula units
N Aa 3 (100 – 68) = 32%
present in unit cell, which is 4 for fcc 23. (a) Following generalization can be easily
a = edge length of unit cell. M = Molecular mass derived for various types of lattice arrangements
4´ M in cubic cells between the edge length (a) of the
2.72 = cell and r the radius of the sphere.
6.02 ´ 10 ´ (404 ´ 10 -10 )3
23
a
(Q 1pm = 10-10 cm) For simple cubic : a = 2r or r =
2
2.72 ´ 6.02 ´ (404)3 For body centred cubic :
M= = 26.99 = 27 g mol–1
4 ´ 107 4 3
a= r or r = a
1 3 4
16. (d) No. of A2 + ions = ´ 8 = 2 For face centred cubic :
4
No. of B+ ions = 4 × 1 = 4 1
a = 2 2 r or r = a
No. of atoms in ccp, 2 2
1 1 Thus the ratio of radii of spheres will be simple :
O2 - = 8 ´ + 6 ´ = 4
8 2 bcc : fcc
Hence the formula of the oxide will be a 3 1
A2B4O4 or AB2O2. = : a: a
2 4 2 2
17. (a) Number of octahedral voids in ccp is equal 24. (d) Number of atoms per unit cell = 1
to effective number of atoms. Atoms touch each other along edges. Hence
In ccp, effective number of atoms are 4 so, 4 a
octahedral voids. r=
2
So, 1 octahedral voids per atom. (r = radius of atom and a = edge length)
18. (a) For fcc structure, 2 a = 4r 4 3
pr
p
2 ´ 408 Therefore % fraction = 3 = = 0.52
= 2r (2r = Diameter) (2r ) 3 6
2
Diameter = 288.5 ; 288 pm 25. (c) In body centred cubic lattice one molecule
of CsBr is within one unit cell.
19. (a) For bcc lattice, diagonal = a 3 .
Atomic mass of unit cell = 133 + 80 = 213 a.m.u
The distance between the two oppositely
Volume of cell = (436.6 × 10–10)3 cm3
EBD_8336
150 CHEMISTRY
Z ´ at.wt. therefore number of atoms per unit cell = 1. Thus
Density =
Av.no. ´ vol.of unit cell formula of the compound is AB.
1´ 213 29. (d) Given : Order of Bragg diffraction (n) = 2;
Density = 23 3 -30 Wavelength (l) = 1 Å and angle (q) = 60º. We
6.02 ´10 ´ (436.6) ´ 10
know from the Bragg’s equation nl = 2d sin q
213 ´ 107 or 2 × 1 = 2d sin 60º
= = 4.25 g / cm3
3
6.02 ´ (436.6) 3 2
Þ 2 ´ 1 = 2.d . Þ d= = 1.15 Å
In the density formula, Z is number of particles 2 3
present in a unit cell and M is molar mass of that
(where d = difference between the scattering
particle. For any diatomic molecule like CsBr, Z =
2 but for any mono atomic molecule like Li, Z = 1
planes)
for bcc lattice. 30. (c) A body-centred cubic system consists of
eight atoms at the corners plus one atom at the
26. (c) centre of cube.
31. (c) For fcc, the edge length of the unit cell,
a = r + 2R + r
where, R = Radius of anion & r = radius of cation
\ 508 = 2 × 100 + 2R Þ R = 154 pm
32. (c) In fluorite structure, each F – ion is
surrounded by four Ca2+ ions whereas, each
Ca2+ is surrounded by eight F– ions, giving a
body centred cubic arrangement. Thus the
co-ordination number of Ca2+ = 8.
33. (c) The no. of atoms is a unit cell may be
calculated by the the formula
An isolated fcc cell is shown here. Each face n n n f ne
Z= c+ b+ +
of the cell is common to two adjacent cells. 8 1 2 4
Therefore, each face centre atom contributes where nc = no. of atom at the corner nb = no. of
only half of its volume and mass to one cell. atoms at body centre nf = no. of atoms at face
Arranging six cells each sharing the remaining centre, ne = no. of atoms at edge centre.
half of the face centred atoms, constitutes An fcc crystal contains
fcc cubic lattice. e.g., Cu and Al. 8 6
27. (a) For the given cubic structure, = + = 4 atoms in a unit cell.
8 2
34. (b) Ni0.98O = (Ni2+)x (Ni3+)0.98–x (O2–)1
No. of X atoms at the corners = 8 ´ 1 = 1
8 Net charge = 0
1 [x × 2] + [(0.98 – x) × 3] + [–2 × 1] = 0
No. of Y atoms at the face-centres = 6 ´ = 3 x = 0.94
2
Fraction of nickel existing as
\ Formula of the compound = XY3
0.94
28. (a) Given: Atoms are present at the corners of Ni2+ = = 0.959 » 0.96
the cube = A and atoms present at body 0.98
35. (d) The semiconductors formed by the
centre = B. We know that a cubic unit cell has 8
introduction of impurity atoms containing one
corners. Therefore contribution of each atom at
1 elecron less than the parent atoms of insulators
the corner = . Since number of atoms per unit are termed as p-type semiconductors. Therefore,
8
1 silicon containing 14 electrons has to be doped
cell is 8, therefore total contribution = 8 ´ = 1 . with boron containing 13 electrons to give a
8
We also know the one atom is in the body centre, p-type semi-conductor.
The Solid State 151
36. (b) For each Sr 2+
ion added, one Na+
ion is from their lattice sites so that the electrical
removed to maintain the electrical neutrality. neutrality is maintained. The defect is called
Hence concentration of cation vacancies Schottky defect.
= mole % of SrCl2 added = 10–4 mole % 39. (d) When electrons are trapped in anion
10 -4 vacancies, these are called F-centres.
= ´ 6.023 ´ 1023 = 6.023 ´ 1017
100
37. (d) When the crystal is irradiated with white +ve –ve
light, the trapped electrons in a hole absorbs e– ion ion
photon for excitation from ground state to excited
state. This gives colour to the compund. F- centre in crystal
Alkali metal halide may have excess metal ion if a 40. (a) p-type of semiconductors are produced
negative ion is absent from its lattice site, leaving a by adding impurity containing less electrons
hole, which is occupied by electron to maintain (i.e. atoms of group 13).
electrical neutrality. The 'holes' occupied by Ge belongs to Group 14 and In to Group 13.
electrons are called F-centres or colour centres.
Hence, on doping, p-type semiconductor is
38. (d) If in an ionic crystal of the type A+. B–, obtained.
equal number of cations and anions are missing
EBD_8336
152 CHEMISTRY
16 Solutions
2020 2019 2018 2017 2016

molality and Kf 1 E
Solubiity and effect of
concentration of temperature on
1 E
solutions molality/molarity/
mole fraction
Vapour pressure,laws Raoult's l aw 1 E 1 A
of solutions and ideal azeoptropes 1 E
and non ideal
solutions vapour pressure 1 A
Colligative properties
depression in
and abnormal 1 A
freezing point
molecular mass
(a) Molarity
Topic 1: Solubility and Concentration of
Solutions (b) Mole fraction
(c) Weight percentage
1. The density of 2 M aqueous solution of NaOH (d) Molality
is 1.28 g/cm3. The molality of the solution is 4. What is the mole fraction of the solute in a 1.00
[Given that molecular mass of NaOH = 40 g mol–1] m aqueous solution ? [2011, 2015 RS]
[NEET Odisha 2019 ] (a) 0.177 (b) 1.770
(a) 1.32 m (b) 1.20 m (c) 0.0354 (d) 0.0177
(c) 1.56 m (d) 1.67 m 5. How many grams of concentrated nitric acid
2. If molality of the dilute solutions is doubled, the solution should be used to prepare 250 mL of
value of molal depression constant (Kf ) will be:- 2.0M HNO3 ? The concentrated acid is 70%
[2017] HNO3 [NEET 2013]
(a) halved (b) tripled (a) 90.0 g conc. HNO3
(c) unchanged (d) doubled (b) 70.0 g conc. HNO3
3. Which of the following is dependent on (c) 54.0 g conc. HNO3
temperature? [2017] (d) 45.0 g conc. HNO3
Solutions 153
6. 25.3 g of sodium carbonate, Na 2CO3 is (a) Molarity (b) Molality

dissolved in enough water to make 250 mL of (c) Formality (d) Normality
solution. If sodium carbonate dissociates Topic 2: Vapour Pressure, Laws of
completely, molar concentration of sodium ions, Solutions and Ideal, Non-ideal Solutions
Na + and carbonate ions, CO32– are respectively
14. The mixture which shows positive deviation
(Molar mass of Na2CO3 = 106 g mol–1) [2010] from Raoult's law is [2020]
(a) 0.955 M and 1.910 M (a) Benzene + Toluene
(b) 1.910 M and 0.955 M (b) Acetone + Chloroform
(c) 1.90 M and 1.910 M (c) Chloroethane + Bromoethane
(d) 0.477 M and 0.477 M (d) Ethanol + Acetone
7. The mole fraction of the solute in one molal 15. Which of the following statements is correct
aqueous solution is: [2005] regarding a solution of two components A and
B exhibiting positive deviation from ideal
(a) 0.009 (b) 0.018
behaviour? [NEET Odisha 2019]
(c) 0.027 (d) 0.036 (a) Intermolecular attractive forces between A-
8. 1 M, 2.5 litre NaOH solution is mixed with another A and B-B are equal to those between A-B.
0.5 M, 3 litre NaOH solution. Then find out the (b) Intermolecular attractive forces between A-
molarity of resultant solution [2002] A and B-B are stonger than those between
(a) 0.80 M (b) 1.0 M A-B.
(c) 0.73 M (d) 0.50 M (c) DmixH = 0 at constant T and P.
(d) DmixV = 0 at constant T and P.
9. Molarity of liquid HCl will be, if density of
16. In water saturated air, the mole fraction of water
solution is 1.17 g/cc [2001] vapour is 0.02. If the total pressure of the
(a) 36.5 (b) 32.05 saturated air is 1.2 atm, the partial pressure of
(c) 18.25 (d) 42.10 dry air is [NEET Odisha 2019]
10. Which of the following statements, regarding (a) 0.98 atm (b) 1.18 atm
the mole fraction (x) of a component in solution, (c) 1.76 atm (d) 1.176 atm
is incorrect? [1999] 17. The mixture that forms maximum boiling
(a) 0 < x < 1 azeotrope is: [2019]
(b) x < 1 (a) Water + Nitric acid
(c) x is always non-negative (b) Ethanol + Water
(c) Acetone + Carbon disulphide
(d) –2 < x < 2
(d) Heptane + Octane
11. A 5% solution of cane sugar (mol. wt. =342) is 18. Which of the following statement about the
isotonic with 1% solution of a substance X. The composition of the vapour over an ideal 1 : 1
molecular weight of X is [1998] molar mixture of benzene and toluene is correct?
(a) 34.2 (b) 171.2 Assume that the temperature is constant at 25°C.
(c) 68.4 (d) 136.8 (Given : Vapour pressure data at 25°C, benzene
12. The number of moles of oxygen in one litre of air = 12.8 kPa, toluene = 3.85 kPa) [2016]
containing 21% oxygen by volume, in standard (a) The vapour will contain a higher
conditions, is [1995] percentage of benzene
(a) 0.186 (b) 0.21 (b) The vapour will contain a higher
percentage of toluene
(c) 0.0093 (d) 2.10
(c) The vapour will contain equal amounts of
13. Which of the following modes of expressing
benezene and toluene
concentration is independent of temperature ? (d) Not enough information is given to make a
[1992, 1995] predication
EBD_8336
154 CHEMISTRY
19. At 100 °C the vapour pressure of a solution of 26. Formation of a solution from two components
6.5 g of a solute in 100 g water is 732 mm. If can be considered as [2003]
Kb = 0.52, the boiling point of this solution will (i) Pure solvent ® separated solvent
be [2016] molecules, DH1
(a) 101 °C (b) 100 °C (ii) Pure solute ® separated solute
(c) 102 °C (d) 103 °C molecules, DH2
20. Which one is not equal to zero for an ideal (iii) Separted solvent ® Solution, DH3
solution: [2015] & solute molecules
(a) DSmix Solution so formed will be ideal if
(b) DVmix
(c) DP = Pobserved - PRaoult (a) DH soln = DH 3 - DH1 - DH 2
(d) DHmix (b) DH soln = DH1 + DH 2 + DH 3
21. PA and PB are the vapour pressure of pure liquid (c) D H soln = D H 1 + D H 2 - D H 3
components, A and B, respectively of an ideal (d) DH soln = DH1 - DH 2 - DH 3
binary solution. If X A represents the mole 27. A solution containing components A and B
fraction of component A, the total pressure of follows Raoult's law when [2002]
the solution will be [2012] (a) A – B attraction force is greater than A – A
(a) pa + xa (pb – pa) (b) pa + xa (pa – pb) and B – B
(c) pb + xa (pb – pa) (d) pb + xa (pa – pb) (b) A – B attraction force is less than A – A and
22. Vapour pressur e of chloroform (CHCl 3 ) B–B
and dichloromethane (CH2Cl2 ) at 25 ºC are (c) A – B attraction force remains same as
200 mm Hg and 41.5 mm Hg respectively. Vapour A–A and B –B
pressure of the solution obtained by mixing (d) Volume of solution is different from sum of
25.5 g of CHCl3 and 40 g of CH2Cl2 at the same volume of solute and solvent
temperature will be : (Molecular mass of CHCl3 28. The beans are cooked earlier in pressure cooker,
= 119.5 u and molecular mass of CH2Cl2 = 85 u). because [2001]
[2012 M] (a) Boiling point increases with increasing
(a) 173.9 mm Hg (b) 615.0 mm Hg pressure
(c) 347.9 mm Hg (d) 285.5 mm Hg (b) Boiling point decreases with increasing
23. An aqueous solution is 1.00 molal in KI. Which pressure
change will cause the vapour pressure of the (c) Internal energy is not lost while cooking in
solution to increase? [2010] pressure cooker
(a) Addition of NaCI (d) Extra pressure of pressure cooker, softens
(b) Addition of Na 2SO4 the beans
(c) Addition of 1.00 molal KI 29. The vapour pressure of a solvent decreased by
(d) Addition of water 10 mm of mercury when a non-volatile solute
24. A solution of acetone in ethanol [2006] was added to the solvent. The mole fraction of
(a) shows a positive deviation from Raoult’s law the solute in the solution is 0.2. What should be
(b) behaves like a non ideal solution the mole fraction of the solvent if the decrease
(c) obeys Raoult’s law in the vapour pressure is to be 20 mm of mercury?
(d) shows a negative deviation from Raoult’s law [1998]
25. The vapour pressure of two liquids ‘P’ and (a) 0.8 (b) 0.6
‘Q’ are 80 and 60 torr, respectively. The total (c) 0.4 (d) 0.2
vapour pressure of solution obtained by 30. The vapour pressure at a given temperature of
an ideal solution containing 0.2 mol of a non-
mixing 3 mole of ‘P’ and 2 mole of ‘Q’ would be
volatile solute and 0.8 mol of solvent is 60 mm of
[2005]
Hg. The vapour pressure of the pure solvent at
(a) 72 torr (b) 140 torr
the same temperature is [1996]
(c) 68 torr (d) 20 torr
Solutions 155
(a) 150 mm of Hg (b) 60 mm of Hg (a) 0.80K (b) 0.40 K [2020]
(c) 75 mm of Hg (d) 120 mm of Hg (c) 0.60 K (d) 0.20 K
31. Vapour pressure of benzene at 30 °C is 121.8 mm. 37. Which one of the following electrolytes has the
When 15 g of a non volatile solute is dissolved same value of van't Hoff's factor (i) as that of
in 250 g of benzene, its vapour pressure the Al2(SO4)3 (if all are 100% ionised) ? [2015]
decreased to 120.2 mm. The molecular weight of (a) K3[Fe(CN)6] (b) Al(NO3)3
the solute (Mo. wt. of solvent = 78) [1995]
(c) K4[Fe(CN)6] (d) K2SO4
(a) 356.2 (b) 456.8
38. The boiling point of 0.2 mol kg–1 solution of X
(c) 530.1 (d) 656.7
in water is greater than equimolal solution of Y
32. According to Raoult's law, relative lowering of
in water. Which one of the following statements
vapour pressure for a solution is equal to
is true in this case ? [2015]
[1995]
(a) moles of solute (a) Molecular mass of X is greater than the
molecular mass of Y.
(b) moles of solvent
(c) mole fraction of solute (b) Molecular mass of X is less than the
(d) mole fraction of solvent molecular mass of Y.
33. The relative lowering of the vapour pressure is (c) Y is undergoing dissociation in water while
equal to the ratio between the number of X undergoes no change.
[1991] (d) X is undergoing dissociation in water.
(a) solute molecules to the solvent molecules 39. Of the following 0.10 m aqueous solutions,
(b) solute molecules to the total molecules in which one will exhibit the largest freezing point
the solution depression? [2014]
(c) solvent molecules to the total molecules in (a) KCl (b) C6H12O6
the solution (c) Al2(SO4)3 (d) K2SO4
(d) solvent molecules to the total number of
40. The freezing point depression constant for water
ions of the solute.
is – 1.86 ºC m–1. If 5.00 g Na2SO4 is dissolved in
34. An ideal solution is formed when its components 45.0 g H2O, the freezing point is changed by
[1988]
– 3.82 ºC. Calculate the van’t Hoff factor for
(a) have no volume change on mixing Na2SO4. [2011]
(b) have no enthalpy change on mixing
(a) 2.05 (b) 2.63
(c) have both the above characteristics
(c) 3.11 (d) 0.381
(d) have high solubility.
41. The van’t Hoff factor i for a compound which
35. All form ideal solution except [1988]
undergoes dissociation in one solvent and
(a) C6H6 and C6H5 CH3 association in other solvent is respectively :
(b) C2H6 and C2H5I [2011]
(c) C6H5Cl and C6H5 Br
(a) less than one and greater than one.
(d) C2H5 I and C2H5 OH.
(b) less than one and less than one.
Topic 3: Colligative Properties and (c) greater than one and less than one.
Abnormal Molecular Masses (d) greater than one and greater than one.
36. The freezing point depression constant (Kf) of 42. A 0.1 molal aqueous solution of a weak acid is
benzene is 5.12 K kg mol–1. The freezing point 30% ionized. If K f for water is 1.86 °C/m, the
depression for the solution of molality 0.078 m freezing point of the solution will be : [2011 M]
containing a non-electrolyte solute in benzene (a) – 0.18 °C (b) – 0.54 °C
is (rounded off upto two decimal places) : (c) – 0.36 °C (d) – 0.24 °C
EBD_8336
156 CHEMISTRY
43. 200 mL of an aqueous solution of a protein 49. 1.00 g of a non-electrolyte solute (molar mass
contains its 1.26 g. The osmotic pressure of this 250 g mol–1) was dissolved in 51.2 g of benzene.
solution at 300 K is found to be 2.57 × 10–3 If the freezing point depression constant, Kf of
bar. The molar mass of protein will be benzene is 5.12 K kg mol–1, the freezing point of
(R = 0.083 L bar mol–1 K–1) [2011 M] benzene will be lowered by [2006]
(a) 51022 g mol–1 (b) 122044 g mol–1 (a) 0.3 K (b) 0.5 K
(c) 31011 g mol–1 (d) 61038 g mol–1 (c) 0.4 K (d) 0.2
44. A solution of sucrose (molar mass = 342 g mol–1) 50. A solution of urea (mol. mass 56 g mol-1) boils
has been prepared by dissolving 68.5 g of at 100.18 °C at the atmospheric pressure. If Kf
and Kb for water are 1.86 and 0.512 K kg mol-1
sucrose in 1000 g of water. The freezing point of
respectively, the above solution will freeze at
the solution obtained will be (Kf for water
= 1.86 K kg mol–1). [2010] [2005]
(a) – 0.372 °C (b) – 0.520 °C (a) 0.654 °C (b) - 0.654 °C
(c) 6.54 °C (d) - 6.54 °C
(d) + 0.372 °C (d) – 0.570 °C
51. Camphor is often used in molecular mass
45. A 0.0020 m aqueous solution of an ionic
determination because [2004]
compound Co(NH 3 ) 5 (NO 2 )Cl freezes at
– 0.00732 °C. Number of moles of ions which (a) it is readily available
1 mol of ionic compound produces on being (b) it has a very high cryoscopic constant
dissolved in water will be (Kf = – 1.86 °C/m) (c) it is volatile
[2009] (d) it is solvent for organic substances
(a) 3 (b) 4 52. A solution contains non-volatile solute of
(c) 1 (d) 2 molecular mass M2. Which of the following can
46. 0.5 molal aqueous solution of a weak acid (HX) be used to calculate the molecular mass of solute
is 20% ionised. If Kf for water is 1.86 K kg in terms of osmotic pressure ? [2002]
mol–1 ,the lowering in freezing point of the
æm ö æ m ö RT
solution is [2007] (a) M 2 = ç 2 ÷ VRT (b) M 2 = ç 2 ÷
è p ø èV ø p
(a) 0.56 K (b) 1.12 K
(c) – 0.56 K (d) – 1.12 K æm ö æm ö p
(c) M 2 = ç 2 ÷ pRT (d) M2 = ç 2 ÷
47. During osmosis, flow of water through a èV ø è V ø RT
semipermeable membrane is [2006] 53. Which of the following colligative property can
(a) from both sides of semipermeable provide molar mass of proteins (or polymers or
membrane with equal flow rates colloids) with greatest precision ? [2000]
(b) from both sides of semipermeable (a) Osmotic pressure
membrane with unequal flow rates (b) Elevation of boiling point
(c) from solution having lower concentration only (c) Depression of freezing point
(d) from solution having higher concentration (d) Relative lowering of vapour pressure
only 54. Which of the following 0.10 m aqueous solutions
48. A solution containing 10 g dm –3 of urea will have the lowest freezing point ? [1997]
(molecular mass = 60 g mol–1) is isotonic with a (a) Al2(SO4)3 (b) C6H12O6
5% solution of a non-volatile solute. The
molecular mass of this non-volatile solute is (c) KCl (d) C12H22O11
[2006] 55. At 25°C, the highest osmotic pressure is
exhibited by 0.1 M solution of [1994]
(a) 300 g mol–1 (b) 350 g mol–1
(a) CaCl2 (b) KCl
(c) 200 g mol–1 (d) 250 g mol–1
(c) Glucose (d) Urea.
Solutions 157
56. Which one of the following salts will have the (b) Glucose will flow towards urea solution
same value of van’t Hoff factor (i) as that of (c) urea will flow towards glucose solution
K4[Fe (CN)6]. [1994] (d) water will flow from urea solution to glucose
(a) Al2(SO4)3 (b) NaCl 59. Which of the following aqueous solution has
(c) Al (NO3)3 (d) Na2SO4. minimum freezing point ? [1991]
57. Which one is a colligative property ? [1992] (a) 0.01 m NaCl (b) 0.005 m C2H5OH
(a) boiling point (b) vapour pressure (c) 0.005 m MgI2 (d) 0.005 m MgSO4.
(c) osmotic pressure (d) freezing point 60. Blood cells retain their normal shape in solution
58. If 0.1 M solution of glucose and 0.1 M solution which are [1991]
of urea are placed on two sides of the semi- (a) hypotonic to blood
permeable membrane to equal heights, then it (b) isotonic to blood
will be correct to say that [1992]
(c) hypertonic to blood
(a) There will be no net movement across the
membrane (d) equinormal to blood.
ANS WER KEY

1 (d ) 7 (b) 13 (b) 19 (a) 25 (a) 31 (a) 37 (c) 43 (d) 49 (c) 55 (a)
2 (c) 8 (c) 14 (d) 20 (a) 26 (b) 32 (c) 38 (d ) 44 (a) 50 (b) 56 (a)
3 (a) 9 (b) 15 (b) 21 (d ) 27 (c) 33 (b) 39 (c) 45 (d) 51 (b) 57 (c)
4 (d ) 10 (d) 16 (d) 22 (N) 28 (a) 34 (c) 40 (b ) 46 (b) 52 (b) 58 (a)
5 (d ) 11 (c) 17 (a) 23 (d ) 29 (b) 35 (d) 41 (c) 47 (c) 53 (a) 59 (a)
6 (b ) 12 (c) 18 (a) 24 (a) 30 (c) 36 (b) 42 (d ) 48 (a) 54 (a) 60 (b )
Hints & Solutions

1. (d) Let, volume of solution = 1 L W 1
Mole of NaOH = 2 4. (d) Molality = ´
M V (kg)
Mass of NaOH solution = volume × density
n
= 1000 × 1.28 = 1280 g = (where nsolute = W/M)
V (kg)
Mass of H2O = (1280 – 2 × 40) = 1200 g = 1.2 kg
n
1.00 m = i.e., 1 mole in 1 kg of water
Mole of NaOH 2 V (kg)
Molality (m) = = = Moles of 1 kg H2O
Mass of solvent (kg) 1.2
1.67 m 1000 g
= = 55.55 mole
2. (c) K f (molal depression constant) only 18 g / mol
depends on the nature of the solvent and is Moles of solute = 1
independent of the concentration of the Mole fraction
solution. nsolute 1
3. (a) Molarity depends on the volume of a = =
nsolute + nwater (1 + 55.55)
solution which can be changed with change in
temperature. = 0.01768 = 0.0177
EBD_8336
158 CHEMISTRY
wt ´ 1000 \ 1000 mL of solution contain cane sugar
5. (d) Molarity (M) =
mol. wt. ´ vol (mL) 5
= ´ 1000 = 50 g/L
wt. 1000 100
2= ×
63 250 1 ´ 1000
63 Similarily 1% solution contains =
wt. = g 100
2 = 10 g/L of X.
100
wt. of 70% acid = ´ 31.5 = 45 g 50 g / L
70 (p1) = C × R × T = ´R´T
6. (b) Concentration of 342
Osmotic pressure of 1% solution of susbtance
25.3 1000
Na 2CO3 = ´ = 0.955 M
106 250 10 g / L
(p2) = ´R´T
M
[Na + ] = 2 × 0.955 = 1.91 M As both are isotonic,
é CO32– ù = 0.955 M So p1 = p2
ë û 50 10
7. (b) One molal solution means one mole solute or ´R´T = ´R´T
342 M
present in 1 kg (1000 g) solvent
342
i.e., mole of solute = 1 \ M (mol. wt. of X) = = 68.4
5
1000g 1000 12. (c) Percentage volume of oxygen = 21%.
Mole of solvent (H2O) = =
18g 18 So, 100 mL of air contains = 21mL of O2
1 \ Volume of oxygen in one litre of air
Mole fraction of solute =
æ 1000 ö 21
ç1 + ÷ = ´ 1000 = 210mL.
è 18 ø 100
18 210
= = 0.01768 ; 0.018. Therefore, no. of moles = = 0.0093
1018 22400
8. (c) From molarity equation
(Q volume of 1 mole of gas at S.T.P. is 22400 mL)
M1V1 + M2V2 = MV
13. (b) The molality involves weights of the
1 × 2.5 + 0.5 × 3 = M × 5.5 solute and the solvent. Since weight does not
4 change with the temperature, therefore molality
M= = 0.727 ; 0.73M
5.5 does not depend upon the temperature.
9. (b) Density = 1.17 g/cc 14. (d) Hydron bond of ethanol gets weakened
Mass by addition of acetone. Thus the mixture of
As d = ethanol and acetone show positive deviation
Volume
from Raoult's law.
volume = 1cc \ mass = 1.17g
15. (b) In case of positive deviation from ideal
No. of moles of solute behaviour A-B interactions are weaker than A-
Now molarity =
Volume of solution in litre A and B-B interactions.
16. (d) Mole fraction of water vapour = 0.02
1.17 ´ 1000 1170 \ Mole fraction of dry air = 1 – 0.02 = 0.98
= = =32.05M
36.5 ´ 1 36.5 Total pressure of saturated air = 1.2 atm
10. (d) The mole fraction can never be equal to –2 Acc. to Dalton’s law of partial pressure,
or 2. It is always between 0 and 1 i.e., 0 < x < 1. PDry air = PTotal xDry air = 1.2 × 0.98 = 1.176 atm
11. (c) 5% cane sugar solution means 100ml of 17. (a) The solutions which show a large negative
solution contain cane sugar = 5g deviation from Raoult’s law form maximum
Solutions 159
boiling azeotrope. Nitric acid and water forms a 21. (d) P = PAXA + PBXB = PAXA + PB (1 – XA)
maximum boiling azeotrope with a boiling point (for binary sol. XA + XB = 1)
of 393.5 K.
Þ PAXA + PB – PBXA
18. (a) Let us consider that A is benzene and B is
toluene Þ PB + XA (PA – PB)
1 : 1 molar mixture of A and B 25.5
1 1 22. (N) n CHCl3 = = 0.213
\ xA = and xB = 119.5
2 2 40
0 0 n CH 2Cl2 = = 0.47
Total pressure of solution (P) = PA xA + PB xB 85
1 1 PT = PA° X A + PB° X B
P = 12.8 × + 3.85 × = 8.325 kPa
2 2 0.213 0.47
1 = 200 ´ + 41.5 ´
0 12.8 ´ 0.683 0.683
yA = PA xA = 2 = 0.768 = 62.37 + 28.55 = 90.92
P 8.325 23. (d) When the aqueous solution of one molal
\ yB = 1 – yA = 1 – 0.768 = 0.232
KI is diluted with water, concentration decreases,
so, the vapour will contain higher percentage of therefore the vapour pressure of the resulting
benzene. solution increases.
24. (a) A solution of acetone in ethanol shows
As the molar composition is same and benzene positive deviation from Raoult's law. It is because
has higher vapour pressure, the vapour will contain
higher percentage of benzene. ethanol molecules are strongly hydrogen
bonded. When acetone is added, these
æ P° - Ps ö n W1 M 2 molecules break the hydrogen bonds and
19. (a) = = ´
èç P° ø÷ N M1 W2 ethanol becomes more volatile. Therefore, its
vapour pressure is increased.
Where, W1 = wt of solute
W2 = wt of solvent 25. (a) Given V.PP = 80 torr
M1 = Mass of solute V.PQ = 60 torr
M2 = Mass of solvent Ptotal = V·PP × XP + V·PQ × XQ
at 100 °C, P° = 760 mm é 3 2ù
= ê80 ´ + 60 ´ ú = 16 × 3 + 12 × 2
760 - 732 6.5 ´ 18 ë 5 5û
=
760 M1 ´ 100 Ptotal = 48 + 24 = 72 torr
M1 = 31.75 g mol–1 26. (b) For an ideal solution, DHmixing = 0
DH = DH1 + DH2 + DH3 (Accroding to Hess's
W1 ´ 1000 law)
DTb = m × Kb = × Kb
M 1 ´ W2
for ideal solutions there is no change in magnitude
0.52 ´ 6.5 ´1000 of the attractive forces in the two components
DTb = = 1.06 °C
31.75 ´100 present.
\ boiling point of solution 27. (c) These two components A and B follows
the condition of Raoult’s law if the force of
= 100 °C + 1.06 °C = 101 °C
attraction between A and B is equal to the force
20. (a) For an ideal solution DSmix > 0 of attraction between A and A or B and B.
28. (a) The beans are cooked earlier in pressure
Entropy will always increase upon mixing two
compounds as disorder increases.
cooker because boiling point increases with
increasing pressure.
EBD_8336
160 CHEMISTRY
29. (b) According to Raoult's law 33. (b) According to Raoult's law, the relative
p° - p n lowering in vapour pressure of a dilute solution
= (mole fraction of solute) is equal to the mole fraction of the solute present
p° n+ N
in the solution.
10
= 0.2 \ p° = 50 mm p° - p n
p° = mole fraction of solute =
p° n+ N
For other solution of same solvent 34. (c) For ideal solution,
20 n DVmixing = 0 and DH mixing = 0 .
= (mole fraction of solute)
p° n + N
35. (d) Ethyl alcohol forms hydrogen bonding
20
Þ = mole fraction of solute with itself, hence it will not form ideal solution
50
with C2H5I.
Þ Mole fraction of solute = 0.4
Hence, mole fraction of solvent = 1 – 0.4 = 0.6 36. (b) DTf = K f m = 5.12 × 0.078 = 0.399 K = 0.40 K
Decrease in vapour pressure µ Mole fraction of 37. ¾¾

® 4K+ + [Fe(CN)6]–
(c) K4[Fe(CN)6] ¬¾
¾
solute.
Thus, depression of 2 × 0.2 mm Hg vapour and Al2(SO4)3 ® 2Al3+ + 3SO2–
4
pressure requires = 2 × 0.2 mole fraction of solute.
\ van’t Hoff factor is 5 for both Al2 (SO4)3 and
30. (c) According to Raoult's law K4[Fe(CN)6]
Po - P 38. (d) DTb = iKb m
= xB
Po Given, (DTb)x > (DTb)y
é .2 1ù \ ix Kb m > iyKb m
ê xB = Mole fraction of solute = .2 + .8 = 5 ú
ê ú (Kb is same for same solvent)
ë P = 60 mm of Hg û ix > iy
So, x is undergoing dissociation in water.
Po - P 1
= or 4 P o = ( P )´5 39. (c) Colligative properties µ no. of particles.
o 5
P Since Al2(SO4)3 contains maximum number of
60 ´ 5 particles, hence will have the largest value of
Þ Po = = 75 mm of Hg freezing point depression.
4
31. (a) Given vapour pressure (p°) = 121.8 mm; 40. (b) Given Kf = – 1.86º cm–1, mass of solute
Weight of solute (w) = 15 g = 5.00 g, mass of solvent = 45.0 g
Weight of solvent (W) = 250 g DTf = i × Kf . m
From Raoult’s law, 5 ´ 1000
3.82 = i × 1.86 ×
142 ´ 45
Po - P w M 121.8 - 120.2 15 78 (Molecular mass of Na2SO4 = 142)
= = ´ = = ´
P o m W 121.8 m 250 \ i = 2.63
41. (c) If compound dissociates in solvent i > 1
15 ´ 78 121.8 and on association i < 1.
or m = ´ = 356.2
250 1.6 42. (d) Given a = 30% i.e., 0.3
32. (c) Relative lowering of vapour pressure HA ¾¾ ® H+ + A–
depends upon the mole fraction of solute. 1–a a a
o 1 – 0.3 0.3 0.3
P -P
i.e., = mole fraction of solute i = 1 – 0.3 + 0.3 + 0.3
Po i = 1.3
Solutions 161
DTf = 1.3 × 1.86 × 0.1 = 0.2418 For isotonic solution, p1=p2

Tf = 0 – 0.2418 = – 0.2418 °C 10 50
´ .0821 ´ T = ´ .0821 ´ T
43. (d) p = CRT (Osmotic pressure) 60 M
wt ´ 1000 M = 300 gm mol–1
p= RT = 2.57 ´ 10-3
Molecular mass ´ V 1 1000
1.26 ´ 1000 49. (c) DT = K f m = 5.12 ´ ´ = 0.4K
= ´ 0.083 ´ 300 250 51.2
Mol.mass ´ 200 50. (b) As DTf = Kf . m
1.26 ´ 0.083 ´ 300 ´1000 DTb = Kb . m
Molecular mass = DT f DT
200 ´ 2.57 ´10-3 Hence, we have m = = b
= 61038 g mol–1 Kf Kb
K
or DT f = DTb f
1000W2 Kb
44. (a) DT f = K f
M 2W1 Þ [ DTb = 100.18 - 100 = 0.18°C]
1.86×1000×68.5 1.86
= = 0.372°C = 0.18 ´ = 0.654°C
342×1000 0.512
As the Freezing Point of pure water is 0°C,
T f = – 0.372°C Q (0 – DTf )
DTf = 0 – Tf
45. (d) DTf = 0 – (– 0.00732°) = 0.00732
DTf = i × Kf × m 0.654 = 0 – Tf
ΔTf 0.00732 \ Tf = – 0.654
i= = =2 Thus the freezing point of solution will be
K f × m 1.86× 0.002
– 0.654°C.
46. (b) As DTf = i Kf m 51. (b) Solvent having high cryoscopic constant
For can be used in determination of molecular mass
HX H + + X- by cryoscopic method.
t=0 1 0 0 m æ m ö RT
52. (b) pV = nRT = RT or M 2 = ç 2 ÷
t eq (1 - 0.20) 0.20 0.20 M èV ø p
Total no. of moles = 1 – 0.20 + 0.20 + 0.20 Where M2 = molecular mass of solute
= 1 + 0.20 = 1.2 and m2 = mass of solute
\ DTf = 1.2 × 1.86 × 0.5 = 1.1160 » 1.12 K 53. (a) Molecular masses of polymers are best
47. (c) During osmosis, water flows through determined by osmotic pressure method .
semipermeable membrane from lower Because other colligative properties give so low
concentration to higher concentration. values that they cannot be measured accurately.
48. (a) Osmotic pressure of urea from the formula
Osmotic pressure measurements can be made at
nRT room temperature and do not require heating which
pV = nRT Þ p =
V may change the nature of the polymer.
10
Þ ´.0821´T [1 dm3 = 1 litre] 54. (a) Depression in F.P. µ No. of particles.
60
5% solution means Al 2 (SO 4 )3 provides five ions on ionisation
100 ml º 5 g
¾® 2 Al 3+ + 3SO 24 –
Al 2 (SO 4 ) 3 ¾
1000 ml º 50 g/L
Osmotic pressure of solution having non- while KCl provides two ions
50 K + + Cl-
KCl
volatile solute p2 = × .0821 × T
M
EBD_8336
162 CHEMISTRY
C6H12O6 and C12H22O11 are not ionised so they 58. (a) As both the solutions are isotonic hence
have single particle. there will be no net movement of the solvent
through the semipermeable membrane between
Hence, Al 2 (SO4 )3 have maximum value of
two solutions.
depression in F.P. or lowest F.P.
59. (a) DTf = i × Kf × m
55. (a) Conc. of particles in CaCl2 sol. will be max. Van't Hoff factor, i = 2 for NaCl,
as i = 3 is max. So it exhibits highest osmotic hence DTf = 0.02 Kf which is maximum in the
pressure.
present case.
Glucose and urea do not dissociate into ions, as
Hence DTf is maximum or freezing point is
they are non-electrolytes. minimum.
60. (b) Blood cells neither swell nor shrink in
56. (a) K 4 [Fe(CN) 6 ] and Al 2 (SO 4 )3 both isotonic solution. As isotonic solution have
dissociates to give 5 ions or i = 5 equal concentration therefore, there is no flow
4 K + + [ Fe(CN ) ]- of solvent.
K 4 [Fe(CN )6 ] 6
and Blood cell shrink when placed in hypertonic
2Al3+ + 3SO 42-
Al 2 (SO 4 )3 solution and swells when placed in hypotonic
solution.
57. (c) Osmotic pressure, elevation in boiling point,
lowering of vapour pressure and depression in
freezing point are colligative properties.
Electrochemistry 163
17 Electrochemistry
2020 2019 2018 2017 2016

Conductance and
ionic mobility 1 E
conductivity
Electrolysis and types electrolysis 1 E
of electrolysis Faraday's l aw 1 A
relation between
equilibrium 1 A
constant and Ecell
Cells and electrode
potential, Nernst relation between
equation equilibrium
1 E
constant and Gibbs
energy
Nernst equation 1 D
Topic 1: Conductance and Conductivity (a) Acetic acid, C2H4O2

(b) Hydrochloric acid, HCl
1. Following limiting molar conductivities are given (c) Ammonia, NH3
as [NEET Odisha 2019] (d) Fructose, C6H12O6
l°m(H2SO4) = x S cm2 mol–1 4. At 25°C molar conductance of 0.1 molar aqueous
l°m(K2SO4) = y S cm2 mol–1 solution of ammonium hydroxide is 9.54
l°m(CH3COOK) = z S cm2 mol–1 ohm-1 cm2mol-1 and at infinite dilution its molar
conductance is 238 ohm-1 cm2 mol-1. The degree
l°m(in S cm2 mol–1) for CH3COOH will be or ionisation of ammonium hydroxide at the same
( x – y) concentration and temperature is : [NEET 2013]
(a) +z (b) x – y + 2z
2 (a) 20.800% (b) 4.008%
(c) x + y + z (d) x – y + z (c) 40.800% (d) 2.080%
2. Ionic mobility of which of the following alkali 5. Limiting molar conductivity of NH4OH
metal ions is lowest when aqueous solution of (i.e., L°m(NH4OH)) is equal to : [2012]
their salts are put under an electric field ? [2017] ° ° °
(a) K (b) Rb (a) Lm (NH 4Cl ) + Lm (NaCl) -L m(NaOH)
(c) Li (d) Na ° ° °
(b) Lm (NaOH) + L m (NaCl) -Lm (NH4 Cl )
3. Aqueous solution of which of the following ° ° °
compounds is the best conductor of electric
(c) Lm (NH 4OH) + L m(NH4Cl) -Lm( HCl)
° ° °
current ? [2015 RS] (d) Lm ( NH Cl) + Lm( NaOH ) -L m( NaCl)
4
EBD_8336
164 CHEMISTRY
6. Molar conductivities (L°m) at infinite dilution of (c) infinite dilution, each ion makes definite
NaCl, HCl and CH3COONa are 126.4, 425.9 and contribution to conductance of an
91.0 S cm2 mol–1 respectively. L°m for CH3COOH electrolyte whatever be the nature of the
will be : [2012 M] other ion of the electrolyte.
(a) 425.5 S cm2 mol–1 (b) 180.5 S cm2 mol–1 (d) infinite dilution, each ion makes definite
(c) 290.8 S cm2 mol–1 (d) 390.5 S cm2 mol–1 contriubtion to equivalent conductance of
7. An increase in equivalent conductance of a an electrolyte, whatever be the nature of
strong electrolyte with dilution is mainly due to: the other ion of the electrolyte.
[2010] 11. The ionic conductance of Ba 2+ and Cl – are
(a) increase in ionic mobility of ions respectively 127 and 76 ohm–1 cm2 at infinite
(b) 100% ionisation of electrolyte at normal dilution. The equivalent conductance
dilution (in ohm–1 cm2) of BaCl2 at infinite dilution will be :
(c) increase in both i.e. number of ions and (a) 139.5 (b) 203 [2000]
ionic mobility of ions (c) 279 (d) 101.5
(d) increase in number of ions 12. Specific conductance of a 0.1 N KCl solution at
23ºC is 0.012 ohm–1 cm–1. Resistance of cell
8. Which of the following expressions correctly
containing the solution at same temperature was
represents the equivalent conductance at infinite
found to be 55 ohm. The cell constant is [2000]
dilution of Al2 (SO4)3,? Given that L °Al3+ and
(a) 0.918 cm–1 (b) 0.66 cm–1
(c) 1.142 cm –1 (d) 1.12 cm–1
L°SO2 - are the equivalent conductances at
4 13. Equivalent conductances of NaCl, HCl and
infinite dilution of the respective ions. [2010] CH3COONa at infinite dilution are 126.45, 426.16
1 ° 1 and 91 ohm–1 cm2 respectively. The equivalent
(a) L
3 Al3+
+ L°
2 SO 24- conductance of CH3COOH at infinite dilution
would be [1997]
(b) 2L ° + 3L° (a) 101.38 ohm–1 cm2 (b) 253.62 ohm–1 cm2
Al3+ SO 24- (c) 390.71 ohm–1 cm2 (d) 678.90 ohm–1 cm2
14. If 0.01 M solution of an electrolyte has a
(c) L° + L°
Al3+ SO24 - resistance of 40 ohms in a cell having a cell
constant of 0.4 cm–1, then its molar conductance
æL ° + L ° 2- ö ´ 6
(d) è Al3+ SO4 ø in ohm–1 cm2 mol–1 is [1997]
(a) 102 (b) 104
M (c) 10 (d) 103
9. The equivalent conductance of solution of
32 15. On heating one end of a piece of a metal, the
a weak monobasic acid is 8.0 mho cm2 and at other end becomes hot because of [1995]
infinite dilution is 400 mho cm2. The dissociation (a) resistance of the metal
constant of this acid is: [2009] (b) mobility of atoms in the metal
(a) 1.25 × 10–6 (b) 6.25 × 10–4 (c) energised electrons moving to the other end
(c) 1.25 × 10–4 (d) 1.25 × 10–5 (d) minor perturbation in the energy of atoms
10. Kohlrausch’s law states that at : [2008] 16. If 0.5 A current is passed through acidified silver
(a) finite dilution, each ion makes definite nitrate solution for 100 minutes. The mass of
contribution to equivalent conductance of silver deposited on cathode, is (eq.wt.of silver
an electrolyte, whatever be the nature of nitrate = 108) [1995]
the other ion of the electrolyte. (a) 2.3523 g (b) 3.3575 g
(b) infinite dilution each ion makes definite (c) 5.3578 g (d) 6.3575 g
contribution to equivalent conductance of 17. Which of the following is an insulator ?[1992]
an electrolyte depending on the nature of (a) Graphite (b) Aluminium
the other ion of the electrolyte. (c) Diamond (d) Silicon.
Topic 2: Electrolysis and Types of Electrolysis (a) Hg is more inert than Pt

(b) More voltage is required to reduce H+ at
18. On electrolysis of dil. sulphuric acid using Hg than at Pt
Platinum (Pt) electrode, the product obtained at (c) Na is dissolved in Hg while it does not
anode will be [2020] dissolve in Pt
(a) Oxygen gas (b) H2S gas
(d) Conc. of H+ ions is larger when Pt electrode
(c) SO2 gas (d) Hydrogen gas
is taken
19. The number of Faradays(F) required to produce
26. Standard electrode potentials are : Fe+2/Fe
20 g of calcium from molten CaCl2 (Atomic mass
[Eº = – 0.44]; Fe+3/Fe+2 [Eº = + 0.77] ; If Fe+2,
of Ca = 40 g mol–1) is: [2020]
Fe+3 and Fe blocks are kept together, then [2001]
(a) 2 (b) 3
(a) Fe+2 increases
(c) 4 (d) 1
(b) Fe+3 decreases
20. When 0.1 mol MnO42– is oxidised, the quantity
Fe +2
of electricity required to completely oxidise (c) remains unchanged
MnO42– to MnO4– is: [2014] Fe +3
+2
(d) Fe decreases
(a) 96500 C (b) 2 × 96500 C
(c) 9650 C (d) 96.50 C 27. On passing a current of 1.0 ampere for 16 min and
21. The weight of silver (at wt. = 108) displaced by a 5 sec through one litre solution of CuCl2, all
quantity of electricity which displaces 5600 mL copper of the solution was deposited at cathode.
of O2 at STP will be :- [2014] The strength of CuCl2 solution was (Molar mass
(a) 5.4 g (b) 10.8 g of Cu= 63.5; Faraday constant = 96,500 Cmol–1)
(c) 54.9 g (d) 108.0 g [1996]
22. How many grams of cobalt metal will be (a) 0.01 N (b) 0.01 M
deposited when a solution of cobalt (II) chloride (c) 0.02 M (d) 0.2 N
is electrolyzed with a current of 10 amperes for 28. On electrolysis of dilute sulphuric acid using
109 minutes (1 Faraday = 96,500 C; Atomic mass platinum electrodes, the product obtained at the
of Co = 59 u) [NEET Kar. 2013] anode will be [1992]
(a) 0.66 (b) 4.0 (a) hydrogen (b) oxygen
(c) 20.0 (d) 40.0 (c) hydrogen sulphide (d) sulphur dioxide.
23. Al2O3 is reduced by electrolysis at low potentials Topic 3: Cells and Electrode Potential,
and high currents. If 4.0 × 104 amperes of current
Nernst Equation
is passed through molten Al 2 O 3 for
6 hours, what mass of aluminium is produced? !
29. For a cell involving one electron Ecell = 0.59 V
(Assume 100% current efficiency and At. mass
of Al = 27 g mol–1) [2009] at 298 K, the equilibrium constant for the cell
(a) 8.1 × 104 g (b) 2.4 × 105 g reaction is : [2019]
(c) 1.3 × 104 g (d) 9.0 × 103 g
é 2.303RT ù
24. 4.5 g of aluminium (at. mass 27 amu) is êGiven that = 0.059 V at T = 298 Kú
deposited at cathode from Al 3+ solution by a ë F û
certain quan tity of electric charge. The (a) 1.0 × 10 2 (b) 1.0 × l0 5
volume of hydrogen produced at STP from (c) 1.0 × l010 (d) 1.0 × l030
H+ ions in solution by the same quantity of 30. For the cell reaction [2019]
electric charge will be [2005] 2Fe3+(aq) + 2I– (aq) ® 2Fe2+ (aq) + I2(aq)
(a) 44.8 L (b) 22.4 L 0.24 V at 298 K. The standard Gibbs energy (D,
(c) 11.2 L (d) 5.6 L G°) of the cell reaction is:
25. In electrolysis of NaCl, when Pt electrode is
[Given that Faraday constant F = 96500 C mol–1]
taken, then H2 is liberated at cathode while with
Hg cathode, it forms sodium amalgam. This is (a) –46.32 kJ mol–1 (b) –23.16 kJ mol–1
because [2002] (c) 46.32 kJ mol–1 (d) 23.16 kJ mol–1
EBD_8336
166 CHEMISTRY
31. In the electrochemical cell :- [2003, 2017] (a) 0.500 V (b) 0.325 V
Zn | ZnSO4 (0.01M) | | CuSO4 (1.0 M) | Cu, the emf (c) 0.650 V (d) 0.150 V
of this Daniel cell is E1. When the concentration 38. Standard electrode potential for Sn4+ / Sn2+ couple
of ZnSO4 is changed to 1.0M and that of CuSO4 is + 0.15 V and that for the Cr3+ / Cr couple is
changed to 0.01M, the emf changes to E2. From – 0.74 V. These two couples in their standard state
the followings, which one is the relationship are connected to make a cell. The cell potential
RT will be : [2011]
between E1 and E2? (Given, = 0.059) (a) + 1.19 V (b) + 0.89 V
F
(a) E1 < E2 (b) E1 > E2 (c) + 0.18 V (d) + 1.83 V
(c) E2 = 0 ¹ E1 (d) E1 = E2 39. If the E°cell for a given reaction has a negative
32. The pressure of H2 required to make the potential value, then which of the following gives the
of H2-electrode zero in pure water at 298 K is : correct relationships for the values of DG° and
[2016] Keq ? [2011]
–14 –12 (a) DG° > 0 ; Keq > 1 (b) DG° < 0 ; Keq > 1
(a) 10 atm (b) 10 atm
(c) DG° < 0 ; Keq < 1 (d) DG° > 0 ; Keq < 1
(c) 10–10 atm (d) 10–4 atm
40. A solution contains Fe2+, Fe3+ and I– ions. This
33. A device that converts energy of combustion of
solution was treated with iodine at 35°C. E° for
fuels like hydrogen and methane, directly into
Fe3+ / Fe2+ is + 0.77 V and E° for I2/2I– = 0.536 V.
electrical energy is known as : [2015]
The favourable redox reaction is : [2011 M]
(a) Electrolytic cell (b) Dynamo
(a) I2 will be reduced to I–
(c) Ni-Cd cell (d) Fuel Cell (b) There will be no redox reaction
34. A hydrogen gas electrode is made by dipping (c) I– will be oxidised to I2
platinum wire in a solution of HCl of pH = 10 and (d) Fe2+ will be oxidised to Fe3+
by passing hydrogen gas around the platinum 41. For the reduction of silver ions with copper metal,
wire at one atm pressure. The oxidation potential the standard cell potential was found to be
of electrode would be ? [NEET 2013] + 0.46 V at 25°C. The value of standard
(a) 0.59 V (b) 0.118 V Gibbs energy, DG0 will be (F = 96500 C mol–1)
(c) 1.18 V (d) 0.059 V (a) – 89.0 kJ (b) – 89.0 J [2010]
35. Consider the half-cell reduction reaction : (c) – 44.5 kJ (d) – 98.0 kJ
Mn2+ + 2e– ® Mn, E° = –1.18 V 42. Consider the following relations for emf of a
Mn2+ ® Mn3+ + e–, E° = –1.51 V electrochemical cell: [2010]
The E° for the reaction 3Mn 2+ ® Mn0 + 2Mn3+, (i) emf of cell = (Oxidation potential of anode)
and possibility of the forward reaction are, – (Reduction potential of cathode)
respectively [NEET Kar. 2013] (ii) emf of cell = (Oxidation potential of anode)
+ (Reduction potential of cathode)
(a) – 2.69 V and no (b) – 4.18 V and yes (iii) emf of cell = (Reduction potential of anode)
(c) + 0.33 V and yes (d) + 2.69 V and no + (Reduction potential of cathode)
36. Standard electrode potential of three metals X, Y (iv) emf of cell = (Oxidation potential of anode)
and Z are – 1.2 V, + 0.5 V and – 3.0 V, respectively. – (Oxidation potential of cathode)
The reducing power of these metals will be : Which of the above relations are correct?
[2011] (a) (ii) and (iv) (b) (iii) and (i)
(a) Y > Z > X (b) X > Y > Z (c) (i) and (ii) (d) (iii) and (iv)
43. Given: [2009]
(c) Z > X > Y (d) X > Y > Z
(i) Cu2+ + 2e– ® Cu, Eo = 0.337 V
37. The electrode potentials for [2011] (ii) Cu2+ + e– ® Cu+, Eo = 0.153 V
Cu2+(aq) + e– ¾¾ ® Cu+(aq) Electrode potential, Eo for the reaction,
and Cu+(aq) + e– ¾¾ ® Cu(s) Cu + + e– ® Cu, will be :
are + 0.15 V and + 0.50V, respectively. The value (a) 0.90 V (b) 0.30 V
of E°Cu 2+ /Cu will be : (c) 0.38 V (d) 0.52 V
44. On the basis of the following E° values, the 51. Cu(aq) is unstable in solution and undergoes
strongest oxidizing agent is : [2008] simultaneous oxidation and reduction according
[Fe(CN)6]4– ® [Fe(CN)6]3– + e–; E° = – 0.35 V to the reaction : [2000]
Fe2+ ® Fe3+ + e– E° = – 0.77 V 2Cu + (aq)
Cu 2+ (aq) + Cu( s )
(a) [Fe(CN)6]4– (b) Fe2+ choose correct Eº for above reaction if Eº
(c) Fe3+ (d) [Fe(CN)6]3– Cu2+/Cu = 0.34 V and Eº Cu2+/Cu+ = 0.15 V
45. The equilibrium constant of the reaction: (a) –0.38 V (b) +0.49 V
Cu(s) + 2Ag + (aq) ¾¾ ® Cu 2+ (aq) + 2Ag(s) ; (c) +0.38 V (d) –0.19 V
52. What is the Eºcell for the reaction
E° = 0.46 V at 298 K is [2007]
(a) 2.0 × 1010 (b) 4.0 × 1010 Cu 2+ (aq) + Sn 2+ (aq) +
Cu(s) + Sn 4+ (aq)
(c) 4.0 × 1015 (d) 2.4 × 1010 at 25ºC if the equilibrium constant for the reaction
is 1 × 106? [1999]
46. If E ° 2+ = - 0.441V and E ° 3+ 2+
Fe /Fe Fe /Fe (a) 0.5328 V (b) 0.3552 V
= + 0.771V, the standard EMF of the reaction
(c) 0.1773 V (d) 0.7104 V
Fe + 2Fe3+ ® 3Fe2+ will be [2006]
(a) 1.653 V (b) 1.212 V 53. For the cell reaction, [1998]
(c) 0.111 V (d) 0.330 V Cu2+ (C1, aq) + Zn(s) = Zn 2+ (C2, aq) + Cu(s) of
47. A hypothetical electrochemical cell is shown below an electrochemical cell, the change in free energy,
DG, at a given temperature is a function of
A|A + (xM)||B+ (yM)|B [2006] (a) ln (C1) (b) ln (C2/C1)
The emf measured is +0.20 V. The cell reaction is (c) ln (C2) (d) ln (C1 + C2)
(a) A+ + e–® A; B++ e– ® B 54. Without losing its concentration ZnCl2 solution
(b) The cell reaction cannot be predicted cannot be kept in contact with [1998]
(c) A + B+ ® A+ + B (a) Au (b) Al
(d) A+ + B ® A + B+ (c) Pb (d) Ag
48. The standard e.m.f. of a galvanic cell involving
55. Eº for the cell, Zn Zn 2+ (aq) Cu 2+ (aq) Cu is
cell reaction with n = 2 is found to be 0.295 V
1.10 V at 25ºC. The equilibrium constant for the
at 25°C. The equilibrium constant of the
cell reaction:
reaction would be 2+ 2+
(Given F = 96500 C mol–1; R = 8.314JK–1mol–1) Zn + Cu (aq) Cu + Zn (aq) ,
[2004] is of the order of [1997]
(a) 2.0 × 1011 (b) 4.0 × 1012 (a) 10–18 (b) 10–37
(c) 1.0 × 102 (d) 1.0 × 1010 (c) 1018 (d) 1037
49. On the basis of the information available from 56. Standard potentials (Eº) for some half-reactions
the reaction are given below : [1997]
4 2 4 + - 2 +
(1) Sn + 2e ® Sn ; E º = +0.15 V
Al + O 2 ® Al 2 O 3 , DG = – 827 kJ mol–1 of
3 3 (2) 2 Hg2 + + 2e - ® Hg 2 2+ ; E º = +0.92 V
O2. The minimum e.m.f required to carry out an
electrolysis of Al2O3 is (F = 96500 C mol–1) (3) PbO 2 + 4H + + 2e - ® Pb 2+ + 2H 2O ;
(a) 8.56 V (b) 2.14 V [2003] E° + 1.45 V
(c) 4.28 V (d) 6.42 V Based on the above, which one of the following
50. Which reaction is not feasible? [2002] statements is correct ?
(a) 2KI + Br2 ® 2KBr + I2 (a) Sn4+ is a stronger oxidising agent than Pb4+
(b) 2KBr + I 2 ® 2KI + Br2 (b) Sn2+ is a stronger reducing agent than
(c) 2KBr + Cl 2 ® 2KCl + Br2 Hg22+
(c) Hg2+ is a stronger oxidising agent than Pb4+
(d) 2H 2O + 2F2 ® 4HF + O 2
(d) Pb2+ is a stronger reducing agent than Sn2+
EBD_8336
168 CHEMISTRY
57. The correct relationship between free energy and The cell potential will be : [NEET 2013]
equilibrium constant K of a reaction is [1996] (a) 0.42 V (b) 0.84 V
(a) DG° = - RT ln K (b) DG = RT ln K (c) 1.34 V (d) 1.10 V
(c) DG° = RT ln K (d) DG = - RT ln K 61. Standard free energies of formation (in kJ/mol)
58. An electrochemical cell is set up as: Pt; H2 at 298 K are – 237.2, – 394.4 and – 8.2 for H2O(l),
(1atm) | HCl(0.1 M) || CH3COOH (0.1 M)| H2 CO2(g) and pentane (g), respectively. The value
(1atm); Pt. The e.m.f of this cell will not be zero, of E°cell for the pentane-oxygen fuel cell is :
because [1995] (a) 1.968 V (b) 2.0968 V [2008]
(a) the temperature is constant (c) 1.0968 V (d) 0.0968 V
(b) e.m.f depends on molarities of acids used 62. The efficiency of a fuel cell is given by [2007]
(c) acids used in two compartments are different DG DG
(a) (b)
(d) pH of 0.1 M HCl and 0.1 M CH3COOH is DS DH
not same DS DH
(c) (d)
59. The standard reduction potentials at 25°C of DG DG
Li+ / Li, Ba2+ / Ba, Na+ / Na and Mg2+ /Mg are 63. In the silver plating of copper, K[Ag(CN)2] is
– 3.03, – 2.73, – 2.71 and – 2.37 respectively. used instead of AgNO3. The reason is [2002]
Which one of the following is the strongest (a) A thin layer of Ag is formed on Cu
oxidising agent? [1994] (b) More voltage is required
(a) Na+ (b) Li+ (c) Ag+ ions are completely removed from
solution
(c) Ba2+ (d) Mg2+
(d) Less availability of Ag+ ions, as Cu cannot
Topic 4: Commercial Cells and Corrosion displace Ag from [Ag(CN)2]– ion
60. A button cell used in watches functions as 64. The most convenient method to protect the
following bottom of ship made of iron is [2001]
Zn(s) + Ag2O(s) + H2O(l) (a) Coating it with red lead oxide
(b) White tin plating
2Ag(s) + Zn2+(aq) + 2OH–(aq)
(c) Connecting it with Mg block
If half cell potentials are : (d) Connecting it with Pb block
Zn2+(aq) + 2e– ® Zn(s); Eo = – 0.76 V 65. The most durable metal plating on iron to protect
Ag2O(s) + H2O (l) + 2e– ® 2Ag(s) + against corrosion is [1994]
2OH–(aq); Eo = 0.34 V (a) nickel plating (b) copper plating
(c) tin plating (d) zinc plating.
ANSWER KEY
1 (a) 8 (c) 15 (c) 22 (c) 29 (c) 36 (c) 43 (d) 50 (b) 57 (a) 64 (c)
2 (c) 9 (d) 16 (b) 23 (a) 30 (a) 37 (b) 44 (c) 51 (c) 58 (d) 65 (d)
3 (b) 10 (d) 17 (c) 24 (d) 31 (b) 38 (b) 45 (c) 52 (c) 59 (d)
4 (b) 11 (b) 18 (a) 25 (b) 32 (a) 39 (d) 46 (b) 53 (b) 60 (d)
5 (d) 12 (b) 19 (d) 26 (b) 33 (d) 40 (c) 47 (c) 54 (b) 61 (c)
6 (d) 13 (c) 20 (c) 27 (a) 34 (a) 41 (a) 48 (d) 55 (d) 62 (b)
7 (a) 14 (d) 21 (d) 28 (b) 35 (a) 42 (a) 49 (b) 56 (b) 63 (d)
Hints & Solutions

1. (a) According to Kohlrausch’s law
l°m(AB) = l°m(A+) + l°m(B–) K Conductivity
lceq = =
So, l°m(CH3COOH) = l°m(CH3COO–) + l°m(H+) N Normality
So l°m(CH3COOH) On increasing dilution, both conductivity and
normality decreases. But the decreases in
1 1 conductivity is more than compensated by decrease
= l°m(CH3COOK) + l° (H SO ) – l° (K SO )
2 m 2 4 2 m 2 4 in its normality. Hence, effectively l ceq increases
x y æ x – yö on dilution.
=z+ – = z + çè ÷
2 2 2 ø 8. (c) Equivalent conductance of an electrolyte
at infinite dilution is given by the sum of
2. (c) Li+ being smallest, has maximum charge
equivalent conductances of the respective ions
density.
at infinite dilution.
\ Li+ is most heavily hydrated among all 9. (d) Degree of dissociation,
alkali metal ions. Effective size of Li+ in aqueous
L 8.0
solution is therefore, largest. So, moves slowest a= = = 2 ´ 10 -2
under electric field. L ¥ 400
3. (b) HCl completely dissociates to give Hr and
C a2
( )
1 2
Cl– ions, hence act as very good electrolyte. Ka = » C a2 = ´ 2 ´ 10-2
While others are non- electrolytes. (1 - a) 32
Lm 9.54 = 1.25 ´ 10 -5
4. (b) a = = = 0.04008 = 4.008 %. 10. (d) Kohlrausch’s Law states that at infinite
L ¥m 238
dilution, each ion migrates independently of its
o o o
5. (d) co-ion and contributes to the total equivalent
L m( NH4 Cl ) = L mNH +4 + L mCl-
o o o
conductance of an electrolyte a definite share
L m( NaOH ) = L mNa + + L mOH - which depends only on its own nature.
o o o From this definition we can see that option (d) is
L( NaCl ) = L mNa + + L mCl- the correct answer.
o o 11. (b) The ionic conductance or equivalent
\ Lm ( NH 4+ ) + Lm ( OH - ) conductance are given as:
o o o l¥ = 127 ohm–1 cm2 equivalent–1
= Lm ( NH 4+ ) ( ) ( )
+ Lm Cl- + Lm Na + Ba 2 +
o éo o ù l ¥ – = 76 ohm–1 cm2 equivalent–1
+ L m( OH- ) - ê L m( Na + ) + L m( Cl- ) ú Cl
ë û The equivalent conductance of BaCl2 at infinite
o o o dilution will be given by:
L m( NH4 OH )= L m( NH 4Cl ) + L m ( NaOH )
Ù¥
BaCl 2 = l
¥
+ l ¥ – = 127 + 76
o Ba 2 Cl
- L m( NaCl ) = 203 ohm–1 cm2 equivalent–1
o o o o
6. (d) L CH3COOH = L CH 3COONa + L HCl - L NaCl If equivalent conductance (conductivity) of cation
= 91 + 425.9 – 126.4 = 390.5 and anion are l ¥+eq and l ¥–eq and equivalent
conductance of electrolyte is l¥eq in infinite dilution,
7. (a) Strong electrolytes are completely ionised
at all concentrations. On increasing dilution, the then,
number of ions remains the same but the ionic Ù¥ ¥ ¥
eq =l + eq + l - eq
mobility increases.
EBD_8336
170 CHEMISTRY
17. (c) Diamond is an insulator, because of no free
At infinite dilution, if molar conductances of cation, electrons.
anion and electrolyte are l¥ ¥
+ m , l - m and
l ¥m 18. (a) During the electrolysis of dil. sulphuric acid
respectively for the electrolyte Ax B y, th en using Pt electrodes following reaction occurs.
xAy+ + yBx–
AxBy At cathode : 4H+ (aq) + 4e– ¾® 2H2 (g)
¥ 1 ¥ 1 At anode : 2H2O (l) ¾® O2 (g) + 4H+ (aq) + 4e–
l eq = l+ m + l¥ - m and
y x 19. (d) 1 equivalent of any substance is deposited
l¥ ¥ ¥
m = xl + m + yl - m by 1 F of charge.
12. (b) Given specific conductance of the solution 20 g calcium contains,
(k) = 0.012 ohm–1 cm–1 and resistance (R) = 55 Given mass
ohm. We know that cell constant = Specific Number of equivalents =
Equivalent mass
conductance × Observed resistance = 0.012 × (Equivalent mass of Ca
55 = 0.66 cm–1.
Atomic mass 40
13. (c) By Kohlraush's law, Ù°eq NaCl = 126.45 = = = 20 )
Valency 2
l° + l° = 126.45 ....(1) 20
Na + Cl - = =1
l° + + l° = 426.16 20
H Cl -
...(2)
So, 1 Faraday of charge is required to deposit 1
l° + l° = 91 ....(3) equivalent of Ca.
CH3OO – Na +
( +6) ( +7)
on adding (2) and (3) then subtract (1) from it 20. (c) Mn O 24 - ¾® MnO4- + e -
l° °
- + l + = 517.16 - 126.45 0.1 mole
CH3COO H
Quantity of electricity required = 0.1F
Ù°(CH3COOH) = 390.71ohm -1 cm 2 = 0.1 × 96500 = 9650 C
14. (d) Given molarity = 0.01 M 21. (d) wO = nO × 32
2 2
Resistance = 40 ohm; 5600
l wO = ´ 32 = 8g = 1 equivalent of O2
-1 2 22400
Cell constant = 0.4cm
A = 1 equivalent of Ag = 108
Specific conductivity ( k) 22. (c) Applying,
cell constant 0.4 Eit
= = = 0.01 ohm -1 cm -1 w = Zit =
resistance 40 96500
1000k Equivalent weight of cobalt (II) = 59/2
Molar conductance ( Ù m ) =
Molarity I = 10 A
1000 ´ .01 Time (t) = 109 min = 109 × 60 sec
= = 103 ohm -1cm 2 mol -1
.01 Substituting these values we get,
15. (c) When one end of a metal is heated, the 59 ´ 10 ´ 109 ´ 60
free electrons are energised and move to the w= = 20.0
2 ´ 96500
other end. It heats up the other end of the metal.
23. (a) As Q = i × t
16. (b) Given current (i) = 0.5 A;
Time (t) = 100 minutes × 60 = 6000 sec \ Q = 4.0 × 104 × 6 × 60 × 60 C
Equivalent weight of silver nitrate (E) = 108. = 8.64 × 10 8 C
According to Faraday's first law of electrolysis Now since 96500 C liberates 9 g of Al
Eit 108 ´ 0.5 ´ 6000 8.64 × 108 C liberates 9
´ 8.64 ´ 108 g Al
W= = = 3.3575 g.
96500 96500 96500
= 8.1 × 104 g of Al
24. (d) No. of gram equivalent of H+ = No. of eq. of 2SO42–(aq) ¾¾
® S2O82–(aq) + 2e–, E° = +1.96 V
4.5 For dilute sulphuric acid, first reaction is
Al3+ = = 0.5
9 preferred but for concentrated acid, second
27 reaction is preferred.
Eq. wt of Al3+ = = 9
3 ° =
2.303RT
29. (c) E cell log K
No. of gm eq. of H+ = no. of mole of H+ nF
Hence, Mass of H+ = 0.5 × 1g = 0.5 g ° = 0.59 V , n = 1
Given : E cell
We know that, 2g H2 at STP = 22.4 L
0.059
22.4 0.59 = log K
\ 0.5 g H2 at STP = ´ 0.5 = 5.6 L 1
2 0.59
= log K
25. (b) If mercury is used as cathode, H+ ions are 0.059
not discharged at mercury cathode because 10 = log k
mercury has a high over voltage for hydrogen. K = 1010
30. (a) DG = –nFE°
In electrolysis of NaCl, following ionisations take = –2 × 96500 × 0.24 = – 46320 J/mol
place: = – 46.32 kJ/mol
NaCl Na+ + Cl– 31. (b) For cell,
H2O H+ + OH– Zn|ZnSO4(0.01 M) || CuSO4(1.0 M)|Cu
Na+ and H+ ions move towards cathode.
However, only H+ ions are discharged more readily 2.303RT log [ Zn 2+ ]
than Na+ ions because in electrochemical series, Ecell = E °cell -
hydrogen is lower than sodium.
nF [Cu 2+ ]
At cathode : 2H+ + 2e– ¾® H2(g) 2.303RT ( 0.01)
If mercury is used as cathode, then Na+ ions are \ E1 = E °cell - ´ log
2´ F 1
discharged at cathode in preference to H+ ions,
yielding sodium, which dissolves in mercury to
When concentrations are changed for ZnSO4
form sodium amalgam. and CuSO4, we can write
At cathode : Na+ + e– ¾® Na(s) 2.303RT 1
E2 = E °cell - ´ log
Na(s) + Hg(s) ¾® Na – Hg(s) 2F 0.01
26. (b) The reduction potential is higher in case of \ E1 > E2
E°(Fe3+/Fe2+) = +0.77V. Thus, Fe3+ will readily 32. (a) 2H+(aq) + 2e– ® H2(g)
reduce to Fe2+ and quantity of Fe3+ will decrease. P
\ E = E0 – 0.0591 log H 2
W q 2 [ H + ]2
27. (a) By Faraday's Ist Law, =
E 96500 PH 2
(where q = it = total electric charge) 0 = 0 – 0.0295 log
we know that no of equivalent (10 -7 )2
PH 2
W it 1 ´ 965 1 =1
= = = = (10-7 )2
E 96500 96500 100
(where i = 1 A, t = 16 × 60 + 5 = 965 sec.) PH 2 = 10–14 atm
Since, we know that 33. (d) A device that converts energy of
1 combustion of fuels, directly into electrical
no. of equivalent 100 energy is known as fuel cell.
Normality = = = 0.01 N 34. (a) H2 ¾¾ ® 2H+ + 2e–
Volume (in litre) 1
1 atm 10-10
28. (b) During electrolysis of sulphuric acid, the
following processes are possible at cathode: E 0.059 (10-10 )2
+ =0– log
H 2 /H
2H2O(l) ¾¾ ® O2(g) + 4H+(aq) + 4e–, 2 1
E° = +1.23 V E + = +0.59 V
H 2 /H
EBD_8336
172 CHEMISTRY
35. (a) DE° = E°red + E°oxd = –1.81 – 1.51 = –2.69 40. (c) Given Fe+3/Fe2+ = + 0.77 V
Since DE° is negative and I2 / 2I– = 0.536V
\ DG = –nFE°, DG will have positive value so, Reduction potential of Fe3+ / Fe2+ > I2 / I–, so
forward reaction is not possible. Fe3+ will be reduced and I– will be oxidised.
+
The value of electrode potential of a half-cell 41. (a) Cu + 2 Ag (aq) ® Cu 2+
¾¾ (aq) + 2 Ag(s)
reaction does not depend on stoichiometric co-
efficient. e.g. Here, n = 2 , 0 = + 0.46 V
Ecell
Mn2+ ¾® Mn3+ + e– ; E° = –1.51V
2Mn2+ ¾® 2Mn3+ + 2e– ; E° = – 1.51V ΔGo = –nE°F = – 2×0.46×96500 kJ ; – 89 kJ
1000
36. (c) As th e value of standard reduction
potential decreases the reducing power increases 42. (a) Ecell = Ecathode – Eanode
i.e., Þ Ecell = Ered/cathode + Eoxi/anode
Z > X > Y
( -3.0) ( -1.2) ( +0.5) Þ Ecell = - Eoxi/cathode + Eoxi/anode
Hence, option (a) is correct.
37. (b) Cu 2+ + 1e - ® Cu +
43. (d) Cu2+ + 2e– ® Cu; DGo = – nEo F
E1o = 0.15V ; DG1o = -n1E1o F
= – 2 × F × 0.337 = – 0.674 F ....(i)
Cu + + 1e - ® Cu Cu+ ® Cu2+ + e– ; DGo = – nEo F
E2o = 0.50V ; DG2o = - n2 E2o F = – 1 × F × – 0.153 = 0.153 F ....(ii)
On adding eqn (i) & (ii)
Cu 2+ + 2e - ® Cu Cu+ + e– ® Cu ;
DG° = DG°1 + DG°2 DGo = – 0.521 F = – nE°F;
– nE° F = –1 n1 E1o F + (–1) n2 E2o F Here n = 1 \ E° = + 0.52 V
n1E1o + n2 E2o 0.15 ´ 1 + 0.50 ´ 1 44. (c) From the given data we fin d Fe 3+
E° = =
Þ 0.325 V
n 2 (E °
(Fe3+ /Fe 2 + ) )
= +0.77V is strongest oxidizing
agent.
When exchange of electrons (n) is different for all
three reactions, we can not use the formula for More the positive value of reduction potential,
standard electrode potential (Ecell). e.g. more is the tendency to get reduced (better
Cu2+ + e– ¾¾ ® Cu+ (n = 1) oxidising agent).
Cu+ + e– ¾¾ ® Cu (n = 1) 0.0591
o
Cu2+ + 2e– ¾¾ ® Cu (n = 2) 45. (c) As Ecell = log K c
n
E° ¹ E° + E° 0.0591
Cu 2+ /Cu Cu 2+ /Cu + Cu + /Cu
\ 0.46 = log K c
38. (b) The couple for which SRP value is high, 2
will act as cathode and the other couple will act 2 ´ 0.46
as an anode. \ log K c = = 15.57
0.0591
o o o
Ecell = Ecathode – Eanode or Kc = Antilog 15.57 = 3.7 × 1015 » 4 × 1015
= 0.15 V –(–0.74 V) = +0.89 V 46. (b)
39. (d) Standard Gibbs free energy is given as Fe ¾® Fe 2 + + 2e– [Anode] E = –0.441V
DG° = – nE° F [Fe 3+
+ e – ¾® Fe 2 + ] ´ 2 [Cathode] E = +0.771V
If E°cell < 0 i.e. – ve
DG° > 0 Fe + 2Fe 3+ ¾® 3Fe 2+
o o o
Further DG° = – RT ln Keq Ecell = Ecathode - EAnode
DG° > 0 when Keq < 1 = 0.771 – (–0.441) = 0.771 + 0.441 = 1.212 V
47. (c) The cell reacton is as follows :
53. (b) DG = - nE ° F
+
A® A + e– RT C2
+ For concentration cell, E = ln
B + e® B nF C1
+ +
Adding A + B ® A + B In it R, T, n and F are constant
So E is based upon ln C2 / C1
0.0591
48. (d) E° = log10 K RT
n Now DG = -nEF = - nF ´ ln C2 / C1
Here, n = 2, E ° = 0.295 nF
= –RT ln C2/C1
2 ´ 0.295 At constant temperature DG is based upon
\ log10 K = = 10 or K = 1 × 1010
0.0591 lnC2/C1.
49. (b) DG = –nEF, Al ® Al 3+ + 3e– 54. (b) Without losing its concentration ZnCl2
For 1 mol of Al, n = 3 solution cannot be kept in contact with Al
4 4 because Al is more reactive than Zn due to high
\ for mol of Al, n = 3 ´ = 4
3 3 electrode (reduction) potential.
According to question,
55. (d) Given for the reaction
827 ´1000 = 4 ´ E ´ 96500
Zn(s) + Cu 2+ (aq)
Cu(s) + Zn 2+ (aq),
827 ´ 1000
E= = 2.14V Eº = +1.10 V.
4 ´ 96500
At equilibrium
50. (b) 2KBr + I 2 ¾¾ ® 2KI + Br2
° 0.0591
reaction is not possible because Br – ion is not \ Ecell = log10 K eq
n
oxidised to Br2 with I2 due to higher electrode here (n ® number of exchange of electrons)
(oxidation) potential of I2 than bromine.
0.0591 2.20
51. (c) 2 Cu + ¾¾
® Cu +2 + Cu or 1.10 = log10 Keq = log10 K eq
2 0.059
2 e - + Cu +2 ¾¾
® Cu ; E1º = 0.34V ; ...(i) = 37.22 or Keq = 1.66 × 1037
e - + Cu +2 ¾¾
® Cu + ; E2º = 0.15V ; ...(ii) 56. (b) Sn 2+ ¾¾
® Sn 4+ + 2e - ; E o = -0.15 V
Cu + + e - ¾¾
® Cu; E3º = ? ... (iii) Hg 22+ ¾¾
® 2 Hg 2+ + 2e – ; E o = -0.92 V
Now, DG1º = -nFE1º = -2 ´ 0.34 F Thus, Sn2+ can more easily get oxidized than
Hg22+ or Sn2+ is stronger reducing agent than
DG2º = -1 ´ 0.15F , DG3º = -1 ´ E3º F
Hg22+.
Again, DG1º = DG2º + DG3º 57. (a) The relation between free energy change
and equilibrium constant is given by Nernst
Þ -0.68F = -0.15F - E3º F
equation
Þ E3º = 0.68 - 0.15 = 0.53V RT
Ecell = E º - ln Q
º
Ecell º
= Ecathode (Cu + / Cu ) nF
At equilibrium, E cell = 0 and Q = KC
º
- Eanode (Cu +2 / Cu + )
RT
= 0.53 – 0.15 = 0.38 V. \ Eº = ln K … (i)
nF
52. ° = 2.303 RT log K = .0591 log K
(c) Ecell Again DGº = – nFEº … (ii)
eq eq
nF n
put in (i)
.0591
= log 106 = .0591 × 3 = 0.1773V -DG º RT
2 = ln K ; DG º = - RT ln K
nF nF
EBD_8336
174 CHEMISTRY
58. (d) For a concentration cell having different 3387000 3387000
0
concentrations of ions. or Ecell = =
32 ´ 96500 3088000
0.0591 C
E= log 1 3387
n C2 or V = 1.0968 V
If all the concentrations are identical then 3088
obviously the cell voltage is zero. But as the pH DG
62. (b) Efficiency of a fuel cell ( h) =
of 0.1 M HCl (strong acid) & pH of 0.1M DH
CH3COOH(weak acid) is not same, therefore
DH is the required energy (input) and DG is the
the cell voltage will not be zero. useful energy obtained (output).
59. (d) Higher the reduction potential, stronger is
the oxidising agent. 63. (d) In th e silver platin g of copper,
60. (d) E°Cell = E°OP + E°RP = 0.76 + 0.34 = 1.10 V K[Ag(CN) 2 ] is used in stead of AgNO 3 .
61. (c) Writing the equation for pentane-oxygen Copper being more electropositive readily
fuel cell at respective electrodes and over all precipitate silver from their salt solution
reaction, we get Cu + 2AgNO 3 ¾¾ ® Cu(NO3 ) 2 + Ag
At Anode:
whereas in K[Ag (CN)2] solution a complex anion
C 5 H12 + 10H 2 O ® 5CO 2 + 32H + + 32e - [Ag(CN)2]– is formed and hence Ag+ are less
(pentane)
available in the solution and therefore copper
At Cathode:
cannot displace Ag from its complex ion.
8O 2 + 32H + + 32e- ® 16H 2 O 64. (c) For bottom of ship to be protected, it is
Over all :C5 H12 + 8O 2 ® 5CO2 + 6H 2 O connected with more reactive metal than iron
like magnesium. This technique is called cathodic
Calculation of DG° for the above reaction
protection.
DG° = [5×(–394.4) + 6× (–237.2)] – [–8.2] 65. (d) This is because zinc has higher oxidation
= – 1972.0 – 1423.2 + 8.2 = – 3387.0 kJ potential than Ni, Cu and Sn.
= – 3387000 Joules.
From the overall equation we find n = 32 The process of coating of iron surface with zinc is
0 known as galvanization. Galvanized iron sheets
Using the relation, DG° = – nFEcell and maintain their lustrue due to the formation of
substituting various values, we get protective layer of basic zinc carbonate.
0
– 3387000 = –32×96500× Ecell (F = 96500C)
Chemical Kinetics 175
18 Chemical Kinetics
2020 2019 2018 2017 2016

first order reaction
1 E 1 A
rate law
Rate of reaction, rate rate of reaction 1 E
laws and rate constant difference between
first and second 1 A
order reaction
half life of zero
1 A
order reaction
Order of reaction and order of the
1 A 1 A
half life period reaction
half life of first
1 A
order reaction
Theories of rate of collision frequency 1 E
reaction effect of catalyst 1 E
Topic 1: Rate of Reaction, Rate Laws and 1 d [H 2 ] 1 d [ NH3 ]

Rate Constant (a) - =-
3 dt 2 dt
1. The rate constant for a first order reaction is d [N2 ] d [ NH3 ]
4.606 × 10–3 s–1. The time required to reduce 2.0 (b) - =2
dt dt
g of the reactant to 0.2 g is : [2020] d [ N 2 ] 1 d [ NH3 ]
(a) 200 s (b) 500 s (c) - =
(c) 1000 s (d) 100 s dt 2 dt
2. If the rate constant for a first order reaction is k, d [H 2 ] d [ NH3 ]
(d) 3 =2
the time (t) required for the completion of 99% dt dt
of the reaction is given by : [2019] 4. The correct difference between first and second
(a) t = 0.693/k (b) t = 6.909/k order reactions is that [2018]
(c) t = 4.606/k (d) t = 2.303/k (a) The rate of a first-order reaction does not
3. For the chemical reaction depend on reactant concentrations, the
N2(g) + 3H2(g) 2NH (g) rate of a second-order reaction does
3
the correct option is: [2019] depend on reactant concentrations
EBD_8336
176 CHEMISTRY
(b) The half-life of a first-order reaction does (d) 1.25 × 10–2 mol L–1s–1 and 6.25 × 10–3
not depend on [A]0, the half-life of a mol L–1s–1
second-order reaction does depend on 9. The rate of the reaction
[A]0 2NO + Cl2 ¾¾ ® 2NOCl is given by the rate
(c) The rate of a first-order reaction does equation rate = k [NO]2 [Cl2] [2010]
depend on reactant concentrations, the The value of the rate constant can be increased by:
rate of a second-order reaction does not (a) increasing the concentration of NO.
depend on reactant concentrations (b) increasing the temperature.
(d) A first-order reaction can be catalyzed, a (c) increasing the concentration of the Cl 2
second-order reaction cannot be catalyzed (d) doing all of these
5. The rate constant of the reaction A ® B is 10. For the reaction, N2 + 3H2—® 2NH3, [2009]
0.6 × 10–3 mole per second. If the concentration
d [ NH3 ]
of A is 5 M then concentration of B after 20 = 2 × 10–4 mol L–1 s–1 , the value of
minutes is : [2015 RS] dt
(a) 1.08 M (b) 3.60 M – d [ H2 ]
would be :
(c) 0.36 M (d) 0.72 M dt
6. In a reaction, A + B ® Product, rate is doubled (a) 4 × 10–4 mol L–1 s–1
when the concentration of B is doubled, and (b) 6 × 10–4 mol L–1 s–1
rate increases by a factor of 8 when the (c) 1 × 10–4 mol L–1 s–1
concentrations of both the reactants (A and B) (d) 3 × 10–4 mol L–1 s–1
are doubled. Rate law for the reaction can be 11. In the reaction [2009]
written as : [2012]
2 BrO3– (aq) + 5Br - (aq) + 6H + ® 3Br2 (l)
(a) Rate = k [A][B] (b) Rate = k [A]2 [B]2
(c) Rate = k [A] [B] (d) Rate = k [A]2 [B] +3H2 O(l)
7. The rate of the reaction 2N2O5 ® 4NO2 + O2 can The rate of appearance of bromine (Br2) is related
be written in three ways : [2011 M] to rate of disappearance of bromide ions as
-d[N 2 O5 ] following:
= k [N 2 O5 ] d[Br2 ] 5 d[Br – ]
dt (a) = –
d[NO2 ] dt 3 dt
= k ¢ [N 2 O5 ] d[Br2 ] 5 d[Br – ]
dt (b) =
d[O2 ] dt 3 dt
= k" [N2O5 ] d[Br2 ] 3 d[Br – ]
dt (c) =
The relationship between k and k ' and between dt 5 dt
k and k ¢¢ are : d [Br2 ] 3 d[Br – ]
(d) = -
(a) k ' = 2k ; k ' = k (b) k ' = 2k ; k ¢¢ = k / 2 dt 5 dt
(c) k ' = 2k ; k ¢¢ = 2k (d) k ' = k ; k ¢¢ = k 12. For the reaction 2 A + B ® 3C + D
8. For the reaction [N 2O 5 (g) ® 2NO 2 (g) + which of the following does not express the
1/2 O2(g)] the value of rate of disappearance of reaction rate ? [2006]
N2O5 is given as 6.25 × 10–3 mol L–1s–1. The rate d[ B ] d[ D]
(a) - (b)
of formation of NO2 and O2 is given respectively dt dt
as : [2010] 1 d[A] 1 d[C]
(c) – (d) -
(a) 6.25 × 10–3 mol L–1s–1 and 6.25 × 10–3 2 dt 3 dt
mol L–1s–1 13. Consider the reaction [2006]
(b) 1.25 × 10–2 mol L–1s–1 and 3.125 × 10–3 N2 (g) + 3H2 (g) ® 2 NH3 (g)
mol L–1s–1 d[ NH 3 ]
(c) 6.25 × 10–3 mol L–1s–1 and 3.125 × 10–3 The equality relationship between and
dt
mol L–1s–1 d[ H 2 ]
- is
dt
d[NH 3 ] 2 d[H 2 ] 19. When initial concentration of the reactant is

(a) + =- doubled, the half-life period of a zero order
dt 3 dt
d[NH3 ] 3 d[H 2 ] reaction [2018]
(b) + =- (a) is halved (b) is doubled
dt 2 dt
d[NH 3 ] d[H 2 ] (c) remains unchanged (d) is tripled
(c) =- 20. Mechanism of a hypothetical reaction [2017]
dt dt X2 + Y2 ® 2XY is given below :
d[NH3 ] 1 d[H 2 ]
(d) =- (i) X2 ® X + X(fast)
dt 3 dt
d[ B ] (ii) X + Y2 XY + Y (slow)
14. 3 A ® 2B , rate of reaction is equal to
dt (iii) X + Y ® XY (fast)
[2002]
2 d[ A]
(a) - 3 d[ A] (b) - The overall order of the reaction will be :
2 dt 3 dt (a) 2 (b) 0
1 d [ A] d[ A] (c) 1.5 (d) 1
(c) - (d) + 2
3 dt dt 21. A first order reaction has a specific reaction rate
of 10–2 s–1. How much time will it take for 20 g of
15. For the reaction 2 N 2O 5 ® 4NO 2 + O 2 , rate
the reactant to reduce to 5 g ? [2017]
and rate constant are 1.02 × 10–4 mol lit–1 s–1 and (a) 138.6 sec (b) 346.5 sec
3.4×10–5 s–1 respectively then concentration of (c) 693.0 sec (d) 238.6 sec
N2O5 at that time will be [2001] 22. The rate of a first -order reaction is 0.04
(a) 1.732 M (b) 3 M mol l –1s–1 at 10 seconds and 0.03 mol l –1s–1 at
(c) 3.4 × 105 M (d) 1.02 × 10–4 M 20 seconds after initiation of the reaction. The
16. In the following reaction, how is the rate of half-life period of the reaction is [2016]
appearance of the underlined product related to (a) 24.1 s (b) 34.1 s
the rate of disappearance of the underlined (c) 44.1 s (d) 54.1 s
reactant ? [2000] 23. When initial concentration of a reactant is
BrO3- (aq) + 5Br - (aq) + 6H + (aq) doubled in a reaction, its half-life period is not
affected. The order of the reaction is : [2015]
¾¾ ® 3Br2 (l) + 3H 2 O(l) (a) First
-
(a) d[Br2 ] = - 5 d[Br ] (b) Second
dt 3 dt (c) More than zero but less than first
d[Br2 ] d[Br - ] (d) Zero
(b) =-
dt dt 24. A reaction is 50% completed in 2 hours and 75%
- completed in 4 hours. The order of reaction is
(c) d[Br 2 ] 3 d[Br ]
= [NEET Kar. 2013]
dt 5 dt
(a) 0 (b) 1
d[Br2 ] 3 d[Br - ]
(d) =- (c) 2 (d) 3
dt 5 dt 25. For a reaction between A and B the order with
17. The rate of reaction depends upon the [1995] respect to A is 2 and the order with respect to B
(a) volume (b) force is 3. The concentrations of both A and B are
(c) pressure (d) conc. of reactants doubled, the rate will increase by a factor of:
Topic 2: Order of Reaction and Half Life [NEET Kar. 2013]
Period (a) 10 (b) 12
(c) 16 (d) 32
18. A first order reaction has a rate constant of 26. In a zero-order reaction for every 10° rise of
2.303 × 10–3 s–1. The time required for 40 g of temperature, the rate is doubled. If the
this reactant to reduce to 10 g will be temperature is increased from 10°C to 100°C, the
[NEET Odisha 2019] rate of the reaction will become : [2012]
[Given that log102 = 0.3010] (a) 256 times (b) 512 times
(a) 602 s (b) 230.3 s (c) 64 times (d) 128 times
(c) 301 s (d) 2000 s
EBD_8336
178 CHEMISTRY
27. Which one of the following statements for the 32. The bromination of acetone that occurs in acid
order of a reaction is incorrect ? [2011] solution is represented by this equation. [2008]
(a) Order can be determined only experimentally. CH3COCH3 (aq) + Br2 (aq) ®
(b) Order is not influenced by stoichiometric CH3COCH2Br (aq) + H+ (aq) + Br– (aq)
coefficient of the reactants. These kinetic data were obtained for given
(c) Order of reaction is sum of power to the reaction concentrations.
concentration terms of reactants to express Initial Concentrations, M
the rate of reaction.
[CH3 COCH3] [Br2] [H+]
(d) Order of reaction is always whole number.
0.30 0.05 0.05
28. The unit of rate constant for a zero order reaction
is [2011 M] 0.30 0.10 0.05
(a) mol L–1 s–1 (b) L mol–1 s–1 0.30 0.10 0.10
(c) L2 mol–2 s–1 (d) s–1 0.40 0.05 0.20
29. During the kinetic study of the reaction, Initial rate, disappearance of Br2, Ms–1
2A + B ® C + D, following results were obtained: 5.7×10–5
5.7 × 10–5
Run [A]/mol L–1 [B]/mol L–1 Initial rate of
1.2 × 10–4
formation of
–1 –1 3.1 × 10–4
D/mol L min
–3
Base on these data, the rate equations is:
I 0.1 0.1 6.0 × 10 (a) Rate = k [CH3COCH3][H+]
–2
II 0.3 0.2 7.2 × 10 (b) Rate = k [CH = COCH3][Br2]
–1
III 0.3 0.4 2.88 × 10 (c) Rate = k [CH3 COCH3] [Br2] [H+]2
IV 0.4 0.1 2.40 × 10
–2
(d) Rate = k [CH3COCH3][Br2] [H+]
33. The reaction of hydrogen and iodine
Based on the above data which one of the
monochloride is given as: [2007]
following is correct? [2010]
2
H 2 (g) + 2ICl(g) ¾¾ ® 2HCl(g) + I2 (g)
(a) rate = k [A] [B] (b) rate = k[A] [B] The reaction is of first order with respect to H2(g)
and ICI(g), following mechanisms were proposed.
(c) rate = k [A]2 [B]2 (d) rate = k [A] [B]2
Mechanism A:
30. Half life period of a first-order reaction is 1386
H 2 (g) + 2ICl(g) ¾¾
® 2HCl(g) + I 2 (g)
seconds. The specific rate constant of the
Mechanism B:
reaction is: [2009]
–2 –1 H 2 (g) + ICl(g) ¾¾
® HI(g);slow
(a) 0.5 × 10 s (b) 0.5 × 10 s–1
–3
(c) 5.0 × 10 s–2 –1 (d) 5.0 × 10–3 s–1 HI(g) + ICl(g) ¾¾ ® HCl(g) + I 2 (g);fast
31. For the reaction A + B ¾¾ ® products, it is Which of the above mechanism(s) can be
consistent with the given information about the
observed that: [2009]
reaction?
(1) On doubling the initial concentration of A
(a) A and B both (b) neither A nor B
only, the rate of reaction is also doubled
(c) A only (d) B only
and
34. In a first-order reaction A ® B, if k is rate
(2) On doubling the initial concentrations of
constant and inital concentration of the reactant
both A and B, there is a change by a factor A is 0.5 M, then the half-life is [2007]
of 8 in the rate of the reaction.
log 2 log 2
The rate of this reaction is given by: (a) (b)
k k 0.5
(a) rate = k [A] [B]2 (b) rate = k [A]2 [B]2
ln 2 0.693
(c) rate = k [A] [B] (d) rate = k [A]2 [B] (c) (d)
k 0.5k
35. If 60% of a first order reaction was completed in 43. The plot of concentration of the reactant vs.
60 minutes, 50% of the same reaction would be time for a reaction is a straight line with a negative
completed in aproximately [2007] slope. The reaction follows a [1996]
(a) 45 minutes (b) 60 minutes (a) zero order rate equation
(c) 40 minutes (d) 50 minutes (b) first order rate equation
(log 4 = 0.60, log 5 = 0.69) (c) second order rate equation
36. For a first order reaction A ¾® B the reaction (d) third order rate equation
rate at reactant concentration of 0.01 M is 44. A substance 'A' decomposes by a first order
found to be 2.0 ´ 10-5 mol L-1 s-1. The half reaction starting initially with [A] = 2.00 m and
life period of the reaction is [2005] after 200 min, [A] becomes 0.15 m. For this
(a) 30 s (b) 220 s reaction t1/2 is [1995]
(c) 300 s (d) 347 s (a) 53.72 min (b) 50.49 min
37. The rate of reaction between two reactants A (c) 48.45 min (d) 46.45 min
and B decreases by a factor of 4 if the 45. Select the rate law that corresponds to data
concentration of reactant B is doubled. The shown for the following reaction [1994]
order of this reaction with respect to reactant A+B ¾ ¾® products.
B is: [2005] Exp. [A] [B] Initial rate
(a) 2 (b) -2 1 0.012 0.035 0.1
(c) 1 (d) -1 2 0.024 0.070 0.8
38. The rate of a first order reaction is 1.5 × 10–2 3 0.024 0.035 0.1
mol L–1 min–1 at 0.5 M concentration of the 4 0.012 0.070 0.8
reactant. The half life of the reaction is [2004]
(a) rate = k [B]3 (b) rate = k [B]4
(a) 0.383 min (b) 23.1 min
(c) 8.73 min (d) 7.53 min (c) rate = k [A] [B]3 (d) rate = k [A]2 [B]2
39. If the rate of the reaction is equal to the rate Topic 3: Theories of Rate of Reaction
constant, the order of the reaction is [2003]
(a) 3 (b) 0 46. An increase in the concentration of the
(c) 1 (d) 2 reactants of a reaction leads to change in
40. The reaction A ® B follows first order kinetics. (a) heat of reaction [2020]
The time taken for 0.8 mole of A to produce 0.6 (b) threshold energy
mole of B is 1 hour. What is the time taken for (c) collision frequency
conversion of 0.9 mole of A to produce 0.675 (d) activation energy
mole of B? [2003] 47. For a reaction, activation energy Ea = 0 and the
(a) 2 hours (b) 1 hour rate constant at 200 K is 1.6 × 106 s–1. The rate
(c) 0.5 hour (d) 0.25 hour constant at 400 K will be [NEET Odisha 2019]
41. 3A ® B + C, it would be a zero order reaction [Given that gas constant, R = 8.314 J K–1 mol–1]
when [2002] (a) 3.2 × 106 s–1 (b) 3.2 × 104 s–1
(a) the rate of reaction is proportional to (c) 1.6 × 10 s 6 –1 (d) 1.6 × 103 s–1
square of concentration of A 48. The addition of a catalyst during a chemical
(b) the rate of reaction remains same at any reaction alters which of the following quantities?
concentration of A [2016]
(c) the rate remains unchanged at any (a) Entropy (b) Internal energy
concentration of B and C (c) Enthalpy (d) Activation energy
(d) the rate of reaction doubles if concentration 49. The activation energy of a reaction can be
of B is increased to double determined from the slope of which of the
42. Half life of a first order reaction is 4 s and the following graphs ? [2015]
initial concentration of the reactants is 0.12 M. ln K l
The concentration of the reactant left after 16 s (a) vs.T (b) ln K vs.
is [1999] T T
(a) 0.0075 M (b) 0.06 M (c) T l (d) ln K vs. T
(c) 0.03 M (d) 0.015 M vs.
ln K T
EBD_8336
180 CHEMISTRY
50. What is the activation energy for a reaction if its 1 1
(c) k vs (d) log k vs
rate doubles when the temperature is raised from log T T
20°C to 35°C? (R = 8.314 J mol–1 K–1) 56. The activation energy for a simple chemical
[NEET 2013] reaction A ® B is Ea in forward direction. The
(a) 269 kJ mol–1 (b) 34.7 kJ mol–1 activation energy for reverse reaction [2003]
(c) 15.1 kJ mol–1 (d) 342 kJ mol–1
(a) Is always double of Ea
51. A reaction having equal energies of activation
(b) Is negative of Ea
for forward and reverse reaction has :
(c) Is always less than Ea
[NEET 2013]
(a) DG = 0 (b) DH = 0 (d) Can be less than or more than Ea
(c) DH = DG = DS = 0 (d) DS = 0 57. When a biochemical reaction is carried out in
52. Activation energy (E a ) and rate constants laboratory in the absence of enzyme then rate of
(k1 and k2) of a chemical reaction at two different reaction obtained is 10–6 times, then activation
temperatures (T1 and T2) are related by : energy of reaction in the Presence of enzyme is
[2012 M] 6
(a) [2001]
k E æ1 1ö RT
(a) ln 2 = – a ç - ÷ (b) Different from Ea obtained in laboratory
k1 R è T1 T2 ø
(c) P is required
k2 E æ 1 1ö (d) Can't say anything
(b) ln =- aç - ÷
k1 R è T2 T1 ø 58. Activation energy of a chemical reaction can be
determined by [1998]
k2 E æ 1 1ö (a) evaluating rate constant at standard
(c) ln =- aç + ÷
k1 R è T2 T1 ø temperature
k E æ1 1ö (b) evaluating velocities of reaction at two
(d) ln 2 = a ç - ÷ different temperatures
k1 R è T1 T2 ø
(c) evaluating rate constants at two different
53. For an endothermic reaction, energy of temperatures
activation is E a and enthalpy of reaction of (d) changing concentration of reactants
DH(both of these in kJ/mol). Minimum value of 59. In a reversible reaction the energy of activation
Ea will be. [2010] of the forward reaction is 50 kcal. The energy of
(a) less than DH (b) equal to DH activation for the reverse reaction will be
(c) more than DH (d) equal to zero (a) < 50 kcal [1996]
54. The rate constants k1 and k2 for two different (b) either greater than or less than 50 kcal
reactions are 1016 . e–2000/T and 1015 . e–1000/T, (c) 50 kcal
respectively. The temperature at which k1 = k2 is : (d) > 50 kcal
60. A chemical reaction is catalyzed by a catalyst X.
2000 [2008] Hence X [1995]
(a) 1000 K (b) K
2.303 (a) reduces enthalpy of the reaction
1000 (b) decreases rate constant of the reaction
(c) 2000 K (d) K (c) increases activation energy of the reaction
2.303
55. The temperature dependence of rate constant (d) does not affect equilibrium constant of the
(k) of a chemical reaction is written in terms of reaction
* 61. For an exothermic reaction, the energy of
Arrhenius equation, k = Ae- Ea / RT . Activation activation of the reactants is [1994]
energy ( Ea* ) of the reaction can be calculated (a) equal to the energy of activation of products
by plotting [2003] (b) less than the energy of activation of products
1 (c) greater than the energy of activation of
(a) log k vs (b) k vs T products
log T
(d) Sometimes greater and sometimes less than
that of the products
ANSWER KEY
1 (b) 8 (b) 15 (b) 22 (a) 29 (d) 36 (d) 43 (a) 50 (b) 57 (b)
2 (c) 9 (b) 16 (d) 23 (a) 30 (b) 37 (b) 44 (a) 51 (b) 58 (c)
3 (c) 10 (d) 17 (d) 24 (b) 31 (a) 38 (b) 45 (a) 52 (b, d) 59 (b)
4 (b) 11 (d) 18 (a) 25 (d) 32 (a) 39 (b) 46 (c) 53 (c) 60 (d)
5 (d) 12 (d) 19 (b) 26 (b) 33 (d) 40 (b) 47 (c) 54 (d) 61 (b)
6 (d) 13 (a) 20 (c) 27 (d) 34 (c) 41 (b) 48 (d) 55 (d)
7 (b) 14 (b) 21 (a) 28 (a) 35 (a) 42 (a) 49 (b) 56 (d)
Hints & Solutions

1. (b) First order rate equation is 5. (d) Rate constant k = 0.6 × 10–3 mole per second.
2.303 [A ] (unit mole per second shows zero order reaction)
k= log 0 For a zero order reaction
t [ A]
[A] = [A]0 – kt
2.303 2 and [A0] – [A] = [B] = kt
Þ 4.606 ´ 10 -3 = log
t 0.2 = 0.6 × 10–3 × 20 × 60 = 0.72 M
2.303 103 6. (d) According to statement given in the
Þt= ´ log10 = = 500 sec question, it is clear that
4.606 ´ 10-3 2
r µ [A]2 and r µ [B]
2. (c) For a first order reaction, That means, order of reaction with respect to B
2.303 [A]o is 1 and w.r.t A is 2.
t= log Hence, Rate = k[A]2[B]1
k [A]
for 99% completion of the reaction, 7. (b) Rate of disappearance of reactants = Rate
of appearance of products
2.303 100
t= log 1 d(N 2 O5 ) 1 d(NO2 ) d(O 2 )
k 100 - 99 - = =
2.303 2 dt 4 dt dt
t= log 102 1 1
k k (N 2 O5 ) = k ¢ (N 2 O5 ) = k ¢¢ (N 2 O5 )
4.606 2 4
t= k k¢
k = = k ¢¢
2 4
3. 2NH3 (g)
(c) N 2 (g) + 3H 2 (g) k
k¢ = 2k, k ¢¢ =
- d [ N 2 ] -1 d [ H 2 ] 1 d [ NH 3 ] 2
= = 8. (b) N 2O5 (g) ¾¾ ® 2 NO 2 (g) + 1/2 O 2 (g)
dt 3 dt 2 dt
4. (b) (t1/2)1st order = Independent of concentration d 1 d d
1
–
dt
[ N2O5 ] = + 2 dt [ NO2 ] = 2 dt [O2 ]
(t1/2)2nd order µ
[A]o
d
Half life for the second order reaction is dt
[ NO2 ] = 1.25 ´ 10-2 mol L–1s–1 and
1
t1/2 = d
K ´ [ A]0
dt
[ O2 ] = 3.125 ´ 10-3 mol L–1s–1
EBD_8336
182 CHEMISTRY
9. (b) 2 NO(g) + Cl2(g) 2 NOCl(g) where r = 1.02 × 10–4, k = 3.4 × 10–5
1.02 × 10–4 = 3.4 × 10–5 [N2O5]
Rate = k [NO]2 [Cl2] [N2O5] = 3M
The value of rate constant can be increased by 16. (d) Rate of reaction
increasing the temperature and is independent
of the initial concerntration of the reactants. 1 d[Br - ] 1 d[Br2 ]
– =+
10. (d) Rate of disappearance of H2 = rate of 5 dt 3 dt
formation of NH3. d[Br2 ] 3 d[Br – ]
=–
1 d[H 2 ] 1 d[NH3 ] dt 5 dt
– = 17. (d) The rate of a reaction is the speed at which
3 dt 2 dt the reactants are converted into products. It
– d[H 2 ] 3 d[NH3 ] 3 –4
depends upon the concentration of reactants.
Þ = = × 2×10 e.g for the reaction
dt 2 dt 2
A + B ¾¾
® Product ; r µ [A][B]
= 3×10 –4 mol L–1s –1
By decreasing volume of gas or increasing pressure
11. (d) Rate of disappearance of Br – of it, concentration will increases. Hence, (a) and
= rate of appearance of Br 2 (c) are also correct options.
1 d[Br – ] 1 d[Br2 ] 18. (a) For a first order reaction
Þ– =
5 dt 3 dt 0.693 0.693
Half life period, t 1 = = s–1
d[Br2 ] 3 d[Br – ] k 2.303 ´ 10 –3
Þ =- 2
dt 5 dt = 300.91 s
t1/2 t1/2
d[C] Now, 40 g ¾¾® 20 g ¾¾¾ ® 10 g
12. (d) In the given options, - will not
3dt So, 40 g substance requires 2 half life periods to
represent the reaction rate. It should not have reduce upto 10 g
\ Time taken in reduction = 2 × 300.91 s
1 d [ C]
–ve sign as it is product; since show the = 601.82 ; 602 s
3 dt
rate of formation of product C, which will be positive. [A]o
19. (b) (t1/2 )zero =
13. (a) If we write rate of reaction in terms of 2k
concentration of NH3 and H2, then \ If [A]o = doubled, t1/2 = doubled
1 d[NH3 ] 1 d[H 2 ] 20. (c) Overall rate = k [X][Y2] … (1)
Rate of reaction = =-
2 dt 3 dt k = rate constant
Assuming step (i) to be reversible, its equilibrium
d[NH3 ] 2 d[H 2 ]
So, =- constant,
dt 3 dt
[ X ]2
[ X2 ] Þ [ X ] = keq [ X 2 ] ;
14. (b) 3A ¾ ¾® 2 B keq = 2
Rate of appearance of B is equal to rate of

1 1
disappearance of A.
1 d[B] 1 d[A] d[B] 2 d[A]
[ X] = 2
keq [ X2 ] 2 … (2)
=- Þ =- From eq (1) and (2)
2 dt 3 dt dt 3 dt
1 1
15. (b) 2 N 2O 5 ® 4 NO 2 + O 2 Rate = kkeq 2 [ X 2 ] 2 [ Y2 ]
From the unit of rate constant, it is clear that the
reaction follow first order kinetics. Hence, 1 3
Overall order = + 1 = = 1.5
by rate law equation, r = k [N2O5] 2 2
r æ 100 -10 ö
The overall reaction rate depends on the rate of 100°C çè
10 ø
÷
the slowest step. 26. (b) =2 = 29 = 512 times
r
10°C
i.e., Overall rate = Rate of slowest step
27. (d) order of reaction can be zero, whole number
21. (a) Half life for a first order reaction, or fractional.
0.693
t1/2 = The order w.r.t a reactant can be negative also as in
K this case:
0.693
So, t1/2 = sec . 2O3 3O2
10-2 Rate - k[O3]2 [O2]–1
Also, for the reduction of 20 g of reactant to 5 g,
two half lives will be required. 28. (a) Rate = k [A]0
\ For 20 g of the reactant to reduce to 5 g, Unit of k = mol L–1 sec–1
time taken, 29. (d) In case of (II) and (III), keepin g
0.693 concentration of [A] constant, when the
t=2× sec = 138.6 sec. concentration of [B] is doubled, the rate
10-2
quadruples. Hence, it is second order with
n
æ1ö respect to B. In case of I & IV, keeping the
N = N0 ç ÷
è 2ø concentration of [B] constant, when the
where N = mass after n number of half life concentration of [A] is increased four times, rate
n = number of half life also increases four times. Hence, the order with
N0 = Initital mass respect to A is one. hence
22. (a) For a first order reaction Rate = k [A] [B]2
2.303 ( a - x1 ) 30. (b) For a first order reaction
K = t - t log a - x
( 2 1) ( 2 ) 0.693 0.693
t1/2 = ; k= = 0.5 × 10–3s–1
2.303 æ 0.04 ö k 1386
log ç
K= (
20 - 10) è 0.03 ÷ø 31. (a) When concentration of A is doubled, rate is
doubled. Hence order with respect to A is one.
2.303 ´ 0.1249 When concentrations of both A and B are
K=
10 doubled, rate increases by 8 times hence order
0.6932 2.303 ´ 0.1249 with respect to B is 2.
t1/2 = 10 \ rate = k [A]1 [B]2
0.6932 ´10 32. (a) Rewriting the given data for the reaction
t1/2 = = 24.1 sec
2.303 ´ 0.1249 H+
CH 3 COCH 3 (aq) + Br2 (aq) ¾¾¾
®
0.693
23. (a) t1/2 = CH3COCH 2 Br(aq) + H + (aq) + Br - (aq)
k
For first order t 1/2 is independent of initial S. Initial concent Initial concentr Initial concentr Rate of
No. -ration of -ation of Br2 -ation of H + disappearance
concentration of reactant. CH 3COCH3 in M in M of Br2 in MS-1
in M d dx
24. (b) For a first order reaction, i.e. - [Br2 ]or
dt dt
t75% = 2 × t50%
1 0.30 0.05 0.05 5.7 ´ 10-5
25. (d) Rate1 = k [A]2[B]3 2 0.30 0.10 0.05 5.7 ´ 10-5
when concentrations of both A and B are 3 0.30 0.10 0.10 1.2 ´ 10-4
doubled then 4 0.40 0.05 0.20 3.1 ´ 10-4
Rate2 = k [2A]2[2B]3 = 32 k [A]2[B]3 This reaction is autocatalyzed and involves

\ Rate will increase by a factor of 32. complex calculation for concentration terms.
EBD_8336
184 CHEMISTRY
We can look at the above results in a simple way Now,
to find the dependence of reaction rate (i.e. rate
2.303 100 2.303
of disappearance of Br 2). t½ = log = ´ log 2
From data (1) and (2) in which concentration of 0.0153 100 - 50 0.0153
CH3COCH3 and H+ remain unchanged and only 2.303
= ´ 0.3010 = 45.31 min.
the concentration of Br 2 is doubled, there is no 0.0153
change in rate of reaction. It means the rate of 36. (d) Given [A] = 0.01 M
reaction is independent of concentration of Br 2. Rate = 2.0 × 10–5 mol L–1 S–1
Again from (2) and (3) in which (CH3CO CH3) For a first order reaction
and (Br2) remain constant but H+ increases from Rate = k [A]
0.05 M to 0.10 i.e. doubled, the rate of reaction -5
changes from 5.7×10 –5 to 1.2 × 10 –4 2.0 ´ 10
k= = 2 × 10–3
(or 12 × 10–5 ), thus it also becomes almost [0.01]
doubled. It shows that rate of reaction is directly 0.693
proportional to [H+]. From (3) and (4), the rate t1/2 = -3 = 347 sec.
2 ´ 10
should have doubled due to increase in conc of
[H+] from 0.10 M to 0.20 M but the rate has 37. (b) Rate1= k [A]x[B]y ... (1)
changed from 1.2× 10–4 to 3.1×10–4. This is due Rate1
to change in concentration of CH3 CO CH3 from = k [A]x [2B]y ... (2)
4
0.30 M to 0.40 M. Thus, the rate is directly
proportional to [CH3 COCH3]. or Rate1 = 4k [A]x[2B]y
From (1) and (2) we get
rate = k [CH3COCH3]1[Br2]0[H+]1
= k [CH3COCH3][H+]. k [A]x [B] y
= k [A]x[2B]y
33. (d) As the slowest step is the rate determining 4
step thus the mechanism B will be more [B] y
= [2B] y
consistent with the given information. Also 4
because it involve one molecule of H2 and one y
molecule of ICl, it can be expressed as : 1 æ 2B ö 1
or =ç ÷ Þ = 2y or (2)–2 = 2y
r = k [H2][ICl] 4 è Bø 4
Which shows that the reaction is of first order y = –2.
w.r.t. both H2 & ICl. 38. (b) For a first order reaction, A ® products
34. (c) For a first order reaction r
2.303 a r = k [A] or k =
k= log10 [A]
t a-x 1.5 ´ 10 -2
when t = t½ Þk = = 3 × 10–2
0.5
2.303 a 0.693 0.693
k= log10 Further, t1/2 = = = 23.1 min.
t½ a-a/2 k 3 ´ 10-2
2.303 ln 2
or t½ = log10 2 = 39. (b) Q r = k [A]n
k k
35. (a) For a first order reaction if n = 0
2.303 a r = k [A]0
k= log or r = k thus for zero order reactions rate is equal
t a-x
when t = 60 and x = 60% to the rate constant.
2.303 100 2.303 100 40. (b) A ® B For a first order reaction
k= log = log = 0.0153 given a = 0.8 mol, (a – x) = 0.8 – 0.6 = 0.2
60 100 - 60 60 40
2.303 0.8 2.303 -2 -1

k= log or k = 2.303 log 4 = ´ (0.301 + 0.824) = 1.29 ´ 10 min .
1 0.2 200
Further
again a = 0.9, a – x = 0.9 – 0.675 = 0.225
0.693 0.693
2.303 0.9 (t1/2 ) = = = 53.49 min .
k= log k 1.29 ´ 10-2
t 0.225 45. (a) From data 1 and 3, it is clear that keeping (B)
2.303 const, When [A] is doubled, rate remains
2.303log 4 = log 4
t unaffected. Hence rate is independent of [A].
Hence t = 1 hour from 1 and 4, keeping [A] constant, when [B] is
41. (b) For reaction 3A ¾ ¾® B + C doubled, rate become 8 times. Hence
If it is zero order reaction r = k [A]0, i.e the rate rate µ [ B]3 .
remains same at any concentration of 'A'. 46. (c) The number of collisions per second per
unit volume of the reaction mixture is known as
For zero order reaction rate of reaction is
collision frequency (Z) . collision frequency µ
independent of reactant concentration.
no. of reacting molecules or atoms. Higher the
42. (a) t1/2 = 4 s T = 16 concentration of reactant molecules higher is
the probability of collision and so the collision
T 16
n= = =4 (Q T = n × t½) frequency.
t1/2 4
n 4 47. (c) From Arrhenius equation
æ 1ö æ 1ö 0.12
A = Ao ç ÷ = 0.12 ´ ç ÷ = = 0.0075 M k400 Ea é T2 – T1 ù
è 2ø è 2ø 16 log =
k200 2.303R êë T1T2 úû
where Ao = initial concentration &
A = concentration left after time t. Since, given that Ea = 0
43. (a) For a zero order reaction, concentration k400
decreases at a contant rate with time. Hence, the \ log =0
k200
plot is a straight line with a negative slope.
k400
Þ k =1
[Co] 200
Zero order So, k400 = k200

reaction
[C] So rate constant at 400, k = 1.6 × 106 s–1
48. (d) A catalyst provides an alternative route for
the reaction with a lower activation energy.
Time
49. (b) Arrhenius equation
For zero order reaction Ea
K =A.e - Ea / RT Þ ln K = ln A –
[C 0 ] - [C] RT
K=
t – Ea
slope =
[C0] = –Kt + [C0] R
Þ slope = –K, interecept = [C0] so, activation energy of reaction can be
1
44. (a) Given initial concentration (a) = 2.00 m; determined from the slope of ln K vs
Time taken (t) = 200 min and final concentration T
(a – x) = 0.15 m. For a first order reaction, rate constant, Arrhenius Equation
-Ea RT
2.303 a 2.303 2.00 K = Ae - Ea RT , where e represents the
k= log = log fraction of molecules
t a-x 200 0.15
EBD_8336
186 CHEMISTRY
2000 1000
k Ea æ1 1ö or ln 10 = -
50. (b) log 2 = çè T - T ÷ø T T
k1 2.303 R 1 2 1000
or 2.303 log 10 =
Ea é 1 1 ù T
log 2 = 2.303 ´ 8.314 ê - ú or 2.303 × 1 × T=1000 [\ log 10 = 1]
ë 293 308 û
1000
Ea 15 or T = K
0.3 = × 2.303
2.303 ´ 8.314 293 ´ 308
55. (d) k = Ae - Ea / RT
0.3 ´ 2.303 ´ 8.314 ´ 293 ´ 308 Ea
Ea = . or log T = log A -
15 2.303 RT
= 34673 J mol-1 = 34.7 kJ mol-1 Comparing the above equation with
y = mx + c
51. (b) DH = Ea f - Eab = 0
1
y = log k, x =
52. (b, d) According to Arrhenius equation T
k 2 Ea æ 1 1 ö Thus a plot of log10k vs 1/T should be a straight
ln = - line, with slope equal to – Ea /2.303R and
k1 R çè T1 T2 ÷ø
intercept equal to log A
k2 E æ 1 1ö
ln =– a ç - ÷ Ea
k1 R è T2 T1 ø Slope =
log k 2.303R
53. (c)
Ea 1/T
Energy
- Ea
DH \ Slope =
2.303 R
or Ea = –2.303R ´ Slope
Reaction coordinate 56. (d) The activation energy of reverse reaction
Ea > DH will depend upon whether the forward reaction
2000 is exothermic or endothermic.
-
54. (d) Given, k1 = 1016.e T
As DH = Ea (forward reaction) – Ea (backward reaction)
-
1000 For exothermic reaction
and k2 = 1015.e T DH = –ve
When k1 and k2 are equal at any temperature T, \ –DH = Ea(f) – Ea(b)
we have or Ea( f ) = Ea(b) – DH
2000 1000 \ Ea( f ) < Ea(b)
- -
1016.e T 15
= 10 .e T for endothermic reaction
DH = + ve
2000 1000
15
-
15
- \ DH = Ea(f ) – Ea(b) or Ea(f ) = DH + Ea(b)
or 10 ´ 10 .e T
= 10 .e T
\ Ea(f ) > Ea(b).
2000 1000
- -
T T 57. (b) The presence of enzyme (catalyst) increases
or 10.e =e
the speed of reaction by lowering the energy
2000 1000 barrier, i.e. a new path is followed with lower
or ln 10 - =-
T T activation energy.
If reaction is exothermic,
ET
E'T DH = - ve Ea(b) > Ea(f)
Ea
If reaction is endothermic
Products
DH = + ve Ea(b) < Ea(f)
Energy
Ea
1
60. (d) A catalyst affects equally both forward and
Reactants + catalyst backward reactions, therefore it does not affect
Progress of reaction
equilibrium constant of reaction.
Here ET is the threshold energy. 61. (b) Ea (Forward) + DH = Ea (backword)
Ea and Ea is energy of activation of reaction in For Exothermic reaction, DH = –ve and
1
absence and presence of catalyst respectively. \ activation energy of reactant is less than the
58. (c) We know that the activation energy of energy of activation of products.
chemical reaction is given by formula =
Threshold energy
k Ea éT2 - T1 ù
log 2 = ê ú, where k is the rate
k1 2.303R êë T1T2 ú
û
1
constant at temperature T1 and k2 is the rate

constant at temperature T2 and E a is the E
Ea(FR) E¢a(B.R.)
activation energy. Therefore, activation energy A
of chemical reaction is determined by evaluating
DH
rate constant at two different temperatures. B
59. (b) DH = Ea(f) - Ea(b)
Thus, energy of activation for reverse reaction Progress of Reaction
depend upon whether reaction is exothermic or
endothermic
EBD_8336
188 CHEMISTRY
19 Surface Chemistry
2020 2019 2018 2017 2016

characteristics of
Adsorption 1 E
adsorption
Catalysis and theoreies
catalysis 1 E
of catalysis
zeta potential 1 E
Colloids and emulsions colloidal solutions 1 A 1 E
coagulation 1 E
Topic 1: Adsorption 4. In Freundlich Adsorption isotherm, the value of

1/n is [2012]
1. The correct option representing a Freundlich
(a) between 0 and 1 in all cases
adsorption isotherm is [NEET Odisha 2019]
x x (b) between 2 and 4 in all cases
(a) = kp–1 (b) = kp0.3 (c) 1 in case of physical adsorption
m m
x x (d) 1 in case of chemisorption
(c) = kp2.5 (d) = kp–0.5
m m 5. If x is amount of adsorbate and m is amount of
2. Which one of the following characteristics is adsorbent, which of the following relations is
associated with adsorption ? [2016] not related to adsorption process ? [2011]
(a) DG is negative but DH and DS are positive (a) x / m = f (p) at constant T.
(b) DG, DH and DS all are negative (b) x / m = f (T) at constant p.
(c) DG and DH are negative but DS is positive
(c) p = f (T) at constant (x / m).
(d) DG and DS are negative but DH is positive
x
3. Which of the following statements is correct for (d) = p´ T
the spontaneous adsorption of a gas? [2014] m
(a) DS is negative and, therefore, DH should 6. The Langmuir adsorption isotherm is deduced
be highly positive using the assumption: [2007]
(b) DS is negative and therefore, DH should (a) the adsorption sites are equivalent in their
be highly negative ability to adsorb the particles
(c) DS is positive and, therefore, DH should (b) the heat of adsorption varies with coverage
be negative (c) the adsorbed molecules interact with each other
(d) DS is positive and, therefore, DH should (d) the adsorption takes place in multilayers.
also be highly positive
Surface Chemistry 189
7. For adsorption of a gas on a solid, the plot of 12. Which mixture of the solutions will lead to the
log x/m vs log p is linear with slope equal to formation of negatively charged colloidal
(n being whole number) [1994, 2006] [AgI]I– sol. ? [2019]
(a) k (b) log k (a) 50 mL of 1 M AgNO3 + 50 mL of 1.5 M KI
1 (b) 50 mL of 1 M AgNO3 + 50 mL of 2 M KI
(c) n (d)
n
(c) 50 mL of 2 M AgNO3 + 50 mL of 1.5 M KI
8. Accor ding to the adsorption theor y of
catalysis, the speed of the reaction increases (d) 50 mL of 0.1 M AgNO3 + 50 mL of 0.l M KI
because [2003] 13. On which of the following properties does the
(a) adsorption lowers the activation energy of coagulating power of an ion depend? [2018]
the reaction (a) The magnitude of the charge on the ion
(b) the concentration of reactant molecules at alone
the active centres of the catalyst becomes (b) Size of the ion alone
high due to strong adsorption
(c) The sign of charge on the ion alone
(c) in the process of adsorption, the activation
(d) Both magnitude and sign of the charge
energy of the molecules becomes large
on the ion
(d) adsorption produces heat which increases
the speed of the reaction 14. Fog is colloidal solution of [2016]
9. Which is not correct regarding the adsorption (a) Liquid in gas (b) Gas in liquid
of a gas on surface of solid? [2001] (c) Solid in gas (d) Gas in gas
(a) On increasing temperature, adsorption 15. Which property of colloidal solution is
increases continuously independent of charge on the colloidal particles:-
(b) Enthalpy and entropy changes are –ve [2014, 2015]
(c) Adsorption is more for some specific (a) Electrophoresis (b) Electro-osmosis
substances (c) Tyndall effect (d) Coagulation
(d) This phenomenon is reversible
16. The protecting power of lyophilic colloidal sol
Topic 2: Catalysis and Theories of Catalysis is expressed in terms of [2012]
10. Which one of the following statements is not (a) Coagulation value
correct? [2017] (b) Gold number
(a) The value of equilibrium constant is (c) Critical miscelle concentration
changed in the presence of a catalyst in (d) Oxidation number
the reaction at equilibrium 17. Which one of the following forms micelles in
(b) Enzymes catalyse mainly bio-chemical aqueous solution above certain concentration?
reactions [2005]
(c) Coenzymes increase the catalytic activity
(a) Dodecyl trimethyl ammonium chloride
of enzyme
(d) Catalyst does not initiate any reaction (b) Glucose
(c) Urea
Topic 3: Colloids and Emulsions (d) Pyridinium chloride
11. Measurin g Zeta potential is useful in 18. Which of the following forms cationic micelles
determining which property of colloidal above certain concentration? [2004]
solution? [2020] (a) Sodium dodecyl sulphate
(a) Solubility (b) Sodium acetate
(b) Stability of the colloidal particles (c) Urea
(c) Size of the colloidal particles
(d) Cetyl trimethyl ammonium bromide
(d) Viscosity
EBD_8336
190 CHEMISTRY
19. Position of non-polar and polar part in micelle 22. At the Critical Micelle Concentration (CMC) the
is [2002] surfactant molecules [1998]
(a) polar at outer surface and non-polar at inner (a) decompose
surface (b) dissociate
(b) polar at inner surface and non-polar at outer (c) associate
surface (d) become completely soluble
(c) distributed all over the surface 23. The ability of an ion to bring about coagulation
(d) present in the surface only of a given colloid depends upon [1997]
20. Which is used for ending charge on colloidal (a) its size
solution? [2000]
(b) the magnitude of its charge
(a) Electrons
(c) the sign of the charge alone
(b) Electrolytes
(d) both magnitude and sign of its charge
(c) Positively charged ions
24. During dialysis [1996]
(d) Compounds
(a) only solvent molecules can diffuse
21. Hardy-Schulze rule explains the effect of
electrolytes on the coagulation of colloidal (b) solvent molecules, ions and colloidal
solution. According to this rule, coagulation particles can diffuse
power of cations follow the order [1999] (c) all kinds of particles can diffuse through
(a) Ba+2 > Na+ > Al+3 (b) Al+3 > Na+ > Ba+2 the semi-permeable membrane
(c) Al+3 > Ba+2 > Na+ (d) Ba+2 > Al+3 > Na+ (d) solvent molecules and ions can diffuse
ANSWER KEY
1 (b) 4 (a) 7 (d) 10 (a) 13 (d) 16 (b) 19 (a) 22 (c)
2 (b) 5 (d) 8 (a) 11 (b) 14 (a) 17 (a) 20 (b) 23 (d)
3 (b) 6 (a) 9 (a) 12 (b) 15 (c) 18 (d) 21 (c) 24 (d)
Hints & Solutions

1. (b) According to Freundlich isotherm 2. (b) Adsorption is spontaneous process,
x therefore change in the free energy (DG) for the
= kp1/n ; where (n > 1) process is negative.
m x According to Gibbs Helmholtz eqn.
x 1 m DG = DH – TDS
So, = kp0.3 as = 0.3 DS is negative because adhering of gas
m n
So, answer is (b). molecules to the surface lowers the randomness.
p
\ DG can be –ve only when DH is –ve.
3. (b) For adsorption DS < 0 and for a
1 x
When = 0, = constant, adsorption is spontaneous change DG = – ve
n m
independent of pressure. hence DH should be highly negative which is
clear from the equation
1 x x
When = 1, = kp, µ p, adsorption varies DG = DH – TDS
n m m
directly with pressure. = – DH – T(– DS) = – DH + TDS
So if DH is highly negative, DG will also be (– ve)
Surface Chemistry 191
4. (a) According to Freundlich Adsorption 8. (a) A catalyst lowers the activation energy of
isotherm the reaction.
1 1
x Rate of reaction µ
= KP n activation energy
m
1 9. (a) On increasing temperature, adsorption of
at low pressure =1 a gas on surface of solid decreases. Solid adsorb
n
x greater amount of substances at lower
\ µ P1
m temperature.
1 10. (a) A catalyst speeds up both forward and
at high pressure =0
n backward reaction with the same rate.
x So, equilibrium constant is not affected by the
= constant
m presence of a catalyst at any given temperature.
i.e. the value of n varies between 0 to 1 11. (b) In colloidal solution, the potential
x difference between the fixed layer and the
5. (d) = f (P) at constant T and
m diffused layer of opposite charge is known as
x Zeta potential.
= f (T) at constant T Greater the Zeta potential more will be the
m
stability of colloidal particle.
Thus, it can be stated that for constant value of
x/m, pressure and temperature can take different 12. (b) AgNO3 + KI ¾¾
® AgI + KNO 3
values or Negatively
charged colloid
P = f (T) at constant (x/m). A solution of AgNO3 and KI will form a
x negatively charged colloidal sol, [AgI]I–, only
But ¹ P×T
m when KI is present in excess (i.e., KI behaves
6. (a) Langmuir adsorption isotherm is based on as a solvent).
the assumption that every adsorption site is Millimole of KI is maximum in option (2)
equivalent and the ability of a particle to bind (50 × 2 = 100)
there is independent of whether or not nearby 13. (d) According to Hardy Schulze rule,
sites are occupied. coagulating power of an ion depends on both
7. (d) According to Freundlich adsorption magnitude and sign of the charge on the ion.
isotherm. Greater the valence of the flocculating ion added,
At intermediate pressure, extent of adsorption greater is the coagulating power.
x x 1
= kp1/n or log = log k + log p;
m m n 14. (a) Fog is a colloidal system having dispersed
phase as liquid and dispersion medium as gas.
15. (c) Tyndall effect is an optical property, and it
Slope = 1/n is independent of charge on colloidal particles.
log x 16. (b) The lyophobic sols are less stable than
m
lyophilic sols. The lyophilic sols are thus used
log k
to protect the lyophobic sols. This property of
lyophilic sols is known as protective action of
log p lyophilic sols.
x Which can be represented by gold number.
plot of log vs log p is linear with slope
m 17. (a) Micelle formation is shown by surfactants
detergents (Dodecyl trimethyl ammonium
=1
n chloride) in their aqueous solutions.
EBD_8336
192 CHEMISTRY
18. (d) Cetyl trimethyl ammonium bromide, 23. (d) According to the Hardy Schulze rule, the
coagulating effect of an ion on dispersed phase
[C16 H 33 (CH 3 )3 N + Br - ] is a cationic micelle
of opposite charge increases with the valency
of the ion. Therefore, more the charge on
19. (a) o- Polarhead oppositely charged ion, higher is the coagulation
n- Non-polar tail value.
(micelle)
Positive ion can coagulate negatively charged
20. (b) On addition of electrolyte, charge of colloid and vice-versa. So, the ability depends on
colloidal particles will get neutralized and both magnitude and sign of its charge but the power
coagulation will occur. of coagulation depends only on the magnitude of
21. (c) According to this law the coagulating charge.
effect of an ion on dispersed phase of opposite
24. (d) Dialysis is a process of removing a
charge increases with the valency of the ion.
dissolved substance from a colloidal solution
The precipitating power of Al3+ , Ba++, Na+ ions
by means of diffusion thr ough suitable
is in order Al3+ > Ba2+ > Na+.
membrane. Colloidal particles cannot pass
22. (c) The critical micelle concentration is the through animal membrane. Only solvent
lowest concentration at which micelle formation molecules and ions (in case of electrodialysis)
appears. When surfactants are present above can diffuse.
that CMC, they can act as emulsifiers that will
solubilise a compound (oil, dirt, etc.) which is
normally insoluble in the solvent being used.
General Principles and Processes of Isolation of Elements 193
20
General Principles
and Processes of
Isolation of Elements
2020 2019 2018 2017 2016

occurrence of
Occurrence of metals 1 E
metals
metallurgical
Metallurgical 1 A 1 E 1 A
processes
processes
Ellingham diagram 1 A
Topic 1: Occurrence of Metals Topic 2: Metallurgical Processes

1. Which one is malachite from the following ? 5. Identify the correct statement from the following:
[2019] [2020]
(a) CuFeS2 (a) Blister copper has blistered appearance
(n) Cu(OH)2 due to evolution of CO2.
(c) Fe3O4 (b) Vapour phase refining is carried out for
(d) CuCO3.Cu(OH)2 Nickel by Van Arkel method.
2. "Metals are usually not found as nitrates in their (c) Pig iron can be moulded into a variety of
ores". shapes.
Out of the following two ((i) and (ii)) reasons which (d) Wrought iron is impure iron with 4%
is/are true for the above observation ? [2015] carbon.
(i) Metal nitrates are highly unstable. 6. Identify the incorrect statement.
[NEET Odisha 2019]
(ii) Metal nitrates are highly soluble in water.
(a) Gangue is an ore contaminated with
(a) (i) and (ii) are false
undesired materials.
(b) (i) is false but (ii) is true
(b) The scientific and technological process
(c) (i) is true but (ii) is false
used for isolation of the metal from its ore is
(d) (i) and (ii) are true known as metallurgy.
3. Which one of the following is a mineral of iron? (c) Minerals are naturally occurring chemical
[2012] substances in the earth’s crust.
(a) Malachite (b) Cassiterite (d) Ores are minerals that may contain a metal.
(c) Pyrolusite (d) Magnetite 7. Considering Ellingham diagram, which of the
4. Identify the alloy containing a non-metal as a following metals can be used to reduce
constituent in it. [2012] alumina? [2018]
(a) Invar (b) Steel (a) Fe (c) Zn
(c) Bell metal (d) Bronze (c) Cu (d) Mg
EBD_8336
194 CHEMISTRY
8. Extraction of gold and silver involves leaching 13. Which of the following statements, about the
with CN– ion. Silver is later recovered by [2017] advantage of roasting of sulphide ore before
(a) distillation reduction is not true? [2007]
(b) zone refining (a) The DGfo of the sulphide is greater than
(c) displacement with Zn those for CS2 and H2S.
(d) liquation
9. Match items of Column I with the items of (b) The DGfo is negative for roasting of
Column II and asign the correct code : [2016] sulphide ore to oxide.
(c) Roasting of the sulphide to the oxide is
Column-I Column-II
thermodynamically feasible.
(A) Cyanide process (i) Ultrapure Ge
(d) Carbon and hydrogen are suitable reducing
(B) Froth flotation (ii) Dressing of ZnS agents for metal sulphides.
process 14. Sulphide ores of metals are usually concentrated
(C) Electrolytic (iii) Extraction of Al by froth flotation process. Which one of the
reduction following sulphide ores offer an exception and
(D) Zone refining (iv) Extraction of Au concentrated by chemical leaching? [2007]
(v) Purification of Ni (a) Galena (b) Copper pyrite
Code : (c) Sphalerite (d) Argentite
(A) (B) (C) (D) Topic 3: Purification and Uses of Metals
(a) (iv) (ii) (iii) (i)
(b) (ii) (iii) (i) (v) 15. The metal oxide which cannot be reduced to
metal by carbon is [NEET Kar. 2013]
(c) (i) (ii) (iii) (iv)
(a) Fe2O3 (b) Al2O3
(d) (iii) (iv) (v) (i)
(c) PbO (d) ZnO
10. In the extraction of copper from its sulphide ore,
16. Which of the following pairs of metals is purified
the metal finally obtained by the reduction of
by van Arkel method ? [2011]
cuprous oxide with : [2012, 2015 RS]
(a) Ga and In (b) Zr and Ti
(a) iron (II) sulphide (b) carbon monoxide
(c) Ag and Au (d) Ni and Fe
(c) copper (I) sulphide (d) sulphur dioxide
17. The method of zone refining of metals is based
11. Which of the following elements is present as
on the principle of [2003]
the impurity to the maximum extent in the pig iron ?
(a) Greater solubility of the impurity in the
(a) Manganese (b) Carbon [2011] molten state than in the solid
(c) Silicon (d) Phosphorus (b) Greater mobility of the pure metal than that
12. The following reactions take place in the blast of the impurity
furnace in the preparation of impure iron. Identify (c) Higher melting point of the impurity than
the reaction pertaining to the formation of the that of the pure metal
slag. [2011 M] (d) Greater noble character of the solid metal
(a) Fe2O3(s) + 3 CO(g) ®2 Fe (l) + 3 CO2 (g) than that of the impurity
(b) CaCO3 (s) ®CaO (s) + CO2 (g) 18. Method used for obtaining highly pure silicon
(c) CaO (s) + SiO2(s) ® CaSiO3 (s) used as a semiconductor material, is [1994, 96]
(d) 2C(s) + O2 (g) ®2 CO(g) (a) Oxidation (b) Electrochemical
(c) Crystallization (d) Zone refining
ANS WER KEY

1 (d) 3 (d) 5 (c) 7 (d) 9 (a) 11 (b) 13 (d) 15 (b) 17 (a)
2 (b) 4 (b) 6 (a) 8 (c) 10 (c) 12 (c) 14 (d) 16 (b) 18 (d)
General Principles and Processes of Isolation of Elements 195
Hints & Solutions

1. (d) Molachite is a green copper carborate Cu2S + 2Cu2O ® 6Cu + SO2
hydroxide mineral with chemical composition 11. (b) Pig iron or cast iron contains 3 – 5% carbon
CuCO3.C4(OH)2. and varying amounts of Mn, Si, P and S which
2. (b) Metal nitrates are highly soluble in water makes the iron hard and brittle.
and are very stable for e.g. NaNO3 and KNO3. 12. (c) In blast furnace at about 1270 K, calcium
3. (d) [Fe3O4 Þ Magnetite] carbonate is almost completely decomposed to
[CuCO3 Cu(OH)2 – Malachite] give CaO which acts as a flux and combines with
[Pyrolusite – MnO2] [Cassiterite – SnO2]. SiO2 present as impurity (gangue) in the ore to
4. (b) Invar is a nickel iron alloy, Bell metal is an form calcium silicate (fusible slag)
alloy of about 80% copper and 20% tin, Bronze CaO(s) (basic flux) + SiO2 (s) (acidic flux)
is also an alloy of copper and tin. ¾¾ ® CaSiO3 (s) (slag)
Steel : It always have few % of carbon. 13. (d) The sulphide ore is roasted to oxide before
5. (c) The iron obtained from blast furnace reduction because the DG°f of most of the
contains about 4% carbon and smaller amount sulphides are greater than those of CS2 and H2S,
of impurities like S, P, Si, Mn. This form of iron is therefore, neither C nor H can reduce metal
known as pig iron. It can be moulded into variety sulphide to metal. Further, the standard free
of shapes. Blister copper has blistered appearence energies of formation of oxide are much less than
due to evolution of SO2.van Arkel method is used those of SO2. Hence, oxidation of metal sulphides
for refining of Zirconium or Titatanium. to metal oxide is thermodynamically favourable.
6. (a) Gangue is the commercially worthless 14. (d) Leaching is the selective dissolution of the
material which is contaminating the ore. desired mineral leaving behind the impurities in
7. (d) Mg has more – DG value than alumina. So a suitable dissolving agent, e.g. Argentitie or
it will be in the lower part of Ellingham diagram. Silver glance, Ag2S is an ore of silver. Silver is
Metals which have more – DG value can reduce extracted from argentite by the mac-Arthur and
those metal oxides which have less – DG value. Forest process (leaching process).
8. (c) Zn being more reactive than Ag and Au, Ag 2S + 4NaCN ® 2Na[Ag ( CN )2 ] + Na 2S
displaces them.
15. (b) Al2O3 cannot be reduced by carbon.
Leaching
4Ag + 8NaCN + 2H2O + O2 ¾¾¾¾ ® In Ellingham diagram, place of aluminium oxidation
4Na[Ag(CN)2] + 4NaOH is much below than that of carbon. Thus, carbon
Soluble Sodium dicyanoargentate (I) cannot reduce Al2O3 to Aluminium metal.
Soluble cyanide compound can be treated with Zn
to give metal by displacement. 16. (b) Zr and Ti are purified by van Arkel method.
2Na[Ag(CN)2] + Zn ¾¾¾¾¾¾
Displacement
® Zr(s) + 2I 2 (g) ¾¾
® ZrI 4 (g)
Na2[Zn(CN)4] + 2Ag¯ On the hot
ZrI4 (g) ¾¾¾ ¾¾
® Zr(s) + 2I 2 (g)
filament
9. (a) Highly electropositive metals like Al, K, Na 17. (a) Zone refining is based on the difference in
etc. are extracted by the electrolytic reduction. solubility of impurities in molten and solid state
• zone refining method is used for obtaining of the metal. This method is used for obtaining
metals of high purity e.g. Ge. metals of very high purity.
• Froth flotation process is suitable for 18. (d) Si obtained by reduction of SiCl4 with H2 is
sulphide ores. further purified by zone refining method to get
• Cyanide process is used for the extraction Si of very high purity.
of gold.
Silicon is purified by zone-refining process because
10. (c) 2 Cu2S (s) + 3O2 (g) ® 2Cu2O(s) + 2SO2(g)
the impurities present in it are more soluble in the
The unchanged Cu2S, mixed with Cu2O and liquid phase than in the solid phase.
heated strongly in absence of air
EBD_8336
196 CHEMISTRY
21 The p -Block Elements

(Group 15, 16, 17 and 18)
2020 2019 2018 2017 2016
Topic Nam e Sub-Topic QNS. LOD QNS. LOD QNS. LOD QNS. LOD QN S. LOD
oxi da ti on s ta tes i n
1 A
N compounds
a cid s trength of
oxophos phorus 1 A
Ni trogen fa mi ly a cid
chemi ca l rea ctions
of nitrogen /
1 A 1 E
ni trogen
compounds
oxoa cids of s ulphur 1 A 1 A
Oxygen fa mil y
s ta bi l ity order of
1 A
hydrides
prepa ra ti on
1 A
proces ses
structure of PCl 5 1 A
interhal ogen
1 A
compounds
Ha l ogen fa mi ly
bond dis s ocia ti on
1 E
entha l py
oxoa cids /oxi dation
s ta tes/electron 1 A 1 A
a ffini ty
hybri dis a ti on a nd
Nobl e ga ses s tructures of noble 1 A
ga s compounds
Topic 1: Nitrogen Family 2. A compound ‘X’ upon reaction with H2 O

produces a colorless gas ‘Y’ with rotton fish
1. Urea reacts with water to form A which will smell. Gas ‘Y’ is absorbed in a solution of CuSO4
decompose to form B. B when passed through Cu2+ to give Cu3P2 as one of the products. Predict
(aq), deep blue colour solution C is formed. What is the compound ‘X’. [NEET Odisha 2019]
the formula of C from the following ? [2020]
(a) Ca3(PO4) 2 (b) Ca3P2
(a) [Cu(NH3)4]2+ (b) Cu(OH)2
(c) NH4Cl (d) As 2 O 3
(c) CuCO3 Cu(OH)2 (d) CuSO4
The p-Block Elements (Group 15, 16, 17 and 18) 197
3. Which of the following oxoacids of phosphorus 11. How many bridging oxygen atoms are present
has strongest reducing property? in P4O10? [2010]
[NEET Odisha 2019] (a) 5 (b) 6
(a) H3PO4 (b) H4P2O7 (c) 4 (d) 2
(c) H3PO3 (d) H3PO2 12. Nitrogen forms N2, but phosphorus is converted
4. The correct order of N-compounds in its into P4 from P, the reason is [2001]
decreasing order of oxidation states is [2018] (a) Triple bond is present between phosphorus
(a) HNO3, NO, N2, NH4Cl atom
(b) pp – pp bonding is strong
(b) HNO3, NO, NH4Cl, N2
(c) pp – pp bonding is weak
(c) NH4Cl, N2, NO, HNO3
(d) Multiple bond is formed easily
(d) HNO3, NH4Cl, NO, N2 13. Which of the following oxy-acids has the
5. Which is the correct statement for the given maximum number of hydrogens directly attached
acids? [2016] to phosphorus? [1999]
(a) Phosphinic acid is a diprotic acid while (a) H4P2O7 (b) H3PO2
phosphonic acid is a monoprotic acid
(c) H3PO3 (d) H3PO4
(b) Phosphinic acid is a monoprotic acid while
14. Repeated use of which one of the following
phosphonic acid is a diprotic acid
fertilizers would increase the acidity of the soil?
(c) Both are triprotic acids
[1998]
(d) Both are diprotic acids
(a) Urea
6. The product obtained as a result of a reaction of
(b) Superphosphate of lime
nitrogen with CaC2 is [2016]
(c) Ammonium sulphate
(a) CaCN2 (b) CaCN
(d) Potassium nitrate
(c) CaCN3 (d) Ca2CN
15. Which of the following species has the highest
7. Strong reducing behaviour of H3PO2 is due to
dipole moment ? [1997]
[2015 RS]
(a) NH3 (b) PH3
(a) presence of one –OH group and two P–H (c) AsH3 (d) SbH3
bonds 16. The structural formula of hypophosphorous
(b) high electron gain enthalpy of phosphorus acid is [1997]
(c) high oxidation state of phosphorus
O O
(d) presence of two –OH groups and one P–H bond.
8. In which of the following compounds, nitrogen P P
(a) H (b) H
exhibits highest oxidation state ? [2012] OH OH
H OH
(a) N2H4 (b) NH3
(c) N3H (d) NH2OH O O
9. Which of the following statements is not valid P P
for oxoacids of phosphorus? [2012] (c) HO (d) H
OH OOH
(a) Orthophosphoric acid is used in the OH OH
manufacture of triple superphosphate. 17. Brown ring test is used to detect [1994]
(b) Hypophosphorous acid is a diprotic acid. (a) Iodine (b) Nitrate
(c) All oxoacids contain tetrahedral four (c) Iron (d) Bromide
coordinated phosphorus. 18. Which of the following fertilizers has the highest
(d) All oxoacids contain atleast one P = O and nitrogen percentage ? [1993]
one P — OH group. (a) Ammonium sulphate
10. Oxidation states of P in H4 P2O5 , H4 P2O6 , and (b) Calcium cyanamide
H4 P2O7 , are respectively: [2010] (c) Urea
(a) + 3, + 5, + 4 (b) + 5, + 3, + 4 (d) Ammonium nitrate
(c) + 5, + 4, + 3 (d) + 3, + 4, + 5
EBD_8336
198 CHEMISTRY
19. Which one of the following substance is used 29. Pure nitrogen is prepared in the laboratory by
in the laboratory for fast drying of neutral heating a mixture of [1991]
gases? [1992] (a) NH4OH + NaCl (b) NH4 NO3 + NaCl
(a) Phosphorus pentoxide (c) NH4 Cl + NaOH (d) NH4 Cl + NaNO2.
(b) Active charcoal 30. Which of the following statements is not correct
(c) Anhydrous calcium chloride for nitrogen ? [1990]
(d) Na3PO4.
(a) Its electronegativity is very high
20. Number of electrons shared in the formation of
(b) d-orbitals are available for bonding
nitrogen molecule is [1992]
(c) It is a typical non-metal
(a) 6 (b) 10
(c) 2 (d) 8 (d) Its molecular size is small
31. Of the following hybrides which one has the
21. Sugarcane on reaction with nitric acid gives lowest boiling point ? [1989]
[1992]
(a) CO2 and SO2 (a) AsH 3 (b) SbH 3
(b) (COOH)2 (c) PH 3 (d) NH 3
(c) 2 HCOOH (two moles) 32. Which of the following metal evolves hydrogen
(d) No reaction. on reacting with cold dilute HNO3 ? [1989]
22. Nitrogen is relatively inactive elemen t (a) Mg (b) Al
because [1992] (c) Fe (d) Cu.
(a) Its atom has a stable electronic configuration 33. Which one of the following compounds does
(b) It has low atomic radius not exist ? [1989]
(c) Its electronegativity is fairly high (a) NCl5 (b) AsF5
(d) Dissociation energy of its molecule is fairly (c) SbCl5 (d) PF5
high 34. Each of the following is true about white and
23. H3PO2 is the molecular formula of an acid of red phosphorus except that they [1989]
phosphorus. Its name and basicity respectively (a) Are both soluble in CS2
are [1992]
(b) Can be oxidised by heating in air
(a) Phosphorus acid and two
(c) Consist of the same kind of atoms
(b) Hypophosphorous acid and two
(c) Hypophosphorous acid and one (d) Can be converted into one another
35. When orthophosphoric acid is heated to 600°C,
(d) Hypophosphoric acid and two
the product formed is [1989]
24. Aqueous solution of ammonia consists of
(a) PH3 (b) P2O5
[1991]
(c) H3PO3 (d) HPO3
(a) H+ (b) OH–
36. Which of the following is a nitric acid anhydride?
(c) NH4+ (d) NH4+and OH–
[1988]
25. P2O5 is heated with water to give [1991]
(a) NO (b) NO2
(a) Hypophosphorous acid
(b) Phosphorous acid (c) N2O5 (d) N2O3.
(c) Hypophosphoric acid Topic 2: Oxygen Family
(d) Orthophosphoric acid
37. Which of the following oxoacid of sulphur has
26. Basicity of orthophosphoric acid is [1991]
– O – O – linkage? [2020]
(a) 2 (b) 3 (a) H2SO4, sulphuric acid
(c) 4 (d) 5 (b) H2S2O8, peroxodisulphuric acid
27. PCl3 reacts with water to form [1991] (c) H2S2O7, pyrosulphuric acid
(a) PH3 (b) H3PO3, HCl (d) H2SO3, sulphurous acid
(c) POCl3 (d) H3PO4 38. Identify the correct formula of ‘oleum’ from the
28. PH4I + NaOH forms [1991] following. [NEET Odisha 2019]
(a) PH3 (b) NH3 (a) H2S2O8 (c) H2S2O7
(c) P4O6 (d) P4O10 (c) H2SO3 (d) H2SO4
39. Which is the correct thermal stability order for 47. Match List - I (substances) with List - II (processes)
H2E (E = O, S, Se, Te and Po) ? [2019] employed in the manufacture of the substances
(a) H2S < H2O < H2Se < H2Te < H2Po and select the correct option. [2010]
(b) H2O < H2S < H2Se < H2Te < H2Po List - I List - II
(c) H2Po < H2Te < H2Se < H2S < H2O Substances Processes
(d) H2Se < H2Te < H2Po < H2O < H2S 1. Sulphuric acid (i) Haber’s process
40. In which pair of ions both the species contain 2. Steel (ii) Bessemer’s
S – S bond? [2017] process
2 -
(a) S4 O6 ,S2 O3 2 - (b) S2 O7 ,S2 O82 -
2 -
3. Sodium hydroxide (iii) Leblanc process
(c) S4 O62- ,S2 O72 - (d) S2 O72- ,S2 O32 - 4. Ammonia (iv) Contact process
41. Nitrogen dioxide and sulphur dioxide have some Code :
properties in common. Which property is shown 1 2 3 4
by one of these compounds, but not by the (a) (iv) (ii) (iii) (i)
other? [2015] (b) (i) (iv) (ii) (iii)
(a) is a reducing agent (c) (i) (ii) (iii) (iv)
(b) is soluble in water (d) (iv) (iii) (ii) (i)
(c) is used as a food-preservative 48. Which of the following is the most basic oxide?
(d) forms 'acid-rain' [2006]
42. Which of the statements given below is (a) Sb2O3 (b) Bi2O3
incorrect? [2015 RS] (c) SeO2 (d) Al2O3
(a) Cl2O7 is an anhydride of perchloric acid 49. During its reactions, ozone [1999]
(b) O3 molecule is bent (a) can only combine with hydrogen atoms
(c) ONF is isoelectronic with O2N–. (b) accepts electrons
(d) OF2 is an oxide of fluorine (c) loses electrons
43. Acidity of diprotic acids in aqueous solutions (d) shows the role of electrons to be irrelevant
increases in the order : [2014] 50. Which of the following oxides will be the least
(a) H2S < H2Se < H2Te acidic? [1996]
(b) H2Se < H2S < H2Te (a) As4O 6 (b) As 4O10
(c) H2Te < H2S < H2Se (c) P4O10 (d) P4O6
(d) H2Se < H2Te < H2S 51. Oxidation of thiosulphate by iodine gives
44. Which of the following does not give oxygen [1996]
(a) tetrathionate ion (b) sulphide ion
on heating? [NEET 2013]
(c) sulphate ion (d) sulphite ion
(a) Zn(ClO3)2 (b) K2Cr2O7
52. About 20 km above the earth, there is an ozone
(c) (NH4)2Cr2O7 (d) KClO3 layer. Which one of the following statements
45. Sulphur trioxide can be obtained by which of about ozone and ozone layer is true? [1995]
the following reaction : [2012] (a) ozone has a triatomic linear molecule
(a) CaSO 4 + C ¾¾
®
Δ (b) it is harmful as it stops useful radiation
(c) it is beneficial to us as it stops U.V radiation
Fe 2 ( SO4 )3 ¾¾
Δ
(b) ® (d) conversion of O3 to O2 is an endothermic
reaction
Δ
(c) S + H 2SO 4 ¾¾
® 53. By passing H 2S gas in acidified KMnO 4
Δ solution, we get [1995]
(d) H 2SO 4 + PCI5 ¾¾ ®
46. Which one of the following compounds is a (a) S (b) K2S
peroxide ? [2010] (c) MnO2 (d) K2SO3
54. Polyanion formation is maximum in [1994]
(a) KO 2 (b) BaO2 (a) Nitrogen (b) Oxygen
(c) MnO 2 (d) NO 2 (c) Sulphur (d) Boron
EBD_8336
200 CHEMISTRY
55. The acid which has a peroxy linkage is [1994] 63. Identify the incorrect statement related to PCI5
(a) Sulphurous acid (b) Pyrosulphuric acid from the following: [2019]
(c) Dithionic acid (d) Caro’s acid (a) Three equatorial P – Cl bonds make an
56. Which would quickly absorb oxygen? angle of 120° with each other
[1991, 92] (b) Two axial P – Cl bonds make an angle of
(a) Alkaline solution of pyrogallol 180° with each other
(b) Conc. H2SO4
(c) Axial P – Cl bonds are longer than
(c) Lime water
equatorial P – Cl bonds
(d) Alkaline solution of CuSO4
57. Oleum is [1991] (d) PC15 molecule is non-reactive
(a) Castor Oil (b) Oil of vitriol 64. Which of the following statements is not true
(c) Fuming H2SO4 (d) None of them for halogens? [2018]
58. Oxygen will directly react with each of the (a) All form monobasic oxyacids
following elements except [1989] (b) All are oxidizing agents
(a) P (b) Cl (c) Chlorine has the highest electron-gain
(c) Na (d) S. enthalpy
59. The gases respectively absorbed by alkaline (d) All but fluorine shows positive oxidation
pyrogallol and oil of cinnamon are [1989] states
(a) O3, CH4 (b) O2, O3 65. Match the interhalogen compounds of column-I
(c) SO2, CH4 (d) N2O, O3. with the geometry in column II and assign the
60. It is possible to obtain oxygen from air by correct code. [2017]
fractional distillation because [1989] Column-I Column-II
(a) oxygen is in a different group of the periodic 1. XX' (i) T-shape
table from nitrogen
2. XX'3 (ii) Pentagonal bipyramidal
(b) oxygen is more reactive than nitrogen
3. XX'5 (iii) Linear
(c) oxygen has higher b.p. than nitrogen
4. XX'7 (iv) Square-pyramidal
(d) oxygen has a lower density than nitrogen.
61. Hypo is used in photography to [1988] (v) Tetrahedral
(a) reduce AgBr grains to metallic silver Code :
(b) convert metallic silver to silver salt 1 2 3 4
(c) remove undecomposed silver bromide as a (a) (iii) (i) (iv) (ii)
soluble complex (b) (v) (iv) (iii) (ii)
(d) remove reduced silver
(c) (iv) (iii) (ii) (i)
Topic 3: Halogen Family (d) (iii) (iv) (i) (ii)
62. Match the following: [2019] 66 Among the following, the correct order of acidity
(a) Pure nitrogen (i) Chlorine is [2016]
(b) Haber process (ii) Sulphuric acid (a) HClO3 < HClO4 < HClO2 < HClO
(c) Contact proces (iii) Ammonia (b) HClO < HClO2 < HClO3 < HClO4
(d) Deacon’s process (iv) Sodium azide or (c) HClO2 < HClO < HClO3 < HClO4
Barium azide
(d) HClO4 < HClO2 < HClO < HClO3
Which of the following is the correct option ?
67. Which one of the following orders is correct for
(a) (b) (c) (d)
the bond dissociation enthalpy of halogen
(a) (i) (ii) (iii) (iv)
molecules? [2016]
(b) (ii) (iv) (i) (iii)
(a) I2 > Br2 > Cl2 > F2 (b) Cl2 > Br2 > F2 > I2
(c) (iii) (iv) (ii) (i)
(c) Br2 > I2 > F2 > Cl2 (d) F2 > Cl2 > Br2 > I2
(d) (iv) (iii) (ii) (i)
68. The variation of the boiling point of the 74. Which one of the following arrangements does
hydrogen halides is in the order HF > HI > HBr > not give the correct picture of the trends
HCl. [2015 RS] indicated against it ? [2000, 2008]
What explains the higher boiling point of (a) F2 > Cl2 > Br2 > I2 : Oxidizing power
hydrogen fluoride? (b) F2 > Cl2 > Br2 > I2 : Electron gain enthalpy
(c) F2 > Cl2 > Br2 > I2 : Bond dissociation
(a) The electronegativity of fluorine is much
energy
higher than for other elements in the group. (d) F2 > Cl2 > Br2 > I2 : Electronegativity.
(b) There is strong hydrogen bonding between 75. Which one of the following orders correctly
HF molecules represents the increasing acid strengths of the
(c) The bond energy of HF molecules is greater given acids? [2005, 2007]
than in other hydrogen halides. (a) HOClO < HOCl < HOClO3 < HOClO2
(d) The effect of nuclear shielding is much (b) HOClO2 < HOClO3 < HOClO < HOCl
reduced in fluorine which polarises the HF (c) HOClO3 < HOClO2 < HOClO < HOCl
(d) HOCl < HOClO < HOClO2 < HOClO3
molecule.
76. Which one of the following orders is not in
69. Which is the strongest acid in the following : accordance with the property stated against is ?
[NEET 2013] [2006]
(a) HClO3 (b) HClO4 (a) HI > HBr > HCl > HF : Acidic property in
(c) H2SO3 (d) H2SO4 water
70. In which of the following arrangements the given (b) F2 > Cl2 > Br2 > I2 : Electronegativity
sequence is not strictly according to the property (c) F2 > Cl2 > Br2 > I2 : Bond dissociation
indicated against it ? [2012 M] energy
(d) F2 > Cl2 > Br2 > I2 : Oxidising power
(a) HF < HCl < HBr < HI : increasing acidic 77. Which is the best description of the behaviour
strength of bromine in the reaction given below? [2004]
(b) H2O < H2S < H2Se < H2Te : increasing H 2 O + Br2 ® HOBr + HBr
pKa values (a) Proton acceptor only
(c) NH3 < PH3 < AsH3 < SbH3 : increasing (b) Both oxidized and reduced
acidic character (c) Oxidized only
(d) CO2 < SiO2 < SnO2 < PbO2 : increasing (d) Reduced only
oxidising power 78. Which of the following statements is not true ?
71. The correct order of increasing bond angles in (a) HF is a stronger acid than HCl [2003]
the following species are : [2010] (b) Among halide ions, iodide is the most
(a) Cl 2 O < ClO 2 < ClO 2– powerful reducing agent
(c) Fluorine is the only halogen that does not
(b) ClO 2 < Cl 2 O < ClO 2– show a variable oxidation state
(c) Cl 2 O < ClO 2– < ClO 2 (d) HOCl is a stronger acid than HOBr
(d) ClO 2– < Cl 2 O < ClO 2 79. A one litre flask is full of brown bromine vapour.
72. In the case of alkali metals, the covalent character The intensity of brown colour of vapour will not
decreases in the order: [2009] decrease appreciably on adding to the flask
(a) MF > MCl > MBr > MI some [1998]
(b) MF > MCl > MI > MBr (a) pieces of marble
(c) MI > MBr > MCl > MF (b) animal charcoal powder
(c) carbon tetrachloride
(d) MCl > MI > MBr > MF
(d) carbon disulphide
73. Among the following which is the strongest
80. Which one is the correct order of the size of
oxidising agent? [2009]
iodine species? [1997]
(a) Br2 (b) I2
(a) I > I+ > I– (b) I > I– > I+
(c) Cl2 (d) F2
(c) I+ > I– > I (d) I– > I > I+
EBD_8336
202 CHEMISTRY
81. Regarding F– and Cl– which of the following 90. The bleaching action of chlorine is due to [1991]
statements is/are correct? [1996] (a) Reduction (b) Hydrogenation
(i) Cl– can give up an electron more easily than (c) Chlorination (d) Oxidation
F– 91. Bleaching powder reacts with a few drops of
(ii) Cl– is a better reducing agent than F– dilute HCl to give [1989]
(iii) Cl– is smaller in size than F– (a) chlorine
(b) hypochlorous acid
(iv) F– can be oxidized more readily than Cl–
(c) calcium oxide
(a) (i) and (ii) (b) (i), (ii) and (iv) (d) oxygen
(c) (iii) and (iv) (d) only (i) 92. Bleaching powder is obtained by the action of
82. A certain compound (X) when treated with chlorine gas and [1988]
copper sulphate solution yields a brown (a) dilute solution of Ca(OH)2
precipitate. On adding hypo solution, the (b) concentrated solution of Ca(OH)2
precipitate turns white. The compound is [1994] (c) dry CaO
(a) K2CO3 (b) KI (d) dry slaked lime
(c) KBr (d) K3PO4
Topic 4: Noble Gases
83. HI can be prepared by all the following methods,
93. Match the compounds given in column I with
except [1994]
the hybridisation and shape given in column II
(a) PI 3 + H 2 O (b) KI + H 2SO 4 and mark the correct option. [2016]
(c) H 2 + I 2 ¾¾® Pt (d) I 2 + H 2S Column-I Column-II
84. Which among the following is paramagnetic? 1. XeF6 (i) Distorted octahedral
[1994] 2. XeO3 (ii) Square planar
(a) Cl 2 O (b) ClO 2 3. XeOF4 (iii) Pyramidal
4. XeF4 (iv) Square pyramidal
(c) Cl 2O 7 (d) Cl 2O 6 Code :
85. Which one of the following oxides of chlorine is 1 2 3 4
obtained by passing dry chlorine over silver (a) (i) (iii) (iv) (ii)
chlorate at 90°C ? [1994] (b) (i) (ii) (iv) (iii)
(a) Cl2O (b) ClO3 (c) (iv) (iii) (i) (ii)
(c) ClO2 (d) ClO4 (d) (iv) (i) (ii) (iii)
86. The formula for calcium chlorite is [1994] 94. Identify the incorrect statement, regarding the
molecule XeO4: [NEET Kar. 2013]
(a) Ca(ClO 4 )2 (b) Ca(ClO3 )2 (a) XeO4 molecule is tetrahedral
(c) CaClO 2 (d) Ca(ClO 2 ) 2 (b) XeO4 molecule is square planar
87. A solution of potassium bromide is treated with (c) There are four pp – dp bonds
each of the following. Which one would liberate (d) There are four sp3 – p, s bonds
95. Noble gases do not react with other elements
bromine ? [1993]
because [1994]
(a) Hydrogen iodide (b) Sulphur dioxide (a) They are mono atomic
(c) chlorine (d) Iodine (b) They are found in abundance
88. When chlorine is passed over dry slaked lime at (c) The size of their atoms is very small
room temperature, the main reaction product is (d) They are completely paired up and stable
[1992] electron shells
(a) Ca (ClO2 ) 2 (b) CaCl 2 96. Which of the following statements is false ?
[1994]
(c) CaOCl 2 (d) Ca (OCl) 2 (a) Radon is obtained from the decay of radium
89. In the manufacture of bromine from sea water, (b) Helium is inert gas
the mother liquor containing bromides is treated (c) Xenon is the most reactive among the rare
with [1992] gases
(a) Carbon dioxide (b) Chlorine (d) The most abundant rare gas found in the
(c) Iodine (d) Sulphur dioxide
ANS WER KEY

1 (a) 11 (b ) 21 (b ) 31 (c) 41 (c) 51 (a) 61 (c) 71 (d) 81 (d) 91 (a)
2 (b) 12 (c) 22 (d ) 32 (a) 42 (d) 52 (c) 62 (d ) 72 (c) 82 (b) 92 (d )
3 (d ) 13 (b) 23 (c) 33 (a) 43 (a) 53 (a) 63 (d ) 73 (d) 83 (b) 93 (a)
4 (a) 14 (c) 24 (d ) 34 (a) 44 (c) 54 (c) 64 (d ) 74 (b,c) 84 (b) 94 (b )
5 (b ) 15 (a) 25 (d ) 35 (d ) 45 (b) 55 (d) 65 (a) 75 (d) 85 (c) 95 (d )
6 (a) 16 (a) 26 (b ) 36 (c) 46 (b) 56 (a) 66 (b ) 76 (c) 86 (d) 96 (d )
7 (a) 17 (b) 27 (b ) 37 (b ) 47 (a) 57 (c) 67 (b ) 77 (b) 87 (c)
8 (c) 18 (c) 28 (a) 38 (b ) 48 (b) 58 (b) 68 (b ) 78 (a) 88 (d)
9 (b ) 19 (a) 29 (d ) 39 (c) 49 (a) 59 (b) 69 (b ) 79 (a) 89 (b)
10 (d ) 20 (a) 30 (b ) 40 (a) 50 (a) 60 (c) 70 (b ) 80 (d) 90 (d)
Hints & Solutions

1. (a) 5. (b) Phosphinic acid as shown in structure below
NH2CONH2 + H2O (NH4)2CO3 has one P—OH bond, thus, it is monobasic or
(A) monoprotic
D O
P
NH3 (g) + CO3 (g) + H3O (l) H (Monoprotic)
OH
(B) H
Cu 2 + (aq) 2+ Phosphonic acid as shown in structure has two
NH3 (g) ¾¾¾¾® [Cu(NH 3 ) 4 ]
P–OH bonds, thus, it is dibasic or diprotic
(B) (C) O
[Blue coloured
solution]
P
2. (b) H (Diprotic acid)
OH
OH
Ca 3 P2 + 6H 2O ¾¾
® 3Ca(OH)2 + 2PH 3 6. (a) CaC2 + N2 ® CaCN2 + C
(X) (Y)
( rotten fish smell ) 7. (a) The acids which contain P-H bond have
strong reducing properties.
2PH3 + 3CuSO 4 ¾¾
® Cu 3 P2 + 3H 2SO4
(Y)
H3PO2 acid is good reducing agent as it contains
3. (d) Hypophosphorous acid is a good reducing two P–H bonds and reduces, for example, AgNO3
to metallic silver.
agent as it contains two P–H bonds.
4 AgNO3 + 2H2O + H3PO2 —®
4AgNO3 + 2H2O + H3PO2 ¾¾ ®
4Ag + 4HNO3 + H3PO4 4Ag + 4HNO3 + H3PO4
+5 +2 0 -3 8. (c) Compound Oxidation number of

4. (a) HNO3 , NO, N2 , NH4Cl nitrogen
N2H4 = –2
Nitrogen in its elemental form has zero oxidation NH3 = –3
state. N3H = –1/3
NH2OH = –1
EBD_8336
204 CHEMISTRY
13. (b)
O OH OH
9. (b) H P H Hypophosphorous acid (a) H4P2O7 Þ O P O P O
O OH OH
H Pyrophosphoric acid
O
(H3PO2) is a monobasic acid. i.e., it has only
one ionisable hydrogen atom or one OH is P
(b) H3PO2 Þ OH H
O H
Hypophosphorous acid
present H P OH
O
H (c) H3PO3 Þ HO – P – OH
H
Phosphorous acid
+3 +3
O
10. (d) HO - P - O - P - OH = H 4 P2O5
| | (d) H3PO4 Þ HO – P – OH
OH OH
OH
orthophosphoric acid
14. (c) Ammonium sulphate is a salt of weak base
O O
|| || and strong acid, so it produces acidity. Hence
HO - P - P - OH = H 4 P2 O6 aqueous solution of ammonium sulphate
+4 | | +4
increases the acidity of soil.
OH OH
15. (a) Order of dipole moment decreases as
NH3 > PH3 > AsH3 > SbH3
O O (Based upon electronegativity)
|| ||
16. (a) We know that empirical formula of
HO - P - O - P - OH = H 4 P2 O7
+5 | | +5 hypophosphorus acid is H3PO2. In this only
OH OH one ionisable hydrogen atom is present i.e. it is
monobasic. Therefore option (a) is correct
11. (b) O structural formula of it.
bridging P bridging 17. (b) Brown ring test is done for the confirmation
O of NO 3- ions.
O
O
NaNO3 (aq) + H 2SO4 (aq)
P O
¾¾
® NaHSO4 (aq) + HNO3 (aq)
O P
O 6FeSO4 + 2HNO3 +3H 2SO4
O P O ¾¾
® 3Fe 2 (SO 4 )3 +2NO+4H 2O
bridging
O bridging FeSO4 + NO ¾¾
® [Fe(NO)]SO4
oxygen
Ferrous nitroso-sulphate
i.e. 6-bridging oxygen. (Brown ring)
12. (c) Nitrogen form N 2 (i. e. N º N) but 18. (c) Urea (46.6%N). % of N in other compound
phosphorus form P4, because in P2, pp — pp are : ( NH 4 ) 2 SO 4 = 21.2%;
bonding is present which is a weaker bonding.
CaCN 2 = 35.0% and NH 4 NO3 = 35.0%
19. (a) Phosphorus pentoxide has great affinity for 27. (b) PCl3 + 3H 2 O ® H 3PO 3 + 3HCl
water. It forms ortho phosphoric acid on
absorbing water 28. (a) PH 4 I + NaOH ® NaI + PH 3 + H 2 O
i.e. P4 O10 + 6H 2 O ¾¾ ® 4H 3 PO 4 29. (d) Pure nitrogen in the lab can be obtained by
It is thus used as a powerful dehydrating or heating ammonium nitrate. Ammonium nitrate is
drying agent. not a stable compound it dissociate to give
20. (a) Nitrogen molecule is diatomic containing a nitrogen.
triple bond between two N atoms, N º N . Heat
:
:
NH 4 Cl + NaNO 2 ¾¾¾® NH 4 NO 2
Therefore, nitrogen molecule is formed by
sharing six electrons. Heat
¾¾¾® N 2 + 2 H 2 O.
21. (b) Cane sugar is oxidised to oxalic acid
30. (b) In case of nitrogen, d-orbitals are not
(2HNO 3 ¾¾ ® H 2 O + 2NO 2 + O)18 available.
C12 H 22 O11 + 18[O] ¾ ¾® 6 (COOH) 2 31. (c) NH3 undergoes H-bonding and hence has
Cane sugar From HNO3 Oxalic acid the highest b.p. Among the remaining hydrides
+ 5H 2O. i.e. PH3, AsH3 and SbH3 the b.p. increases as
the size of the element increases and hence the
C12H22O11 + 36HNO3 ¾¾ ® magnitude of the van der Waal’s forces of
6(COOH)2 + 36NO2 + 23H2O attraction increases. Thus, PH3 has the lowest
22. (d) N2 molecule contains triple bond between b.p.
N atoms having very high dissociation energy 32. (a) Magnesium and manganese are the metals
(946 kJ mol–1) due to which it is relatively that produce hydrogen with dilute nitric acid
inactive. Mg + 2HNO3 ¾ ¾® Mg (NO3)2 + H2
23. (c) H3PO2 is named as hypophosphorous acid. 33. (a) As Nitrogen does not have d-orbital in its
As it contains only one P – OH group, its basicity valence shell, it cannot form NCl5.
is one. 34. (a) Red phosphorus is not soluble in CS2, only
24. (d) Aqueous solution of ammonia is obtained white P is soluble.
by passing NH3 in H2O which gives NH4+ and
OH– ions. 600°C
35. (d) 2H 3 PO 4 ¾¾¾¾
® 2HPO3
orthophosphoric -2H 2O metaphosphoric
NH 3 + H 2 O NH 4+
+ OH -
acid acid
25. (d) P2O5 have great affinity for water. The final
36. (c) N 2 O 5 + H 2 O ¾¾® 2 HNO 3
product is orthophosphoric acid.
2H2O O O
P4O10 4HPO3
Metaphosphoric
acid 37. (b) HO – S – O – O – S – OH
2H2O O O
2H 2O Peroxodisulphuric acid
4H3PO4 2H4P2O7
orthophosphoric Pyrophosphoric
acid acid Peroxosulphuric acid is also known as Marshall's
26. (b) It is a tribasic acid as all the three hydrogen acid and is one of the most powerful peroxy acid
oxidant.
atoms are ionisable. It forms three series of salts.
+ – 38. (b) Oleum is H2S2O7.
H3PO4 H + H2PO4
39. (c) On going down the group, bond
dissociation enthalpy of the hydrides of oxygen
+ 3– + 2– family decreases. Therefore, thermal stability
3H + PO4 2H + HPO4
also decreases.
EBD_8336
206 CHEMISTRY
O O O increasing size of the central atom. Thus Al2O3
– and Sb2O3 are amphoteric and Bi2O3 is basic.
40. (a) O – S – S – S – S – O S
49. (a) Since ozone can easily lose oxygen atom
O O S O
O (nascent oxygen), it acts as a powerful oxidising
S4 O6 2 - S2 O32 - agent, and hence, reacts with hydrogen atoms.
41. (c) SO2 is widely used in food and drinks 50. (a) As the O.N of the central atom of the
industries for its property as a preservative and compounds increases, acidic strength of that
compound also increases and on moving from
antioxidant while NO2 is not used as food
top to bottom in groups acidic strength of oxides
preservative.
also decrease due to decreasing
42. (d) OF2; among the following O and F, F is more electronegativity in groups.
electronegative than oxygen. +5 +3 +5 +3
So OF2 cannot be called oxide because in that P4O10 > P4O6 > As 4O10 > As 4O6
case fluorine is in +1 oxidation state which is
not possible, so OF2 is called oxygen difluoride. 51. (a) 2 S2 O 3-2 + I 2 ® S 4O 6-2 + 2I -
Tetrathion ate
43. (a) The weakning of M—H bond with increase
52. (c) Ozone layer is beneficial to us, because it
in size of M (where M = S, Se, Te) explains the
stops harmful ultraviolet radiations to reach the
acid character of hydrides.
earth.
On moving down the group, atomic size increases 53. (a) 2 KMnO 4 + 5H 2 S + 3H 2 SO 4 ¾¾®
hence, bond length increases and hence, removal
tendency of H also increases. K 2 SO 4 + 2MnSO 4 + 5S + 8H 2 O.
Thus, in this reaction sulphur (S) is produced.
D
44. (c) (NH4)2Cr2O7 ¾¾® N2 + Cr 2O3 + 4H2O 54. (c) Due to greater tendency for catenation,
D sulphur shows property of polyanion formation
Zn(ClO3)2 ¾¾® ZnCl2 + 3O2 to a greater extent. For example, in polysulphides
D
2 KClO3 ¾¾® 2KCl + 3O2 such as S32 - , S24 - , S52 -
D
4K2Cr2O7 ¾¾® 4K2CrO4 + 2Cr2O3 + 3O2 55. (d) Caro’s acid is H 2SO 5 which contains one
S – O – O – H peroxy linkage. It is also known as
Δ permonosulphuric acid.
45. (b) Fe 2 (SO 4 )3 ¾¾
® Fe2 O3 + SO3
O
O ||
H – O – O – S – OH
46. (b) Ba ||
O
Caro's acid
O 56. (a) Upon oxidation, pyrogallol forms hydroxy-
47. (a) quinone and many other higher molecular mass
(1) Sulphuric acid (iv) Contact process products.
(2) Steel (ii) Bessemer’s
process OH O
HO OH HO ||
(3) Sodium hydroxide (iii) Leblanc process O
||
O (air)
(4) Ammonia (i) Haber’s process ¾¾¾®
2
48. (b) More the oxidation state of the central atom 1-hydroxy,
pyrogallol
(metal), more is its acidity. Hence, SeO2 (O. S. of 2-benzoquinone
Se = +4) is acidic. Further for a given O.S., the
basic character of the oxides increases with the
66. (b) Acidic strength increases as the oxidation
Hydroxy groups are strong activators of aromatic number of central atom increases.
systems, hence pyrogallol is reactive enough to HClO < HClO2 < HClO3 < HClO4
react with oxygen in air.
+1 +3 +5 +7
57. (c) Oleum is H 2S2 O 7 ( H 2SO 4 + SO 3 ) which 67. (b) Bond dissociation enthalpy decreases as
the bond distance increases from F2 to I2. This
is obtained by dissolving SO 3 in H2SO4 and is
is due to increase in the size of the atom, on
called fuming sulphuric acid. moving from F to I.
58. (b) S + O 2 ¾¾ ® SO 2 (burns with blue light) F – F bond dissociation enthalpy is smaller then
4Na + O 2 ¾¾
® 2NaO Cl – Cl and even smaller than Br – Br. This is
because F atom is very small and hence the three
(burns with yellow light)
lone pairs of electrons on each F atom repel the
P4 + 3O 2 ¾¾
® P4 O 6 bond pair holding the F-atoms in F2 molecules.
P4 + 5O 2 ¾¾
® P4 O10 The increasing order of bond dissociation
Cl + O 2 ¾¾ ® No reaction enthalphy is
I2 < F2 < Br2 < Cl2
Chlorine does not react directly with oxygen.
68. (b) The H-bonding is present in HF due to high
59. (b) Alkaline pyrogallol absorbs O2 and oil of
electronegativity of fluorine atom. While H-
cinnamon absorbs O3.
bonding is not present in HI, HBr and HCl.
60. (c) Oxygen has higher b.pt. than nitrogen 69. (b) HClO4 is the strongest acid amongst all
therefore it can be obtained from air by fractional because the oxidation state of Cl is maximum
distillation. (+7).
Air is liquified by making use of the joule-Thomson 70. (b) If acidic nature is high, Ka is high and pKa
effect (cooling by expansion of the gas). Water is low
vapour and CO 2 are removed by solidification. H2O H2S
The remaining constituents of liquid air i.e., liquid Ka 1.8 × 10– 6 1.3 × 10–7
oxygen and liquid nitrogen are separated by means
H2Se H2Te
of fractional distillation.
Ka 1.3 × 10–4 2.3 × 10–3
61. (c) Undecomposed AgBr forms a soluble since pKa = – log Ka
complex with hypo Hence the order of pKa will be
AgBr + 2 Na 2S 2 O3 ® Na 3[ Ag (S 2 O 3 ) 2 ] + NaBr H2O > H2S > H2Se > H2Te
soluble complex 71. (d) (i) As the number of lone pair of electrons
62. (d) increases, bond angle decreases due to repulsion
63. (d) PCl5 is very reactive due to the presence of between lp – lp.
weak axial bonds. It is used in the synthesis of (ii) As the electronegativity of the central atom
various organic compounds. increases, bond angle increasess. Hence, the
64. (d) Due to high electronegativity and small correct order of bond angle:
.
size, F forms only one oxoacid, HOF known as : Cl : :O: Cl :
fluoric (I) acid. < <
O O Cl Cl O O
Flourine has –1 oxidation state in most of its two lone pairs two lone pairs one lone pair
compound. Oxidation number of F is +1 in HOF. and one electron
72. (c) MI > MBr > MCl > MF. As the size of the
anion decreases covalency decreases.
65. (a) XX' ® Linear (e.g. ClF, BrF)
73. (d) Standard reduction potential of halogens
XX3' ® T-Shape (e.g. ClF3, BrF3) are positive and decreases from fluorine to
XX5' ® Square pyramidal (e.g. BrF5 IF5) iodine. Therefore, halogens act as strong
XX7' ® Pentagonal bipyramidal (e.g. IF7) oxidising agent and their oxidising power
decreases from fluorine to iodine.
EBD_8336
208 CHEMISTRY
74. (b and c) Br– I–
& ion act as reducing agents and their
(a) The oxidising power of halogen follow the reducing nature is in increasing order
order F2 > Cl2 > Br2 > I2.
Cl – Br – I –
(b) The correct order of electron gain enthalpy ¾¾¾¾¾¾¾¾¾¾¾®
Reducing nature increases
of halogens is Cl2 > F2 > Br2 > I2. The low value
of F2 than Cl2 is due to its small size. 82. (b) KI reacts with CuSO4 solution to produce
(c) The correct order of bond dissociation cuprous iodide (white precipitate) and I2 (which
gives brown colour). Iodine reacts with hypo
energies of halogens is
(Na2S2O3.5H2O) solution. Decolourisation of
Cl2 > Br2 > F2 > I2. solution shows the appearance of white
(d) It is the correct order of electronegativity precipitate.
values of halogens. 2CuSO4 + 4KI ® 2K 2SO4 + 2CuI + I2
F2 > Cl2 > Br2 > I2 Cuprous iodide (Brown colour
(White ppt.) in solution)
75. (d) HO Cl < HO Cl O < HO Cl O 2 < HO Cl O3
+1 +3 +5 +7
2Na 2S2 O3 + I2 ¾¾
® Na 2S4 O6 + 2NaI
Sod. tetra
As the oxidation number of the central atom thionate
increases, strength of acid also increases. (colourless)
83. (b) HI cannot be prepared by heating iodides

76. (c) Bond dissociation energy of fluorine is less with concentrated H2SO4. The reaction between
because of its small size and repulsion between KI & H2SO4 is as follows:
electrons of two atoms. So option (c) is wrong
8KI + 5H 2 SO 4 ¾¾
® 4K 2 SO 4 + 4I 2 + 4H 2 O + H 2 S
order. The correct order is
[Cl2 > Br2 > F2 > I2] 84. (b) ClO2 contains 7 + 12 i.e. 19 electrons
0 +1 -1 (valence) which is an odd number, i.e. there is
77. (b) H 2O + B r2 ¾¾ ® HOBr+ HBr (are) free electron(s). Hence it is paramagnetic
in nature.
Thus, here oxidation number of Br increases from
85. (c) Pure ClO2 is obtained by passing dry Cl2
0 to +1 and also decreases from 0 to –1. Thus, it over AgClO3 at 90°C.
is oxidised as well as reduced.
90°C
78. (a) F is more electronegative than Cl therefore 2AgClO 3 + Cl 2 (dry ) ¾¾¾®
HF bond is stronger than HCl and hence proton 2AgCl + 2ClO 2 + O 2
is not given off easily. Hence HF is the weakest
hydrohalic acid. 86. (d) Calcium chlorite is Ca (ClO2 ) 2
79. (a) Brown bromine vapour will not react with 87. (c) A stronger oxidising agent (Cl 2 ) displaces
(a) Pieces of marble (CaCO3). a weaker oxidising agent (Br2 ) from its salt
(b) Animal charcoal powder can adsorb it. solution.
(c) In carbon tetrachloride solution it will 2KBr + Cl 2 ® 2KCl + Br2
dissolve. 88. (d)
(d) In carbon disulphide solution, bromine will
dissolve and thus, intensity of brown colour 2 Ca(OH) 2 + 2Cl 2 ® Ca(OCl) 2 + 2H 2O + CaCl2
will decrease. 89. (b) Bromide in the mother liquor is oxidised to
80. (d) We know that positive ion is always smaller Br2 by Cl 2 which is a stronger oxidising agent.
and negative ion is always larger than the 2Br - + Cl2 ® Br2 + 2Cl -
corresponding atom. Therefore the correct order (sea water)
90. (d) Bleaching action of chlorine is due to
of the size is I - > I > I + oxidation in presence of moisture. It is permanent
81. (d) The halide ions act as reducing agents . F– H 2O+Cl2 ® 2HCl+[O]
ion does not show any reducing nature but Cl–, Colouring matter + [O ] ® colourless matter
91. (a) CaOCl 2 + 2HCl ® CaCl 2 + H 2 O + Cl 2

Bleaching powder 94. (b)
92. (d) Cl 2 gas reacts with dry slaked lime,
(Tetrahedral sp 3 )
Ca (OH) 2 at 40°C to give bleaching powder
Xe : Ground state
Ca (OH) 2 + Cl 2 ® CaOCl 2 + H 2O [Kr] 4d 105s25p65d 0
93. (a) XeF6 XeO3 Xe : Excited state
F
F
1442443 14243
Xe sp3 hybridised Form 4 pp-dp bond
F Xe F orbital with oxygen
O O 4 sp3 hybridised orbitals form 4 sigma bond with
F O
F oxygen.
distorted octahedral Pyramidal
XeOF 4 XeF 4 95. (d) On account of highly stable ns 2 np 6
configuration in the valence shell. These
O F F elements have no tendency either to lose, gain
F F or share electrons with atoms of other elements
Xe Xe
i.e., their combining capacity or valency is zero.
F F F F Further all the orbitals in the atoms of these
2lp
elements are doubly occupied i.e electrons are
Square pyramidal Square planar
not available for sharing.
96. (d) The most abundant rare gas found in the
atmosphere is argon and not helium.
EBD_8336
210 CHEMISTRY
22 The d-and f-Block

Elements
2020 2019 2018 2017 2016

d-d transition and
1 A
paramagnetism
Characteristics of d- catalytic
block elements activities/oxidation
1 A
states/reducing
properties
properties of
1 E
KMnO4
Compounds of
properties of
transition metals 1 E
K2 Cr2 O7
reactions of copper 1 E
characteristics of
1 E
Lanthanoids and actinoids
actinoids electronic
1 A
configuration
Topic 1: Characteristics of d-Block Elements 2. Match the catalyst with the process
1. Identify the incorrect statement. [2020] [NEET Odisha 2019]
(a) The transition metals and their compounds Catalyst Process
are known for their catalytic activity due to (i) V2O5 (a) The oxidation of
their ability to adopt multiple oxidation ethyne to ethanal
states and to form complexes. (ii) TiCl4 + Al(CH3)3 (b) Polymerisation of
alkynes
(b) Interstitial compounds are those that are (iii) PdCl2 (c) Oxidation of SO2
formed when small atoms like H, C or N are in the manufacture
trapped inside the crystal lattices of metals. of H2SO4
(iv) Nickel complexes (d) Polymerisation of
(c) The oxidation states of chromium in CrO24 - ethylene
Which of the following is the correct option?
and Cr2 O72 - are not the same. (a) (i)-(c), (ii)-(a), (iii)-(d), (iv)-(b)
(d) Cr2+ (d4) is a stronger reducing agent than (b) (i)-(c), (ii)-(d), (iii)-(a), (iv)-(b)
Fe2+ (d6) in water. (c) (i)-(a), (ii)-(b), (iii)-(c), (iv)-(d)
(d) (i)-(a), (ii)-(c), (iii)-(b), (iv)-(d)
The d-and f-Block Elements 211
3. Which one of the following ions exhibits d-d 10. Sc (Z = 21) is a transition element but Zn (Z = 30)
transition and paramagnetism as well? [2018] is not because [NEET Kar. 2013]
(a) both Sc and Zn do not exhibit variable
(a) CrO2–
4 (b) Cr2 O72–
oxidation states
(c) MnO 2– –
(d) MnO4 (b) both Sc3+ and Zn2+ ions are colourless and
4
form white compounds
4. Magnetic moment 2.84 B.M. is given by :- (c) in case of Sc, 3d orbitals are partially filled
(At. nos, Ni = 28, Ti = 22, Cr = 24, Co = 27) [2015] but in Zn these are completely filled
(a) Ti3+ (b) Cr2+ (d) last electron is assumed to be added to 4s
(c) Co2+ (d) Ni2+ level in case of Zn
5. The number of d-electrons in Fe2+ (Z = 26) is 11. Which one of the following does not correctly
not equal to the number of electrons in which represent the correct order of the property
one of the following? [2015] indicated against it? [2012 M]
(a) p-electrons in Cl (Z = 17) (a) Ti < V < Cr < Mn : increasing number of
oxidation states
(b) d-electrons in Fe (Z = 26)
(b) Ti3+ < V3+ < Cr3+ < Mn3+ : increasing
(c) p-electrons in Ne (Z = 10)
magnetic moment
(d) s-electrons in Mg (Z = 12)
(c) Ti < V < Cr < Mn : increasing melting
6. Which is the correct order of increasing energy points
of the listed orbitals in the atom of titanium ?
(d) Ti < V < Mn < Cr : increasing 2nd ionization
[2015 RS] enthalpy
(a) 3s 4s 3p 3d (b) 4s 3s 3p 3d 12. Four successive members of the first series of
(c) 3s 3p 3d 4s (d) 3s 3p 4s 3d the transition metals are listed below. For which
7. Magnetic moment 2.83 BM is given by which of
the following ions ?
°
(
one of them the standard potential EM2+ /M )
(At. nos. Ti = 22, Cr = 24, Mn = 25, Ni = 28):- value has a positive sign? [2012 M]
[2014] (a) Co (Z = 27) (b) Ni (Z = 28)
(a) Ti3+ (b) Ni2+ (c) Cu (Z = 29) (d) Fe (Z = 26)
(c) Cr3+ (d) Mn 2+ 13. The catalytic activity of transition metals and
their compounds is ascribed mainly to : [2012 M]
8. Reason of lanthanoid contraction is:- [2014]
(a) their magnetic behaviour
(a) Negligible screening effect of ‘f ’ orbitals
(b) their unfilled d-orbitals
(b) Increasing nuclear charge
(c) their ability to adopt variable oxidation state
(c) Decreasing nuclear charge
(d) their chemical reactivity
(d) Decreasing screening effect
14. For the four successive transition elements (Cr,
9. Which of the following lanthanoid ions is Mn, Fe and Co), the stability of +2 oxidation
diamagnetic ? state will be there in which of the following order?
(At nos. Ce = 58, Sm = 62, Eu = 63, Yb = 70) [2011]
[NEET 2013] (a) Mn > Fe > Cr > Co
(a) Sm2+ (b) Eu2+ (b) Fe > Mn > Co > Cr
(c) Yb2+ (d) Ce2+ (c) Co > Mn > Fe > Cr
(d) Cr > Mn > Co > Fe
EBD_8336
212 CHEMISTRY
15. Which of the following ions will exhibit colour (a) V3+ (b) Ti3+
in aqueous solutions? [2010] (c) Mn 3+ (d) Cr3+
3+
(a) La (Z = 57) 3+
(b) Ti (Z = 22) (At.No. Ti = 22, V = 23, Cr = 24, Mn = 25)
(c) Lu3+ (Z = 71) (d) Sc3+ (Z = 21) 23. In which of the following pairs are both the ions
16. Which one of the following ions has electronic coloured in aqueous solutions ? [2006]
configuration [Ar] 3d6 ? [2010] (a) Sc3+, Ti3+ (b) Sc3+, Co2+
(a) Ni3+ (b) Mn 3+ (c) Ni2+, Cu+ (d) Ni2+, Ti3+
(c) Fe3+ (d) Co3+ (At. no. : Sc = 21, Ti = 22, Ni = 28, Cu = 29, Co = 27)
(At. Nos. Mn = 25, Fe = 26, Co = 27, Ni = 28) 24. The aqueous solution containing which one
17. Which of the following pairs has the same size? of the following ions will be colourless?
[2010] (Atomic number: Sc = 21, Fe = 26, Ti = 22, Mn
(a) Fe2+, Ni2+ (b) Zr 4+, Ti4+ = 25) [2005]
(c) Zr4+, Hf 4+ (d) Zn 2+, Hf4+ (a) Sc3+ (b) Fe2+

18. Which of the following oxidation states is the (c) Ti 3+ (d) Mn 2+
most common among the lanthanoids? [2010] 25. Four successive members of the first row
(a) 3 (b) 4 transition elements are listed below with their
atomic numbers. Which one of them is
(c) 2 (d) 5 expected to have the highest third ionization
19. Which one of the elements with the following enthalpy? [2005]
outer orbital configurations may exhibit the (a) Vanadium (Z = 23)
largest number of oxidation states? [2009]
(b) Chromium (Z = 24)
(a) 3d 54s1 (b) 3d 54s2
(c) Manganese (Z = 25)
(c) 3d 24s2 (d) 3d 34s2
(d) Iron (Z = 26)
20. Out of TiF62– , CoF63– , Cu 2 Cl 2 and NiCl2–
4 26. Among the following series of transition metal
(Z of Ti = 22, Co = 27, Cu = 29, Ni = 28), the ions, the one where all metal ions have 3d2
colourless species are: [2009] electronic configuration is (At. nos. Ti = 22;
V = 23; Cr = 24; Mn = 25) [2004]
(a) Cu2Cl2 and NiCl2–
4
(a) Ti 3+ , V 2+ , Cr 3+ , Mn 4+
(b) TiF62– ,and Cu2Cl2 (b) Ti + , V 4+ , Cr 6+ , Mn 7 +
(c) CoF63– ,and NiCl2–
4 (c) Ti 4+ , V 3+ , Cr 2+ , Mn 3+
(d) 3–
TiF62– , and CoF6 ,
(d) Ti 2+ , V 3+ , Cr 4+ , Mn 5+
27. The basic character of the transition metal
21. The correct order of decreasing second
monoxides follows the order
ionisation enthalpy of Ti (22), V(23), Cr(24) and
Mn (25) is : [2008] (Atomic No.,Ti = 22, V = 23, Cr = 24, Fe = 26)
[2003]
(a) Cr > Mn > V > Ti (b) V > Mn > Cr > Ti
(a) TiO > VO > CrO > FeO
(c) Mn > Cr > Ti > V (d) Ti > V > Cr > Mn (b) VO > CrO > TiO > FeO
22. Which one of the following ions is the most (c) CrO > VO > FeO > TiO
stable in aqueous solution? [2007] (d) TiO > FeO > VO > CrO
28. Which one of the following characteristics of 36. The electronic configurations of four elements
the transition metals is associated with their are given below. Which element does not belong
catalytic activity? [2003] to the same family as others ? [1989]
(a) Variable oxidation states (a) [ Xe]4 f 14 5d 10 6s 2 (b) [ Kr ]4d10 5s 2
2 5
(b) High enthalpy of atomization (c) [ Ne]3s 3 p (d) [ Ar ]3d10 4s 2
(c) Parmagnetic behaviour 37. Which one of the following is an ore of silver ?
[1988]
(d) Colour of hydrated ions (a) Argentite (b) Stibnite
29. Which of the following shows maximum number (c) Haematite (d) Bauxite
of oxidation states? [2002] 38. Which of the following metals corrodes readily
in moist air ? [1988]
(a) Cr (b) Fe
(a) Gold (b) Silver
(c) Mn (d) V (c) Nickel (d) Iron
30. Of the following transition metals, the maximum
Topic 2: Compounds of Transition Metals
numbers of oxidation states are exhibited by:
(a) Chromiun (Z = 24) [2000] 39. Name the gas that can readily decolourise
acidified KMnO4 solution : [2017]
(b) Manganese (Z = 25)
(a) SO2 (b) NO2
(c) Iron (Z = 26)
(c) P2O5 (d) CO2
(d) Titanium (Z=22)
40. Which one of the following statements is correct
31. Which of the following forms colourless
compound? [2000] when SO2 is passed through acidified K2Cr2O7
(a) Sc3+ (b) V3+ solution ? [2016]
(c) Ti3+ (d) Cr3+ (a) The solution turns blue

32. Which one of the following elements shows (b) The solution is decolourized
maximum number of different oxidation states in (c) SO2 is reduced
its compounds? [1998] (d) Green Cr2(SO4)3 is formed
(a) Eu (b) La 41. When copper is heated with conc. HNO3 it
(c) Ge (d) Am produces [2016]
33. Which one of the following ionic species will (a) Cu(NO3)2 and NO2
impart colour to an aqueous solution? [1998] (b) Cu (NO3)2 and NO
(a) Ti4+ (b) Cu+ (c) Cu(NO3)2, NO and NO2
(c) Zn2+ (d) Cr3+ (d) Cu(NO3)2 and N2O
34. The common oxidation states of Ti are [1994] 42. Which of the following processes does not
(a) + 2, + 3 (b) + 3, + 4 involve oxidation of iron ? [2015]
(c) – 3, – 4 (d) + 2, + 3, + 4 (a) Decolourization of blue CuSO4 solutution
35. The electronic configuration of Cu (atomic by iron
number 29) is [1991] (b) Formation of Fe(CO)5 from Fe
(a) 1s 2 , 2s 2 2 p6 , 3s 2 3 p 6 , 4s 2 3d 9 (c) Liberation of H2 from steam by iron at high
temperature
(b) 1s 2 , 2s 2 2 p6 , 3s 2 3 p6 3d 10 , 4 s1
(d) Rusting of iron sheets
(c) 1s 2 , 2s 2 2 p 6 ,3 p 2 3 p6 , 4s 2 4 p 6 ,5s 2 5 p1
43. Assuming complete ionization, same moles of
(d) 1s 2 , 2s 2 2 p6 ,3s 2 3 p 6 , 4s 2 4 p 6 3d 3
which of the following compounds will require
EBD_8336
214 CHEMISTRY
the least amount of acidified KMnO 4 for 51. German silver is an alloy of [2000]
complete oxidation [2015 RS] (a) Fe, Cr, Ni (b) Cu, Zn, Ag
(a) FeSO4 (b) FeSO3 (c) Cu, Zn, Ni (d) Cu, Sn, Al
52. Which of the following combines with Fe (II)
(c) FeC2O4 (d) Fe(NO2)2 ions to form a brown complex? [2000]
44. The pair of compounds that can exist together is: (a) NO (b) N2O
[2014] (c) N2O3 (d) N2O5
53. On heating chromite (FeCr 2O4) with Na2CO3 in
(a) FeCl3, SnCl2 (b) HgCl2, SnCl2
air, which of the following product is obtained?
(c) FeCl2, SnCl2 (d) FeCl3, KI [1999]
45. In acidic medium, H2O2 changes Cr2O7–2 to (a) Na2Cr2O7 (b) FeO
CrO5 which has two (–O–O) bonds. Oxidation (c) Fe3O4 (d) Na2CrO4
state of Cr in CrO5 is:- [2014] 54. The addition of excess of aqueous HNO3 to a
(a) + 5 (b) + 3 solution containing [Cu(NH3)4]2+ produces
(c) + 6 (d) – 10 [1999]
46. The reaction of aqueous KMnO4 with H2O2 in (a) Cu+ (b) [Cu(H2O)4]2+
acidic conditions gives: [2014] (c) Cu(OH)2 (d) Cu(NO3)2
(a) Mn4+ and O2 (b) Mn2+ and O2 55. An acidic solution of 'X' does not give precipitate
(c) Mn2+ and O3 (d) Mn4+ and MnO2 on passing H2 S through it. 'X' gives white
precipitate when NH4OH is added to it. The white
47. KMnO4 can be prepared from K2MnO4 as per precipitate dissolves in excess of NaOH solution.
the reaction: Pure 'X' fumes in air and dense white fumes are
3MnO 24 - + 2H 2O
obtained when a glass rod dipped in NH4OH is
put in the fumes. Compound 'X' can be [1999]
2MnO -4 + MnO2 + 4OH -
(a) ZnCl2 (b) FeCl3
The reaction can go to completion by removing (c) AlCl3 (d) SnCl2
OH– ions by adding. [NEET 2013] 56. Which one of the following elements constitutes
(a) KOH (b) CO2 a major impurity in pig iron ? [1998]
(c) SO2 (d) HCl (a) Silicon (b) Oxygen
48. Which of the statements is not true? [2012] (c) Sulphur (d) Graphite
(a) On passing H2S through acidified K2Cr2O7 57. K2Cr2O7 on heating with aqueous NaOH gives
solution, a milky colour is observed. [1997]
(b) Na2Cr2O7 is preferred over K2Cr2O7 in (a) CrO 24- (b) Cr(OH)3
volumetric analysis. (c) Cr2O 72- (d) Cr(OH)2
58. CrO3 dissolves in aqueous NaOH to give [1997]
(c) K2Cr2O7 solution in acidic medium is orange.
(a) Cr2O72– (b) CrO42–
(d) K2Cr 2 O7 solution becomes yellow on
(c) Cr(OH)3 (d) Cr(OH)2
increasing the pH beyond 7.
59. Cuprous compounds such as CuCl, CuCN and
49. Acidified K2Cr2O7 solution turns green when CuSCN are the only salts stable in water due to
Na 2 SO 3 is added to it. This is due to the [1996]
formation of : [2011] (a) high hydration energy of Cu+ ions
(a) Cr2(SO4)3 (b) CrO42– (b) their inherent tendency to not
(c) Cr2(SO3)3 (d) CrSO4 disproportionate
50. Copper sulphate dissolves in excess of KCN to (c) diamagnetic nature
give [2006] (d) insolubility in water
(a) [Cu(CN)4]3– (b) [Cu(CN)4]2– 60. Stainless steel contains iron and [1995]
(c) Cu(CN)2 (d) CuCN (a) Cr + Ni (b) Cr + Zn
(c) Zn + Pb (d) Fe +Cr + Ni
61. The most durable metal plating on iron to protect cyanide solution to form the soluble product
against corrosion is [1994] potassium argento cyanide. The element is
(a) Nickel plating (b) Tin plating [1989]
(c) Copper plating (d) Zinc plating (a) Lead (b) Chromium
(c) Manganese (d) Silver
62. When ( NH 4 ) 2 Cr2O 7 is heated, the gas
70. A blue colouration is not obtained when
evolved is [1994]
[1989]
(a) N2 (b) NO2
(a) Ammonium hydroxide dissolves in copper
(c) O2 (d) N2O sulphate
63. When CuSO 4 is electrolysed using platinum (b) Copper sulphate solution reacts with
electrodes, [1993] K4[Fe(CN)6]
(a) Copper is liberated at cathode, sulphur at (c) Ferric chloride reacts with sod. ferrocyanide
anode (d) Anhydrous CuSO4 is dissolved in water
(b) Copper is liberated at cathode, oxygen at Topic 3: Lanthanoids and Actinoids
anode
71. The reason for greater range of oxidation states
(c) Sulphur is liberated at cathode, oxygen at
in actinoids is attributed to :- [2017]
anode
(a) actinoid contraction
(d) Oxygen is liberated at cathode, copper at
anode (b) 5f, 6d and 7s levels having comparable
energies
64. Cinnabar is an ore of [1991]
(c) 4f and 5d levels being close in energies
(a) Hg (b) Cu
(c) Pb (d) Zn (d) the redioactive nature of actinoids
65. The composition of ‘golden spangles’ is 72. The electronic configurations of Eu(Atomic No.
63), Gd(Atomic No. 64) and Tb (Atomic No. 65)
[1990]
are [2016]
(a) PbCrO4 (b) PbI2
(a) [Xe]4f76s2, [Xe]4f 8 6s2 and [Xe]4f 85d16s2
(c) As 2S3 (d) BaCrO4 (b) [Xe]4f 7 5d1 6s 2 , [Xe]4f 7 5d1 6s2 and
66. Prussian blue is formed when [1989] [Xe]4f 96s2
(a) Ferrous sulphate reacts with FeCl3 (c) [Xe]4f 6 5d 1 6s 2 , [Xe]4f 7 5d 1 6s 2 and
(b) Ferric sulphate reacts with K4[Fe(CN)6] [Xe]4f 85d16s2
(c) Ferrous ammonium sulphate reacts with FeCl3 (d) [Xe]4f 76s2, [Xe]4f 75d16s2 and [Xe]4f 96s2
(d) Ammonium sulphate reacts with FeCl3 73. Because of lanthanoid contraction, which of the
67. Photographic films and plates have an essential following pairs of elements have nearly same
ingredient of [1989] atomic radii ? (Numbers in the parenthesis are
atomic numbers). [2015]
(a) Silver nitrate (b) Silver bromide
(a) Zr (40) and Nb (41) (b) Zr (40) and Hf (72)
(c) Sodium chloride (d) Oleic acid
68. Nitriding is the process of surface hardening of (c) Zr (40) and Ta (73) (d) Ti (22) and Zr (40)
steel by treating it in an atmosphere of [1989] 74. Gadolinium belongs to 4f series. It's atomic
(a) NH3 (b) O3 number is 64. Which of the following is the
correct electronic configuration of gadolinium ?
(c) N2 (d) H2S
[1997, NEET Kar. 2013, 2015 RS]
69. While extracting an element from its ore, the ore
is ground and leached with dil. potassium (a) [Xe]4f 86d2 (b) [Xe]4f 95s1
(c) [Xe] 4f 75d16s2 (d) [Xe] 4f 65d26s2
EBD_8336
216 CHEMISTRY
75. Which of the following exhibit only + 3 oxidation 79. The correct order of ionic radii of Y3+, La3+, Eu3+
state ? [2012 M] and Lu3+ is [2003]
(a) U (b) Th (a) La 3+ < Eu 3+ < Lu 3+ < Y 3+
(c) Ac (d) Pa
(b) Y 3+ < La 3+ < Eu 3+ < Lu 3+
76. Identify the incorrect statement among the
following: [2007]
(c) Y 3+ < Lu 3+ < Eu 3+ < La 3+
(a) Lanthanoid contraction is the accumulation (d) Lu 3+ < Eu 3+ < La 3+ < Y 3+
of successive shrinkages. (Atomic nos. Y =39, La = 57, Eu = 63, Lu = 71)
(b) As a result of lanthanoid contraction, the 80. General electronic configuration of lanthanides
properties of 4d series of the transition is [1991, 2002]
elements have no similarities with the 5d (a) (n – 2) f 1 –14 (n –1) s2p6d 0 – 1 ns2
series of elements. (b) (n – 2) f10 –14 (n –1) d 0 – 1 ns2
(c) Shielding power of 4f electrons is quite (c) (n – 2) f 0 –14 (n –1) d10 ns2
weak.
(d) (n – 2) d0 –1 (n –1) f 1 – 14 ns2
(d) There is a decrease in the radii of the atoms
or ions as one proceeds from La to Lu. 81. Which of the following statement is not correct?
77. The main reason for larger number of [2001]
oxidation states exhibited by the actinoids (a) La (OH)3 is less basic than Li(OH)3
than the corresponding lanthanoids, is (b) La is actually an element of transition series
[2005, 2006] rather lanthanides
(a) more energy difference between 5f and (c) Atomic radius of Zr and Hf are same
because of lanthanide contraction
6d orbitals than between 4f and 5d
(d) In lanthanide series ionic radius of Ln +3
orbitals.
ions decreases
(b) lesser energy difference between 5f and
6d orbitals than between 4f and 5d 82. The lanthanide contraction is responsible for
orbitals. the fact that [1997]
(c) larger atomic size of actinoids than the (a) Zr and Y have about the same radius
lanthanoids. (b) Zr and Nb have similar oxidation state
(d) greater reactive nature of the actinoids (c) Zr and Hf have about the same radius
than the lanthanoids.
(d) Zr and Zn have the same oxidation states
78. Lanthanoids are [2004]
(Atomic numbers : Zr = 40, Y = 39, Nb = 41,
(a) 14 elements in the sixth period
(atomic no. = 90 to 103) that are filling 4f Hf = 72, Zn = 30)
sublevel 83. Actinides [1994]
(b) 14 elements in the seventh period (a) Are all synthetic elements
(atomic no. = 90 to 103) that are filling 5f
(b) Include element 104
sublevel
(c) Have any short lived isotopes
(c) 14 elements in the sixth period
(atomic no. = 58 to 71) that are filling 4f (d) Have variable valency
sublevel 84. Among the lanthanides the one obtained by
(d) 14 elements in the seventh period synthetic method is [1994]
(atomic no. = 58 to 71) that are filling 4f sub (a) Lu (b) Pm
level
(c) Pr (d) Gd
ANSWER KEY
1 (c) 10 (c) 19 (b) 28 (a) 37 (a) 46 (b) 55 (a) 64 (a) 73 (b) 82 (c)
2 (b) 11 (c) 20 (b) 29 (c) 38 (d) 47 (b) 56 (d) 65 (b) 74 (c) 83 (d)
3 (c) 12 (c) 21 (a) 30 (b) 39 (a) 48 (b) 57 (a) 66 (b) 75 (c) 84 (b)
4 (d) 13 (c) 22 (d) 31 (a) 40 (d) 49 (a) 58 (b) 67 (b) 76 (b)
5 (a) 14 (a) 23 (d) 32 (d) 41 (a) 50 (a) 59 (d) 68 (a) 77 (b)
6 (d) 15 (b) 24 (a) 33 (d) 42 (b) 51 (c) 60 (d) 69 (d) 78 (c)
7 (b) 16 (d) 25 (c) 34 (b) 43 (a) 52 (a) 61 (d) 70 (b) 79 (c)
8 (a) 17 (c) 26 (d) 35 (b) 44 (c) 53 (d) 62 (a) 71 (b) 80 (a)
9 (c) 18 (a) 27 (a) 36 (c) 45 (c) 54 (b) 63 (b) 72 (d) 81 (a)
Hints & Solutions

1. (c) Oxidation state of Cr in CrO 24- and Cr2O72- 4. (d) Magnetic moment = 2.84 B.M. This
indicates that 2 unpaired electrons are present.
is + 6 i.e. oxidation states are same.
2. (b) (i) V2O5: Used in the oxidation of SO2 in For Ni+2 = 4s0 3d 8
the manufacture of H2SO4 by contact Number of unpaired electrons (n) = 2
process.
Hence, Ni2+ gives magnetic moment of 2.84 B.M.
(ii) TiCl 4 + Al(CH 3) 3 : Used in the
polymerization of ethylene. 5. (a) Fe+2 = 3d 6 (number of ‘d’ electrons = 6)
(iii) PdCl2: Used in the oxidation of ethyne In Cl = 1s2 2s2 2p6 3s2 3p5
to ethanal. total p electrons = 11, which are not equal to
(iv) Nickel complexes: Used in the number of ‘d’ electrons in Fe+2
polymerization of alkynes. p-electrons in Ne = 1s2 2s2 2p6 = 6
3. (c) CrO2–
4 Cr6+ diamagnetic s-electrons in Mg = 1s2 2s2 2p6 3s2 = 6
6. (d) (n + l) rule can be used. Titanium is a multi
Cr2O2–
7 Cr6+ diamagnetic
electron system
MnO4– Mn7+ diamagnetic (n + l) 3s < 3p < 4s < 3d
MnO 2– Mn6+ paramagnetic ¯ ¯ ¯ ¯
4
3d (3 + 0) (3 + 1) (4 + 0) (3 + 2)
|| || || ||
3 4 4 5
Thus, unpaired electron is present, so d–d
If (n + l) values are same, then value of "n" has to
transition is possible. be considered. The orbital with lower n value is
For tetrahedral geometry: filled first.
t2g t2g
7. (b) Magnetic moment
m = n(n + 2)
eg eg
3d 2.83 = n(n + 2)
Before After On solving n = 2
transition transition Ni2+ has two unpaired electrons.
EBD_8336
218 CHEMISTRY
8. (a) The shape of f-orbitals is very much 15. (b) La3+ : 54 e– = [Xe]
diffused and they have poor shielding effect. To3+ : 19 e– = [Ar] 3 d 1 (Colour)
The effective nuclear charge increases due to Lu3+ : 68 e– = [Xe] 4 f 14
imperfect shielding of one electron by another in Sc3+ : 18 e– = [Ar]
the same subshell which causes the contraction in
the size of electron charge cloud. This contraction 16. (d) Ni3+ : [Ar] 3d 7
in size is known as lanthanoid contraction. Mn3+ : [Ar] 3d 4
9. (c) Sm2+(Z = 62) Fe3+ : [Ar] 3d 5
[Xe]4f 6 6s2 – 6 unpaired e– Co3+ : [Ar] 3d 6
Eu2+(Z = 63) 17. (c) Due to lanthanide contraction, the size of
[Xe]4f7 6s2 – 7 unpaired e– Zr and Hf (atom and ions) become nearly similar
Yb2+(Z = 70) 18. (a) +3 oxidation state is most common for
[Xe]4f14 6s2 – 0 unpaired e– lanthanoids. But occasionally +2 and +4 states
Ce2+(Z = 58) are also obtained due to extra stability of
[Xe]4f1 5d1 6s2 – 2 unpaired e– empty, half-filled or filled f-subshell.
Only Yb2+ is diamagnetic. 3d 4s
10. (c) A transition element must have incomplete 19. (b) Mn - 3d5 4s2
d-subshell. Zinc have completely filled d The no. of various oxidation states possible are
subshell having 3d10 configuration. Hence do + 2, + 3, + 4, (+ 5), + 6, + 7.
not show properties of transition elements to 20. (b) In TiF62– ,– Ti is in + 4 O.S. ; 3d 0 = colourless
any appreciable extent except for their ability to
form complexes. In CoF63– –, Co is in + 3 O.S ; 3d5 = coloured
11. (c) The melting points of the transition In Cu2Cl2– Cu is in +1 O.S. ; 3d10 – colourless
elements first rise to a maximum and then fall as
the atomic number increases, manganese have In NiCl 2– 8
4 – Ni is in + 2 O.S ; 3d – coloured
abnormally low melting points. The colour exhibited by transition metal ions is
12. (c) E° +2 = 0.34 volt, due to the presence of unpaired electrons in
Cu /Cu d-orbitals which permits the d - d excitation of
Other has – ve E°R.P. electrons.
E° ++ = – 0.28
Co /Co 21. (a) Ti ; Z (22) is 1s22s22p63s23p64s23d2
E° ++ = – 0.25 V ; Z (23) is 1s22s22p63s23p64s23d3
Ni / Ni
E° ++ Cr ; Z (24) is 1s22s22p63s23p63d54s1
Fe /Fe = – 0.44
Mn ; Z (25) is 1s22s22p63s23d54s2
13. (c) The transition metals and their compounds The second electron in all the cases (except Cr)
are used as catalysts because of the variable is taken out from 4s-orbital and for Cr it is taken
oxidation states. Due to this, they easily absorb
from half-filled 3d-orbital. The force required for
and re-emit wide range of energy to provide the
removal of second electron will be more for Mn
necessary activation energy.
than others (except for Cr) due to having more
14. (a) Cr2+ = positive charge. Based on this, we find the
2+ correct order Mn > V > Ti.
Mn =
2+ i.e. Cr > Mn > V > Ti.
Fe = 3+
22. (d) V =
Co2+=
Ti3+=
Mn 2+ is most stable due to half-filled
Mn3+ =
configuration. Hence, only option (a) can be the
correct answer. Cr3+=
Cr3+ will be most stable in aqueous solution 27. (a) The basic character of the transition metal
according to crystal field theory. It has t
3 monoxide is TiO > VO > CrO > FeO because
2g
configuration, which is most stable among the basic character of oxides decrease with increase
given options. in atomic number.
23. (d) Sc3+ : 1s2, 2s2p6, 3s2p6d0, 4s0; no unpaired Oxides of transitional metals in low oxidation state
electron. i.e., + 2 and + 3 are generally basic except Cr2O3.
Cu+ : 1s2, 2s2p6, 3s2p6d10, 4s0; no unpaired
electron. 28. (a) Transition metals have the ability to utilize
Ni 2+: 1s2, 2s2p6 , 3s2 p6 d 8, 4s0; 2 unpaired (n –1)d -orbitals. Thus variable oxidation states
electron present. enables the transition element to associate with
Ti3+ : 1s2, 2s2p6, 2s2p6d1, 4s0; 1 unpaired electron the reactants in different forms.
present 29. (c) Mn : [Ar] 3d5 4s2
Co2+ : 1s2 , 2s2 p6 , 3s2 p6d7 , 4s0 ; 3 unpaired Shows +2, +3, +4, +5, +6 & +7 oxidation states
electron present 30. (b) Manganese shows max. no. of oxidation
So, from the given option, the only correct states,
combination is Ni2+ and Ti3+ +2, +3, + 4, + 5, + 6, + 7
24. (a) Sc3+® 3d0 4s0 Other metals shows the following oxidation
Fe2+® 3d6 4s0 states
Cr = + 2, +3, + 4, + 5, + 6
4 unpaired e– Fe = + 2, + 3
Ti3+® 3d14s0 Ti = + 2, + 3, + 4
1 unpaired e– 31. (a) Sc +3 ® [Ar]18 3d 0 ; V +3 ® [Ar]18 3d 2
Mn2+ ® 3d5 4s0
Ti +3 ® [Ar]18 3d1 ; Cr +3 ® [Ar]18 3d 3
5 unpaired e– Scandium ion doesn’t contain any unpaired
3+
In Sc there is no unpaired electron. So the electron in d orbitals hence it forms colourless
aqueous solution of Sc3+ will be colourless. compound.
25. (c) For third ionization enthalpy electronic 32. (d) Eu – + 2, + 3
configuration of La – +3
3d 4s
2+ – 4s0 3d3 Gd – + 3
23V Am = +2, +3, +4, +5, +6
2+ – 4s0 3d4 33. (d) We know that chromium (III) salts dissolve
24Cr
2+ 0 5
in water to give violet solution. The violet colour
25Mn – 4s 3d is due to the hydrated chromium (III) in
2+ – 4s0 3d6
26Fe [Cr(H2O)6]3+.
Mn has most stable configuration due to half 34. (b) Ti (22) = [Ar] 3d2 4s2
filled d-orbital. Hence, 3rd ionization energy will minimum oxidation state is +2 and maximum
be highest for Mn. oxidation state is +4.
26. (d) The electronic configuration of different Ti4+ = [Ar]
species given in the option (d) are : Hence, it is most stable state of Ti.
Ti 2+ :1s 2 2s 2 2p 6 3s 2 3p 6 3d 2 Ti3+ = [Ar]3d1
It acts as a good reducing agent as it can readily
V3+ :1s 2 2s 2 2p6 3s 2 3p6 3d 2 oxidized to Ti4+ ion.
Ti2+ = [Ar]3d2
Cr 4+ :1s 2 2s 2 2p 6 3s 2 3p 6 3d 2
It is the most unstable form.
Mn5+ :1s 2 2s 2 2p6 3s 2 3p 6 3d 2 Thus, +3 and +4 are the common oxidation states.
EBD_8336
220 CHEMISTRY
The minimum oxidation state of transition metals 44. (c) Both are reducing agents.
is equal to the number of electrons in 4s shell and 45. (c) The structure of CrO5 is
the maximum oxidation state is equal to the sum of
O O
the 4s and 3d electrons.
Cr
35. (b) Electronic configuration of Cu (29) is 1s2
2s 2 2p6 3s2 3p6 4s1 3d10 and not 1s2, 2s2 2p6 3s2 O O
3p6 4s2, 3d9 due to extra stability of fully filled O
orbitals. Hence, CrO5 has two proxy linkage.
36. (c) [Ne]3s23p5 is the electronic configuration Now suppose the oxi. no. of Cr is x then
of a p-block element whereas other x + (– 1 × 4) + (– 2) = 0
configurations are those of d-block elements \ x=+6
37. (a) Argentite or silver glance (Ag2S) is an ore 46. (b) 2 KMnO4 + 3H2SO4 + 5H2O2 ¾®
of Ag.
38. (d) In moist air, corrosion of iron takes place in K2SO4 + 2MnSO4 + 8H2O + 5O2
i.e. Mn2+ ion and O2.
the form of rust (Fe 2O 3 + Fe(OH)3 ) . As iron is
most reactive among all. 47. (b) HCl and SO2 are reducing agents and can
39. (a) Potassium permanganate has a purple colour. reduce MnO4–. CO2 which is neither oxidising
When sulphur dioxide reacts with potassium and nor reducing will provide only acidic
permanganate, the solution decolourises. medium. It can shift reaction in forward direction
5SO2 + 2KMnO4 + 2H2O ® 2H2SO4 + 2MnSO4 and reaction can go to completion.
+ K2SO4 48. (b) Na2Cr 2O7 is hygroscopic in nature and
40. (d) K2Cr2O7 + SO2 + H2SO4 therefore accurate weighing is not possible in
® K2SO4 + Cr 2(SO4)3 + H2O normal atmospheric conditions. A hygroscopic
green colour substance absorbs moisture from atmosphere
41. (a) Less active metals like Cu, Ag etc. react and this could lead to inaccuracies in weight.
with conc. acid and form nitrate and nitrogen
dioxide. 49. (a) The green colour appears due to the
42. (b) Formation of Fe(CO)5 from Fe involves no formation of Cr3+ion
change in oxidation state of iron. 2– 2– 2–
Cr2O7 + 3SO3 + 8H+ ¾® 3SO4 + 2Cr3+ + 4H2O
43. (a) Considering the same moles of compounds 50. (a) Copper sulphate on treatment with excess
Fe2+ SO2–
4 only Fe
2+ is oxidised by KMnO .
4 of KCN forms complex K 3 [Cu(CN) 4 ] or
( +6) [Cu(CN)4]3–
SO2–
4 in which sulphur is in highest oxidation
state cannot be oxidised. CuSO 4 + 2KCN ¾
¾® Cu ( CN ) 2 + K 2SO 4
Fe 2+ SO32– ¾¾ ® Fe3+ 2 Cu ( CN ) 2 ¾
¾® Cu 2 (CN ) 2 + (CN ) 2
(+4) (+6)
2–
SO3 —® SO4 + 2e
2– –
Cu2(CN)2 + 3KCN ¾® K3[Cu(CN)4] + CuCN
Sulphur can be oxidised to (+6) i.e to SO 2– 51. (c) German Silver Composition : Cu = 56%,
4
Zn = 24%, Ni = 20%
In FeC2 O4 ¾¾ ® Fe3+
Carbon can be oxidised to (+IV) i.e to CO2 52. (a) We know that when nitrogen oxide (NO)
combines with Fe (II) ions, a brown complex is
Fe(NO 2 ) 2 ¾¾® Fe3+
formed. This reaction is called brown ring test
(+3)
+ 2NO2– Nitrogen can be 53. (d) By heating chromite with Na2 CO3, Na2CrO4
oxidised to (+V) is obtained
¯ – – state
2NO3 + 2e 4FeCr2O4 + 8Na2CO3 + 7O2 ¾®
8Na2CrO4 + 2Fe2O3 + 8CO2
(+5)
54. (b) When excess of aq. HNO3 to [C4(H3)4]2+ 63. (b) CuSO 4 Cu 2+ + SO 24 - ;
produces [(4(H2O)4]2+. H + + OH -
H 2 O
Following equillibrium exist in the given aqueous At cathode : Cu2+ + 2e– ¾® Cu
solution At anode : 4OH– ¾® 2H2O + O2 + 4e–
[Cu(H2O)4]2+(aq) + 4NH3(aq) 64. (a) Cinnabar (HgS) is an ore of Hg.
[Cu(NH3)4]2+(aq) + 4H2O(l) 65. (b) PbI2 is yellow and is called golden spangles.
` When HNO3 is added to this solution: 66. (b) Potassium ferrocyanide solution is added
(excess) HNO3 (aq) +NH3 (aq) ¾® to Fe3+ ions in solution to give deep blue solution
NH +4 (aq) + NO 3– (aq) or precipitate.
Thus, amount of NH3(aq) will reduce drastically. 2Fe2(SO4)3 + 3K4[Fe(CN)6] ¾®
With a simple application of Le Chatelier's
principle, the equillibrium will shift towards left Fe4[Fe(CN)6]3 + 6K2SO4
in the first reaction. Hence, [Cu(H2O)4]2+ will form. Prussian blue
67. (b) AgBr is highly photosensitive and is used
NH 4 OH
55. (a) X ¾¾ ¾¾® White ppt in photographic films and plates.
68. (a) When steel is heated in presence of NH3,
excess
¾¾ ¾
¾® Acidic solution (soluble ) iron nitride on the surface of steel is formed which
NaOH ( No. ppt with H 2S) imparts a hard coating. This process is called
Given reactions (white precipitate with H2S in nitriding.
presence of NH4OH) indicate that 'X' should be 69. (d) Cyanide process is used in the metallurgy of
ZnCl2 which explains all given reactions. Ag.
ZnCl2 + 2H2O ¾® Zn(OH)2 + 2HCl 2Ag 2S + 8 NaCN + O 2 + 2 H 2 O ¾
¾®
White fumes
4 Na[Ag(CN ) 2 ] + 4 NaOH + 2S
NH4OH + HCl ¾¾¾® NH4Cl
White fumes
- H 2O
Dense white fumes
2 Na[ Ag (CN ) 2 ] + Zn ¾¾®
ZnCl 2 + 2 NaOH ® Zn(OH) 2 + 2NaCl Na 2 [ Zn (CN ) 4 ] + 2 Ag ¯
2 NaOH
Zn (OH ) 2 ¾¾ ¾¾® Na 2 ZnO 2 + 2H 2 O 70. (b) 2CuSO4 + K4[Fe(CN)6] ¾®
Excess Cu2[Fe(CN)6] + 2K2SO4
56. (d) Pig iron is the most impure form of iron Chocolate ppt.
and contain highest proportion of carbon
(2.5 – 4%). 71. (b) Minimum or comparable energy gap
57. (a) K2Cr2O7 + 2NaOH ¾® between 5f, 6d and 7s subshell makes electron
K2CrO4 + Na2CrO4 + H2O excitation easier, hence there is a greater range
of oxidation states in actinoids.
Hence CrO42– ion is obtained.
72. (d) Eu (63) = [Xe] 4f 7 6s2
58. (b) CrO3 + 2NaOH ® Na 2CrO 4 + H 2 O
Gd (64) = [Xe] 4f 7 5d1 6s2
59. (d) Although Cu2+ state is more stable than Tb (65) = [Xe] 4f 9 6s2
Cu+, but Cu+ ion can be stabilized by formation 73. (b) Zr (40) and Hf (72) are in the same group
of insoluble substances such as CuCl, CuCN (4). Because of lanthanoid contraction, they have
and CuSCN. Cu2+ is more stable than Cu+ nearly same atomic radii.
because of its high hydration energy. 74. (c) Gd (64) = [Xe]4f 7 5d1 6s2
60. (d) Stainless steel contains 73% Fe, 18% Cr
75. (c) Ac (89) = [Rn] [6d1] [7s2]
and 8% Ni.
76. (b) Due to lanthanoid contraction the
61. (d) Galvanisation is the process of deposition
properties of 4d series of the transition element
of zinc metal on the surface of Fe to prevent it have similarities with the 5d series of elements.
from rusting. Zinc forms a protective layer of basic
carbonate (ZnCO3. Zn(OH)2) on it. There is a steady decrease in the radii as the atomic
number of the lanthanide elements increases. For
Heat every additional proton added in nucleus the
62. (a) (NH 4 ) 2 Cr2 O7 ¾¾¾® Cr2O3 + N 2 + 4H 2O
corresponding electron goes to 4f subshell.
EBD_8336
222 CHEMISTRY
77. (b) Lesser energy difference between 5f and 82. (c) We know that regular decrease in the size
6d orbitals than between 4f and 5d orbitals result of the atoms and ions is called lanthanide
in larger no. of oxidation state. contraction. In vertical column of transition
78. (c) Lanthanides are 4 f-series elements starting elements there is a very small change in size and
from cerium (Z = 58) to lutetium ( Z = 71). These some times size is found to be same from second
are placed in the sixth period and in third group. member to third member.The similarity in size of
the atoms of Zr and Hf is evident due to the fact
79. (c) In lanthanide series there is a regular
of lanthanide contraction. Therefore, Zr and Hf
decrease in the atomic as well as ionic radii of
both have same radius 160 pm.
trivalent ions (M3+) as the atomic number
increases. Although the atomic radii do show 83. (d) Actinides have variable valency due to
some irregularities but ionic radii decreases from very small difference in energies of 5f, 6d and 7s
La(103 pm) to Lu (86pm). orbitals. Actinides are the elements from atomic
number 89 to 103.
80. (a) The Lanthanides are transition metals from
atomic numbers 58 (Ce) to 71(Lu). 84. (b) Pm is obtained by synthetic method.
Hence the electronic configuration becomes : Promethium is not present in nature. It is synthetic
1– 14
radioactive lanthanoid.
(n –2) f (n – 1) s2p6 d0 – 1 ns2.
81. (a) La (OH)3 is more basic than Li (OH)3. In
lanthanides, the basic character of hydroxides
decreases as the ionic radius decreases.
Coordination Compounds 223
23 Coordination
Compounds
2020 2019 2018 2017 2016

Coordination number, isomerism 1 A
nomenclature and
isomerism of primary/secondary
coordination 1 D
valency
compounds
ligand strength 1 E
magnetic moment 1 A 1 A
Magnetic
cystal field theory 1 A 1 D
moment,valence bond
theory and crystal field complex formation 1 A
theory geometry/hybridisa
tion and magnetic 1 A 1 A
behaviour
Topic 1: Coordination Number, Nomenclature (c) 2 AgCl, 3 AgCl, 1 AgCl

and Isomerism of Coordination Compounds (d) 1 AgCl, 3 AgCl, 2 AgCl
3. Cobalt (III) chloride forms several octahedral
1. The type of isomerism shown by the complex
complexes with ammonia. Which of the
[CoCl2(en)2] is [2018]
following will not give test of chloride ions with
(a) Geometrical isomerism silver nitrate at 25ºC ? [2015]
(b) Coordination isomerism (a) CoCl3·4NH3 (b) CoCl3·5NH3
(c) Linkage isomerism (c) CoCl3·6NH3 (d) CoCl3·3NH3
(d) Ionization isomerism 4. The sum of coordination number and oxidation
2. The correct order of the stoichiometries of AgCl number of the metal M in the complex
formed when AgNO3 in excess is treated with [M(en)2(C2O4)]Cl (where en is ethylenediamine) is:
the complexes : CoCl3.6NH3, CoCl 3.5NH3, (a) 9 (b) 6 [2015 RS]
CoCl3.4NH3 respectively is :- [2017]
(c) 7 (d) 8
(a) 3 AgCl, 1 AgCl, 2 AgCl
5. The name of complex ion, [Fe(CN)6]3– is :
(b) 3 AgCl, 2 AgCl, 1 AgCl
EBD_8336
224 CHEMISTRY
(a) Hexacyanoiron (III) ion [2015 RS]
with the composition of [Co(NH3 )4 Cl2 ]+ is due
(b) Hexacyanitoferrate (III) ion
to : [2010]
(c) Tricyanoferrate (III) ion
(a) linkage isomerism
(d) Hexacyanidoferrate (III) ion
(b) geometrical isomerism
6. Number of possible isomers for the complex
(c) coordination isomerism
[Co(en)2Cl2]Cl will be (en = ethylenediamine)
(d) ionization isomerism
(a) 2 (b) 1 [2015 RS]
13. Which one of the following complexes is not
(c) 3 (d) 4
expected to exhibit isomerism? [2010]
7. An excess of AgNO3 is added to 100 mL of a
0.01 M solution of dichlorotetraaquachromium (a) [ Ni(en)3 ]2+
(III) chloride. The number of moles of AgCl
precipitated would be : [NEET 2013] 2+
(b) é Ni ( NH3 ) ( H 2 O ) ù
(a) 0.002 (b) 0.003 ë 4 2û
(c) 0.01 (d) 0.001

(c) é Pt ( NH3 ) Cl 2 ù
8. The correct IUPAC name for [CrF2(en)2]Cl is: ë 2 û
[NEET Kar. 2013]
(d) é Ni ( NH3 ) Cl 2 ù
(a) Chlorodifluoridobis (ethylene diamine) ë 2 û
chromium (III) 14. Which of the following does not show optical
(b) Chlorodifluoridoethylenediaminech- isomerism? [2009]
romium (III) chloride (a) [Co(NH3)3Cl3]0
(c) Difluoridobis (ethylene diamine) chromium (b) [Co (en) Cl2 (NH3)2]+
(III) chloride
(c) [Co (en)3]3+
(d) Difluorobis-(ethylene diamine) chromium
(d) [Co (en)2Cl2]+
(III) chloride
(en = ethylenediamine)
9. In a particular isomer of [Co(NH3)4Cl2]0, the
Cl-Co-Cl angle is 90°, the isomer is known as 15. Which of the following will give a pair of
enantiomorphs? [2007]
[NEET Kar. 2013]
(a) [Cr(NH3)6][Co(CN)6]
(a) Linkage isomer (b) Optical isomer
(b) [Co(en)2Cl2]Cl
(c) cis-isomer (d) Position isomer
(c) [Pt(NH3)4] [PtCl6]
10. The complexes [Co(NH3)6] [Cr(CN)6] and
[Cr(NH3)6] [Co(CN)6] are the examples of which (d) [Co(NH3)4Cl2]NO2. (en =NH2CH2CH2NH2)
type of isomerism? [2011] 16. [Co(NH3)4 (NO2)2] Cl exhibits [2006]
(a) Linkage isomerism (a) linkage isomerism, ionization isomerism
(b) Ionization isomerism and geometrical isomerism
(c) Coordination isomerism (b) ionization isomerism, geometrical isomerism
(d) Geometrical isomerism and optical isomerism
11. The complex, [Pt(Py)(NH3)BrCl] will have how (c) linkage isomerism, geometrical isomerism
many geometrical isomers ? [2011] and optical isomerism
(a) 3 (b) 4 (d) linkage isomerism, ionization isomerism
(c) 0 (d) 2 and optical isomerism
12. The existence of two different coloured complexes
17. Which one of the following is expected to (c) [Co(NH2)3 (H2O)2 Cl]
exhibit optical isomerism? (d) [Co(NH3)3 (H2O)3]Cl3
(en = ethylenediamine) [2005] 23. Which of the following will give maximum
(a) cis-[Pt(NH3)2 Cl 2] number of isomers? [2001]
(b) trans-[Pt(NH3)2Cl 2] (a) [Ni (C2O4) (en)2]2– (b) [Ni (en) (NH3)4]2+
(c) cis-[Co(en)2Cl 2 ] (c) [Cr (SCN)2 (NH3)4]+ (d) [Co (NH3)4 Cl2]
(d) trans-[Co(en)2Cl 2 ] 24. Which of the following will exhibit maximum
ionic conductivity? [2001]
18. Which of the following is considered to be an
anticancer species ? [2004] (a) K4[Fe(CN)6] (b) [Co(NH3)6] Cl3
(c) [Cu(NH3)4]Cl2 (d) [Ni(CO)4]
Cl CH2 Cl Cl 25. Oxidation number of Ni in [Ni(C2O4)3]4– is
(a) Pt CH2 (b) Pt
(a) 3 (b) 4 [2001]
Cl Cl Cl Cl
(c) 2 (d) 6
Cl 26. Which one of the following complexes will have
H3N H3N Cl
four different isomers ? [2000]
(c) Pt (d) Pt
H3N Cl Cl NH3 (a) [ Co (en ) 2 Cl 2 ]Cl
19. Which of the following coordination compounds (b) [Co(en)(NH3 )2 Cl2 ]Cl
would exhibit optical isomerism? [2004]
(c) [Co(PPh 3 )2 Cl2 ]Cl
(a) pentaamminenitrocobalt(III) iodide
(b) diamminedichloroplatinum(II) (d) [ Co (en ) 3 ]Cl 3
(c) trans-dicyanobis (ethylenediamine) 27. In which of the following compounds does iron
chromium (III) chloride exhibit zero oxidation state? [1999]
(d) tris-(ethylendiamine) cobalt (III) bromide (a) [Fe(H2O)6] (NO3)3 (b) K3[Fe(CN)6]
20. Which one of th e following octahedral (c) K4[Fe(CN)6] (d) [Fe(CO)5]
complexes will not show geometric isomerism? 28. The total number of possible isomers for the
(A and B are monodentate ligands) [2003] complex compound [CuII (NH3)4] [PtII Cl4]
(a) [MA5B] (b) [MA2B4] (a) 3 (b) 6 [1998]
(c) [MA3B3] (d) [MA4B2] (c) 5 (d) 4
21. According to IUPAC nomenclature sodium 29. IUPAC name of [Pt(NH3)3 (Br) (NO2) Cl] Cl is
nitroprusside is named as [2003] [1998]
(a) Sodium pentacyanonitrosyl ferrate (III) (a) Triamminechlorobromonitroplatinum (IV)
(b) Sodium nitroferrocyanide chloride
(c) Sodium nitroferrocyanide (b) Triamminebromonitrochloroplatinum (IV)
chloride
(d) Sodium pentacyanonitrosyl ferrate (II)
(c) Triamminebromochloronitroplatinum (IV)
22. The hypothetical complex chloridodiaquatriammine
chloride
cobalt (III) chloride can be represented as [2002]
(d) Triamminenitrochlorobromoplatinum (IV)
(a) [CoCl(NH3)3 (H2O)2]Cl2
chloride
(b) [Co(NH3)3 (H2O)Cl3]
EBD_8336
226 CHEMISTRY
30. A coordination complex compound of cobalt has (a) [Co( NH 3 ) 6 ]3+
the molecular formula containing five ammonia
molecules, one nitro group and two chlorine (b) [ Co ( H 2 O ) 2 ( NH 3 ) 2 Cl 2 ] +
atoms for one cobalt atom. One mole of this
compound produces three mole ions in an (c) [Cr(H 2 O) 2 Cl 2 ]+
aqueous solution. On reacting this solution with
excess of AgNO3 solution, we get two moles of (d) [Co(CN) 5 NC]
AgCl precipitate. The ionic formula for this 37. An example of double salt is [1989]
complex would be [1998]
(a) Bleaching powder (b) K 4 [Fe(CN) 6 ]
(a) [Co(NH3)4 (NO2) Cl] [(NH3) Cl]
(c) Hypo (d) Potash alum
(b) [Co (NH3)5 Cl] [Cl (NO2)]
Topic 2: Magnetic Moment, Valence Bond
(c) [Co (NH3)5 (NO2)] Cl2 Theory and Crystal Field Theory
(d) [Co (NH3)5] [(NO2)2Cl2]
38. Which of the following is the correct order of
31. The formula for the complex, dichlorobis (urea) increasing field strength of ligands to form
copper (II) is [1997] coordination compounds? [2020]
(a) [Cu{O = C (NH2)2}] Cl2 (a) SCN– < F– < CN– < C2 O 24 -
(b) [Cu{O = C (NH2)2}Cl]Cl
(b) F– < SCN–< C2 O 24 - < CN–
(c) [CuCl2 {O = C(NH2)2}2]
(c) CN– < C2 O 24 - < SCN– < F–
(d) [CuCl2] [{O = C (NH2)2}]2
32. The number of geometrical isomers of the (d) SCN– < F– < C2 O 24 - < CN–
complex [Co(NO2)3 (NH3)3] is [1997] 39. The calculated spin only magnetic moment of
(a) 2 (b) 3 Cr2+ ion is [2020]
(c) 4 (d) zero (a) 4.90 BM (b) 5.92 BM
(c) 2.84 BM (d) 3.87 BM
33. Among the following, the compound that is both
paramagnetic and coloured, is [1996] 40. The Crystal Field Stabilisation Energy (CFSE)
for [CoCl6]4– is 18000 cm–1. The CFSE for
(a) KMnO4 (b) CuF2
[CoCl4]2– will be [NEET Odisha 2019]
(c) K4[Fe(CN)6] (d) K2Cr2O7 –1
(a) 8000 cm (c) 6000 cm–1
34. The number of geometrical isomers for –1
(c) 16000 cm (d) 18000 cm–1
[Pt (NH3)2 Cl2] is [1995]
41. What is the correct electronic configuration of
(a) 2 (b) 1 the central atom in K4[Fe(CN)6] based on crystal
(c) 3 (d) 4 field theory ? [2019]
35. K 3[Al(C 2O 4 )3 ] is called [1994] (a) t24g eg2 (b) t26g eg0
(a) Potassium alumino oxalate (c) e3g t23g (d) eg4 t22g
(b) Potassium trioxalatoaluminate (III) 42. The geometry and magnetic behaviour of the
(c) Potassium aluminium (III) oxalate complex [Ni(CO)4] are [2018]
(d) Potassium trioxalato aluminate (VI) (a) Square planar geometry and diamagnetic
36. Among the following complexes, optical activity (b) Tetrahedral geometry and diamagnetic
is possible in [1994] (c) Tetrahedral geometry and paramagnetic
(d) Square planar geometry and paramagnetic
43. Match the metal ions given in Column I with (c) [Co(CN)6]3– has no unpaired electrons and
the spin magnetic moments of the ions given in will be in a high-spin configuration.
Column II and assign the correct code : [2018] (d) [Co(CN)6]3– has no unpaired electrons and
Column I Column II will be in a low-spin configuration.
a. Co3+ i. 8 BM 48. Among the following complexes the one which
b. Cr3+ ii. 35 BM shows zero crystal field stabilization energy
(CFSE): [2014]
c. Fe3+ iii. 3 BM
(a) [Mn(H2O)6]3+ (b) [Fe(H2O)6]3+
d. Ni2+ iv. 24 BM
(c) [Co(H2O)6]2+ (d) [Co(H2O)6]3+
v. 15 BM 49. Which of the following complexes is used as an
a b c d anti-cancer agent: [2014]
(a) iv v ii i (a) mer-[Co(NH3)3Cl3] (b) cis-[PtCl2(NH3)2]
(b) i ii iii iv (c) cis-K2[PtCl2Br2] (d) Na2CoCl4
(c) iii v i ii 50. A magnetic moment of 1.73 BM will be shown
(d) iv i ii iii by one among the following : [NEET 2013]
44. HgCl2 and I2 both when dissolved in water (a) [Ni(CN)4]2– (b) [TiCl4]
containing I – ions, the pair of species formed is: (c) [CoCl6]4– (d) [Cu(NH3)4]2+
(a) HgI2, I– (b) HgI42 - , I3- [2017] 51. Which is diamagnetic? [NEET Kar. 2013]
(a) [Fe(CN)6]3– (b) [Co(F6)]3–
(c) Hg2I2, I– (d) HgI2 , I3- (c) [Ni(CN)4]2– (d) [NiCl4]2–
45. Correct increasing order for the wavelengths of 52. The anion of acetylacetone (acac) forms
absorption in the visible region the complexes Co(acac)3 chelate with Co3+. The rings of the
of Co3+ is :- [2017] chelate are [NEET Kar. 2013]
(a) [Co(H2O)6]3+, [Co(en)3]3+, [Co(NH3)6]3+ (a) three membered (b) five membered
(b) [Co(H2O)6]3+, [Co(NH3)6]3+, [Co(en)3]3+ (c) four membered (d) six membered
(c) [Co(NH3)6]3+, [Co(en)3]3+, [Co(H2O)6]3+ 53. Which among the following is a paramagnetic
(d) [Co(en)3]3+, [Co(NH3)6]3+, [Co(H2O)6]3+ complex? [NEET Kar. 2013]
46. Pick out the correct statement with respect to (a) [Mo(CO)6] (b) [Co(NH3)6]3+
[Mn(CN)6]3- [2017] (c) [Pt(en)Cl2] (d) [CoBr4]2–
(a) It is sp3d2 hybridised and tetrahedral (At. No. of Mo = 42, Pt = 78)
(b) It is d2sp3 hybridised and octahedral 54. Which one of the following is an outer orbital
(c) It is dsp2 hybridised and square planar complex and exhibits paramagnetic behaviour ?
(d) It is sp3d2 hybridised and octahedral [2012]
47. Which of these statements about [Co(CN)6]3– (a) [Ni(NH3)6]2+ (b) [Zn(NH3)6)]2+
is true ? [2015] (c) [Cr(NH3)6]3+ (d) [Co(NH3)6]3+
(a) [Co(CN)6]3– has four unpaired electrons
55. Red precipitate is obtained when ethanol
and will be in a low-spin configuration.
solution of dimethylglyoxime is added to
(b) [Co(CN)6]3– has four unpaired electrons ammoniacal Ni(II). Which of the following
and will be in a high spin configuration. statements is not true ? [2012 M]
EBD_8336
228 CHEMISTRY
(a) Red complex has a square planar geometry. 61. Crystal field stabilization energy for high spin
(b) Complex has symmetrical H-bonding d 4 octahedral complex is: [2010]
(c) Red complex has a tetrahedral geometry. (a) – 1.8 D 0 (b) – 1.6 D 0 + P
(d) Dimethylglyoxime functions as bidentate
ligand. (c) – 1.2 D 0 (d) – 0.6 D 0
62. Which of the following complex ions is expected
OH
H3C C N to absorb visible light? [2009]
dimethylglyoxime =
H3C C N (a) [Ti (en)2(NH3)2]4 +
OH
(b) [Cr (NH3)6]3 +
56. Low spin complex of d 6-cation in an octahedral (c) [Zn (NH3)6]2 +
field will have the following energy : [2012 M]
(d) [Sc (H2O)3 (NH3)3]3+
-12 -12
(a) Do + P (b) D o + 3P (At. no. Zn = 30, Sc = 21, Ti = 22, Cr = 24)
5 5
63. Which of the following complexes exhibits the
-2 -2
(c) D o + 2P (d) Do + P highest paramagnetic behaviour ? [2008]
5 5
(a) [V(gly)2(OH)2(NH3)2]+
(D o= Crystal Field Splitting Energy in an
octahedral field, P = Electron pairing energy) (b) [Fe(en)(bpy)(NH3)2]2+
57. Of the following complex ions, which is (c) [Co(ox)2(OH)2]–
diamagnetic in nature ? [2011]
(d) [Ti(NH3)6]3+
(a) [NiCl4]2– (b) [Ni(CN)4]2–
where gly = glycine, en = ethylenediamine and
(c) [CuCl4]2– (d) [CoF6]3–
bpy = bipyridyl moities)
58. The d-electron configurations of Cr 2+, Mn2+,
Fe2+ and Co2+ are d 4, d 5, d 6 and d 7, respectively. (At.nosTi = 22, V = 23, Fe = 26, Co = 27)
Which one of the following will exhibit minimum 64. In which of the following coordination entities
paramagnetic behaviour? [2011] the magnitude Do (CFSE in octahedral field) will
(a) [Mn(H2O)6]2+ (b) [Fe(H2O)6]2+ be maximum? [2008]
(c) [Co(H2O)6]2+ (d) [Cr(H2O)6]2+ (a) [Co(H2O)6]3+ (b) [Co(NH3)6]3+
(At, nos. Cr = 24, Mn = 25, Fe = 26, Co = 27) (c) [Co(CN)6]3– (d) [Co (C2O4)3]3–
59. Which of the following complex compounds will
(At. No. Co = 27)
exhibit highest paramagnetic behaviour?
[2011M] 65. The d electron configurations of Cr2+, Mn2+, Fe2+
(At. No. : Ti = 22, Cr = 24, Co = 27, Zn = 30) and Ni2+ are 3d 4, 3d 5, 3d 6 and 3d 8 respectively.
(a) [Ti (NH3)6]3+ (b) [Cr (NH3)6]3+ Which one of the following aqua complexes will
exhibit the minimum paramagnetic behaviour?
(c) [Co (NH3)6]3+ (d) [Zn (NH3)6]2+
60. Which of the following complex ion is not [2007]
expected to absorb visible light ? [2010] (a) [Fe(H2O)6]2+ (b) [Ni(H2O)6]2+
(a) [ Ni(CN)4 ] 2-
(b) [Cr(NH3 )6 ] 3+ (c) [Cr(H2O)6]2+ (d) [Mn(H2O)6]2+
(c) [ Fe(H2 O)6 ]2+ (d) [ Ni(H 2O)6 ]2+ (At. No. Cr = 24, Mn = 25, Fe = 26, Ni = 28)
66. [Cr(H2O)6]Cl3 (at no. of Cr = 24) has a magnetic (a) [Cr(CO)6] (b) [Fe(CO)5]
moment of 3.83 B. M. The correct distribution of (c) [Fe(CN)6] –4 (d) [Cr(NH3)6]+3
3d electrons in the chromium of the complex is 73. CuSO4 when reacts with KCN forms CuCN,
which is insoluble in water. It is soluble in excess
( ) , 3d [2006]
1
(a) 3d xy1, 3d x 2 - y 2 yz
1 of KCN due to formation of the following complex
(b) 3dxy1, 3dyz1, 3dxz1 [2002]
(a) K2[Cu(CN)4] (b) K3[Cu(CN)4]
(c) 3dxy1, 3dyz1, 3d1z 2
(c) CuCN2 (d) Cu[K Cu(CN)4]
(d) (3dx2 – y2)1, 3d z 2 , 3dxz1 74. Which statement is incorrect? [2001]
67. Which one of the following is an inner orbital (a) [Ni(CO)4] – Tetrahedral, paramagnetic
complex as well as diamagnetic in behaviour? (b) [Ni(CN)4]2– – Square planar, diamagnetic
(Atomic number: Zn = 30, Cr = 24, Co = 27, (c) [Ni(CO)4] – Tetrahedral, diamagnetic
Ni = 28) [2005] (d) [NiCl4]2– – Tetrahedral, paramagnetic
(a) [Zn(NH3)6] 2+ (b) [Cr(NH3)6] 3+
75. Which one of the following will show
(c) [Co(NH3)6]3+ (d) [Ni(NH3)6]2+ paramagnetism corresponding to 2 unpaired
electrons?(Atomic numbers : Ni = 28, Fe = 26)
68. Among [ Ni( CO ) 4 ], [ Ni( CN ) 4 ] 2 - , [ NiCl 4 ] 2 -
(a) [Fe F6]3– (b) [Ni Cl4]2– [1999]
species, the hybridization states of the Ni atom 3–
are, respectively (At. No. of Ni = 28) [2004] (c) [Fe (CN)6] (d) [Ni (CN)4]2–
76. The number of unpaired electrons in the complex
(a) sp 3 , dsp2 , dsp 2 (b) sp3 , dsp 2 , sp3 [Cr(NH3)6]Br3 is (Atomic number Cr = 24)
(a) 4 (b) 1 [1999]
(c) sp3 , sp 3 , dsp 2 (d) dsp 2 , sp 3 , sp 3
(c) 2 (d) 3
69. CN– is a strong field ligand. This is due to the 77. Which of the following statements is correct ?
fact that [2004]
(Atomic number of Ni = 28) [1997]
(a) it carries negative charge
(a) [Ni(CO)4] is diamagnetic and [NiCl4]2– and
(b) it is a pseudohalide [Ni(CN)4]2– are paramagnetic
(c) it can accept electrons from metal species (b) [Ni(CO)4] and [Ni(CN)4]2– are diamagnetic
(d) it forms high spin complexes with metal and [NiCl4]2– is paramagnetic
species (c) [Ni(CO)4] and [NiCl4]2–are diamagnetic and
70. Considering H2O as a weak field ligand, the [Ni(CN)4]2– is paramagnetic
number of unpaired electrons in [ Mn ( H 2 O ) 6 ]2 + (d) [NiCl4]2– and [Ni(CN)4]2– are diamagnetic
and [Ni(CO)4] is paramagnetic
will be (At. no. of Mn = 25) [2004]
78. Which of the following is common donor atom
(a) three (b) five in ligands? [1995]
(c) two (d) four (a) arsenic (b) nitrogen
71. The number of unpaired electrons in the complex (c) oxygen (d) both 'b' and 'c'
ion [CoF6]3– is (Atomic no.: Co = 27) [2003] 79. The complex ion [Co(NH3)6]3+ is formed by sp3d 2
(a) Zero (b) 2 hybridisation. Hence, the ion should possess
(c) 3 (d) 4 (a) Octahedral geometry [1990]
72. Atomic number of Cr and Fe are respectively 25 (b) Tetrahedral geometry
and 26, which of the following is paramagnetic? (c) Square planar geometry
(d) Tetragonal geometry.
[2002]
EBD_8336
230 CHEMISTRY
Topic 3: Organometallic Compounds 85. Among the following, which is not the p-bonded
organometallic compound? [2003]
80. Iron carbonyl, [Fe(CO)5] is [2018]
(a) Tetranuclear (b) Mononuclear (a) (CH 3 ) 4 Sn
(c) Dinuclear (d) Trinuclear

(b) K [PtCl3 (h2 - C 2 H 4 )]
81. An example of a sigma bonded organometallic
compound is : [2017] (c) Fe (h5 - C5 H 5 ) 2
(a) Grignard's reagent (b) Ferrocene
(c) Cobaltocene (d) Ruthenocene (d) Cr (h6 - C 6 H 6 ) 2
82. Which of the following has longest C–O bond 86. Which of the following organometallic
length? (Free C–O bond length in CO is 1.128Å) compound is s and p bonded? [2001]
[2016] (a) [Fe (h5 – C5H5)2]
(a) [Ni(CO)4] (b) [Co(CO)4]– (b) Fe (CH3)3
(c) [Fe(CO)4]2– (d) [Mn(CO)6]+ (c) K [PtCl3(h2 – C2H4)]
83. Which of the following carbonyls will have the (d) [Co(CO)5 NH3]2+
strongest C – O bond ? [2011 M] 87. Which of the following may be considered to be
(a) [Mn (CO)6]+ (b) [Cr (CO)6 ] an organometallic compound? [1996]
(c) [V (CO)6]– (d) [Fe (CO)5] (a) Nickel tetracarbonyl
84. Which of the following does not have a metal- (b) Chlorophyll
carbon bond? [2004] (c) K3 [Fe (C2O4)3]
(a) Al(OC 2 H 5 )3 (b) C 2 H 5MgBr (d) [Co (en)3] Cl3
(c) K[Pt (C 2 H 4 )Cl 3 ] (d) [ Ni(CO) 4 ]
ANSWER KEY
1 (b) 10 (c) 19 (d) 28 (d) 37 (d) 46 (b) 55 (c) 64 (c) 73 (b) 82 (c)
2 (a) 11 (a) 20 (a) 29 (c) 38 (d) 47 (d) 56 (b) 65 (b) 74 (a) 83 (a)
3 (d) 12 (b) 21 (a) 30 (c) 39 (a) 48 (b) 57 (b) 66 (b) 75 (b) 84 (a)
4 (a) 13 (d) 22 (a) 31 (c) 40 (a) 49 (b) 58 (c) 67 (c) 76 (d) 85 (a)
5 (d) 14 (a) 23 (c) 32 (a) 41 (b) 50 (d) 59 (b) 68 (b) 77 (b) 86 (d)
6 (c) 15 (b) 24 (a) 33 (b) 42 (b) 51 (c) 60 (a) 69 (b) 78 (d) 87 (a)
7 (d) 16 (a) 25 (c) 34 (a) 43 (a) 52 (d) 61 (d) 70 (b) 79 (a)
8 (c) 17 (c) 26 (b) 35 (b) 44 (b) 53 (d) 62 (b) 71 (d) 80 (b)
9 (c) 18 (c) 27 (d) 36 (b) 45 (d) 54 (a) 63 (c) 72 (d) 81 (a)
Hints & Solutions

Mirror image of (II)
(b) ëé Co ( NH 3 )6 ûù Cl3 ¾¾¾¾
3® AgNO
1.
3 mol of AgCl N
N
ëé Co ( NH 3 )5 Cl ûù Cl2 ¾¾¾¾
AgNO
3® N
Co
2 mol of AgCl Cl N
éë Co ( NH 3 )4 Cl 2 ùû Cl ¾¾¾¾
AgNO
3 ® 1 mol of AgCl Cl
Complexes are respectively [Co(NH3 )6] Cl3 , 7. ® AgCl +
(d) [Cr(H2O)4Cl2] Cl + AgNO3 ¾¾
[Co(NH3)5Cl]Cl2 and [Co(NH3)4Cl2]Cl
[Cr(H2O)4Cl2]NO3
2. (a) In the given complex, the CN of Co is 6, wt 1000
and the complex has octahedral geometry. Molarity = ´
en mol. mass vol.
Cl
wt vol. 0.01 ´100
= molarity ´ =
en Co en Co en mol. mass 1000 1000
Cl = 0.001
Cl Cl
trans (optically inactive) cis (optically active) 8. (c) IUPAC name of [CrF2 (en)2]Cl is
3. (d) CoCl3 . 3NH3 will not give test for chloride
Difluoridobis(ethylenediamine) chromium (III)
ions with silver nitrate due to absence of
chloride.
ionisable chloride atoms.
CoCl3 . 3NH3 Þ [Co(NH3)3 Cl3] Cl
90°
AgNO3
Cl NH3
[Co(NH3)3 Cl3] ¾¾¾¾ ® no ppt Co
9. (c)
Secondary valence is fixed for a metal/ion. For NH3
NH3
Co3+, it is six. NH3
cis-isomer
4. (a) [M (en)2 (C2O4)] Cl 10. (c)
C2O4 = bidentate ligand, carry – 2 charge
en = bidentate ligand, carry 0 charge Interchange of ligand between the complexes
\ M carry+ 3 charge; coordination number = 6 give isomers e.g.
\ Sum = + 3 + 6 = 9 [Co (NH3)6] [Cr (CN)6] is an isomer of [Co (CN)6]
5. (d) Hexacyanidoferrate (III) ion. [Cr (NH3)6]
6. (c) [Co (en)2 Cl2] Cl
Coordination isomerism occurs when cationic and
Cl N anionic complexes of different metal ions are
N N N N present in a salt.
Co and Co
N N N Cl
11. (a) Complexes of the type MABCD may exist in
Cl Cl three isomeric forms.
trans cis
(I) (II)
EBD_8336
232 CHEMISTRY
Tetrahedral complexes are symmetrical in all

A B A C
directions. Thus, cannot show geometrical
isomerism.
14. (a) The octahedral coordination compounds of
M M
the type MA3B3 exhibit fac-mer isomerism.
NH3 NH3
D C D B Cl NH3 H3N Cl
(I) (II)
A C Co
Co
Cl NH3 Cl Cl
M NH3
Cl Mer
fac.
B D 15. (b) Non superimposable mirror images are called

(III) optical isomers and may be described as 'chiral'.
They are also called enantiomers and rotate plane
Similarly, [Pt (Py) (NH3) BrCl] may exist in three polarised light in opposite directions.
isomeric form in which
M = Pt, A = Py, B = NH3, C = Br, D = Cl. N N N
N
N Co Cl Cl Co N
12. (b)
N N
Cl Cl
16. (a) The given compound may have linkage
isomerism due to presence of NO2 group which
may be in the form –NO2 or –ONO.
It may have ionisation isomerism due to presence
trans (violet) of two ionisable group –NO2 & –Cl. It may have
Cl + geometrical isomerism in the form of cis-trans
H3N Cl form as follows :
[Co(NH3)4Cl(NO2)]NO2 &
Co [Co(NH3)4(NO2)2]Cl ––– ionisation isomers.
[Co(NH3)4(NO2)2]Cl & [Co(NH3)4(ONO)2]Cl
H3N NH3
NH3 ––– Linkage isomers
NO2 NO2
cis (green)
H3N H3N
13. (d) In éë Ni ( NH 3 )2 Cl 2 ùû , Ni 2 + is in sp 3 NH3 NO2
CO CO
hybridisation, thus tetrahedral in shape. Hence,
the four ligands are not different to exhibit optical H3N NH3 H3N NH3
isomerism. \ Correct choice : (d)
NO2 NH3
(ii) [Mabcd] does not have a plan e of
Trans-form cis-form
symmetry, thus it will show optical isomerism. Geometrical isomers
Whereas, [Ma2b2] has a plane of symmetry, thus
it will show optical isomerism also.
17. (c)
en 23. (c) [Cr(SCN ) 2 ( NH 3 ) 4 ]+ shows linkage and
en + +
Cl Cl geometrical isomerism. Hence, produces maximum
no. of isomers.
Co Co
24. (a) The complex ion which give maximum ions
Cl Cl in solution exhibit maximum ionic conductivity.
en
en K 4 [ Fe(CN) 6 ] ® [ Fe (CN) 6 ]-4 + 4K + ®5 ions
Cis-d-isomer Cis-l-isomer
[Co( NH 3 ) 6 ]Cl 3 ® [Co( NH 3 ) 6 ]3+ + 3 Cl - ® 4 ions
Mirror
Trans-form of [M(AA) 2 a 2]n± does not show [Cu ( NH 3 ) 4 ]Cl 2 ® [Cu ( NH 3 ) 4 ]2+ + 2Cl - ® 3 ions
optical isomerism. [ Ni(CO) 4 ] ® No ions
18. (c) Diaminodichloroplatinum (II) commonly 25. (c) O.N. of Ni in [ N i(C 2 O 4 ) 3 ]
4-
known as cis - platin is found to have anticancer

property. = x + 3( -2) = -4 Þ x = -4 + 6 = 2
19. (d) The optical isomers are pair of molecules 26. (b) Complex [Co(en)(NH3)2Cl2]Cl will have four
which are non superimposable mirror images of different isomers.
each other. (i) Geometrical isomers
3+ N en 3+ Cl
en – N | NH3
N N en – CO
N N Co
en | NH3
|
Co en Cl
N N
N N trans (for Cl)
N en
en NH3
| Cl
N
d form l form
en – CO Plane of symmetry
| Cl
|
Enantiomers
NH3
The two optically active isomers are collectively trans (for NH 3)
called enantiomers. (ii) Optical isomers
20. (a) MA3 B3 – 2 geometrical isomers
Cl Cl
MA2 B4 – 2 geometrical isomers Cl
Cl
MA4 B2 – 2 geometrical isomers en CO CO en
NH3 H3N
The complexes of general formula Ma6 and Ma5b NH3 NH3
octahedral geometry do not show geometrical cis-isomer d- and l -forms
isomerism. (no element of symmetry)
21. (a) IUPAC name of sodium nitroprusside Hence, the compound has 4 different isomers
Na 2 [Fe(CN) 5 NO] is sodium pentacyanoni- 27. (d) In [Fe(CO)5] iron exist in zero oxidation state.
trosoyl ferrate (III) because in it NO is neutral 28. (d) The total number of isomers for the complex
ligand. Hence compound
2×O.N. of Na + O.N. of Fe + 5×O.N. of CN
[Cu II (NH3 )4 ][Pt II Cl 4 ] is four..
1×O.N. of NO = 0
2×(+1) + O.N. of Fe + 5 ×(–1) +1×0 = 0 These four isomers are
O.N. of Fe = 5 – 2 = +3, Hence, ferrate (III) [Cu ( NH 3 )3 Cl] [Pt ( NH 3 )Cl 3 ],
22. (a) Chloridodiaquatriammine cobalt (III)
[Pt(NH3 )3 Cl] [Cu(NH3 )Cl3 ] ,
chloride is [CoCl( NH 3 )3 (H 2O) 2 ]Cl 2
EBD_8336
234 CHEMISTRY
– – – 2– – 2–
[Pt(NH3 )4 ] [CuCl 4 ] I < Br < SCN < Cl < S < F < OH < C2O4
and [Cu(NH3 )4 ] [ PtCl4 ] . 4–
< H2O < NCS < EDTA < NH 3 < en < CN < CO
The isomer [Cu (NH3)2 Cl2][Pt (NH3)2 Cl2] does So, correct order is
not exist as both the parts are neutral.
SCN - < F- < C2 O42- < CN -
For writing all combination of structural isomers,
we have to keep the same value of primary valence Strong and weak field ligands affect the electronic
and secondary valence of central atom/ion for all configuration of elements of first transition series.
the isomers. Second and third transition series electrons pair
up irrespective of nature of ligand provided pairing
29. (c) We know that IUPAC name of of electrons is allowed.
[Pt(NH3)3 (Br) (NO2)Cl]Cl is triammine-
bromochloronitroplatinum (IV) chloride. 39. (a) Electronic configuration of Cr2+ – [Ar] 3d4
30. (c) As it forms two moles of silver chloride thus n=4
it has two moles of ionisable Cl.
m n = n(n + 2)
[Co(NH3 )5 NO2 ]Cl 2 ® [Co(NH3 )5 NO 2 ]2+ + 2Cl -
2Cl - + 2AgNO3 ® 2AgCl + 2NO 3- \ m n = 4(4 + 2) = 24 BM = 4.9 BM
31. (c) [CuCl2{(O = C(NH2)2}2] 4
40. (a) Q Dt = D0
32. (a) [Co( NO 2 )3 ( NH 3 )3 ] 9
4
Possible geometrical isomers Dt = × 18000 cm–1 = 8000 cm–1
NH3 NH3 9
H3N NH3 O2N NH3 41. (b)
4-
K 4 ëé Fe ( CN )6 ûù ® 4K + + [Fe(CN) 6 ]4 -
¾¾
Co Co
O2N NO2 NH3 NO2 x–6=–4
x=+2
NO2 NO2 Fe: 4s2 3d6
fac mer Fe2+ : 3d6
Total geometrical isomers = 2
33. (b) CuF2 is both paramagnetic and coloured eg
due to unpaired electron in d-orbital (3d 94s0). t2g
34. (a) [Pt (NH3)2 Cl2] is a disubstituted complex In spherical field
and shows only cis-& trans-isomers CN– is a strong field ligand and causes pairing of
H3N Cl electrons.
Cl NH 3
Pt Pt 42. (b) Ni(28) : [Ar]3d8 4s2

Q CO is a strong field ligand, so unpaired
Cl NH3 Cl NH3 electrons get paired. Hence, configuration
cis trans would be:
35. (b) IUPAC name is potassium trioxalato-
sp3–hybridisation
aluminate (III).
36. (b) It is optically active when two Cl atoms are
in cis position. 3d
CO CO CO CO
37. (d) Potash alum K 2SO4 .Al2 (SO4 )3·24H 2O 4s 4p
is a double salt. For, four ‘CO’ligands hybridisation would be

38. (d) According to spectrochemical series, the sp3 and thus the complex would be diamagnetic
order of ligand field strength is and of tetrahedral geometry.
43. (a) Co3+ = [Ar] 3d 6 , unpaired e–(n) = 4 As, coordination number of Mn = 6, so it will
Spin magnetic moment form an octahedral complex.
\ [Mn(CN)6]3– =
= 4(4 + 2) = 24 B.M.
Cr3+ = [Ar] 3d 3 , unpaired e–(n) = 3 [Ar] ´´ ´´ ´´ ´´ ´´ ´´
Spin magnetic moment
3d 4s 4p
= 3(3 + 2) = 15 B.M. d2s 3
Fe3+ = [Ar] 3d 5 , unpaired e–(n) = 5 47. (d) In [Co(CN)6]–3, O.N. of Co is +3

\ Co+3 = 3d 6 4s 0
= 5(5 + 2) = 35 B.M.
CN– is a strong field ligand
Ni2+ = [Ar] 3d 8 , unpaired e–(n) = 2
\ Pairing of electrons occurs so in this complex
no unpaired electron is present and it is low spin
= 2(2 + 2) = 8 B.M. complex.
44 (b) In a solution containing HgCl2, I2 and I–, 48. (b) Due to d 5 configuration CFSE is zero.
both HgCl2 and I2 compete for I–. 49. (b) cis-platin
Since formation constant of [HgI4]2– is very
large (1.9 × 10 30 ) as compared with I 3– 50. (d) [Cu(NH3)4]2+ hybridisation dsp2
(Kf = 700). Cu+2 – 3d9 has one unpaired e-
\ I– will preferentially combine with HgCl2.
HgCl2 + 2I– ® HgI2 ¯ + 2Cl–
Red ppt
2- So, magnetic moment
HgI2 + 2I- ® [ HgI 4 ]
soluble m= n ( n + 2 ) = 1(1 + 2 )
45. (d) The order of strength of ligand is
en > NH3 > H2O = 3 = 1.73
For strong ligand, the value of D0 for the complex
is higher. 51. (c) Ni+2 ® 3d 8 =
Hence, the increasing order of wavelengths of CN– is a strong ligand and causes pairing of 3d
absorption is: electrons of Ni2+.
[Co(en)3]3+ < [Co(NH3)6]3+ < [Co(H2O)6]3+ \ It is diamagnetic.
Higher value of D0 means higher stability, which 52. (d) Structure of Co(acac)3:
means it will absorb high energy photons. High
energy photons have low value of wavelength. C
O 1 O C
46. (b) In the complex [Mn(CN)6]3–, O.S. of Mn is + 3 C
Co O
E.C. of Mn+3 ® 3d 4 O
3d 4s 4p C O2
6 O
5 C C 3
The presence of a strong field ligand CN– causes 4
pairing of electrons. Hence, the rings of chelate are six membered ring.
53. (d) Co2+ Þ [Ar]3d74s0, here, Br– is a weak field
Þ ligand so will not cause pairing of d-electrons
3d 4s 4p in Co2+.
d 2 sp3 \ [CoBr 4 ] 2– will exhibit paramagnetic
behaviour due to unpaired electrons.
EBD_8336
236 CHEMISTRY
54. (a) [Ni(NH3)6 ]2+ accordance with the fact that the ligand involved
here is strong i.e., CN– ion.
6 2
Ni2+ = 3d 8, according to CFT = t 2g eg therefore, Ni2+ (after rearrangement)
hybridisation is sp 3 d 2 & complex is 3d 4s 4p
paramagnetic and outer orbital.
55. (c) Nickel ions are frequently detected by the
formation of red precipitate of the complex of Hence, now dsp2 hybridization involving one
nickel dimethylglyoxime, when heated with 3d, one 4s and two 4p orbitals, takes place leading
dimethylglyoxime. to four dsp2 hybrid orbitals, each of which
CH3 C NOH accepts four electron pairs from CN– ion forming
+ Ni2+ [Ni (CN)4]2– ion.
CH3 C NOH
[Ni (CN)4]2–
Dimethylglyoxime 3d 4s 4p
OH O
×× ×× ×× ××
CH3 C N 2+
N C CH3
Ni
CH3 C N N C CH3 four dsp2 hybrid bonds
Thus, the complex is diamagnetic as it has no
O OH unpaired electron.
Nickel dimethylglyoxime
58. (c) Cr2+, d 4
2+
Ni =
3d 4s 4p 4 unpaired e- s
dmg is a strong field ligand, so electrons will Mn2+, d 5
rearrange as:
2+
5 unpaired e- s
Ni = ×× ×× ×× ××
3d 4s 4p Fe2+, d 6
dsp 2 4 unpaired e- s
Thus, the complex is square plan ar geometry.
Co2+, d7
56. (b) for d 6, t2g6 eg0 (in low spin)
C.F.S.E = – 0.4 × 6D0 + 3P 3 unpaired e- s
Minimum paramagnetic behaviour
12
= - D + 3P = [Co (H2O)6]2+
5 o 59. (b)
[P is pairing energy for one electron] (a) [Ti(NH3)6]3+ : 3d1 configuration and thus has
57. (b) Ni2+ = 3d8 4sº one unpaired electron.
(b) [Cr(NH3)6]3+ : In this complex Cr is in +3
oxidation state.
Since, the coordination number of Ni in this Cr3+ : 3d 3 4so
complex is 4, the configuration of Ni2+ at first
sight shows that the complex is paramagnetic with
two unpaired electron. However, experiments Cr3+ ion [Cr (NH3)6]3+
show that the complex is diamagnetic. This is
possible when the 3d electrons rearrange against NH3NH3 NH3 NH3NH3NH3
the Hund’s rule as shown below. This is in
Thus, the complex is paramagnetic.
(c) [Co(NH3)6]3+ : In this complex, cobalt ion is Zn= [Ar] 3d 10 4s2; Zn2+= 3d10
in + 3 oxidation state with 3d 6 configuration. Sc = [Ar] 3d 1 4s2; Sc3+ = 3d 0
Co3+,[Ar]3d 6 63. (c) More the number of unpaired electrons present
3d 4s 4p in a complex more is its paramagnetic behaviour.
x -1 -1 0
(a) [V ( gly ) (OH) (NH3 ) ]+
2 2 2
[Co(NH3)6]3+ x + 2(–1) + 2(–1) + 2(0) = +1
Þ x = +5
V5+ = [Ar]; no unpaired electron
NH3 NH3 NH3 NH3 NH3 NH3
x 0 0 0
(inner orbital or d 2sp3 hybrid orbital low spin (b) [Fe(en)(bpy )(NH3 ) ]2 +
2
complex) diamagnetic x = +2
(d) In this complex Zn exists as Fe2+ = [Ar] 3d 6
Zn2+ ion But due to presence of strong field ligands, en,
Zn2+ ion : 3d10 4s0 bpy and NH3; the electrons will try to pair up.
Thus, the complex will contain no unpaired
electron.
Zn2+ ion in [Zn(NH3)4]2+ e -2 –1
(c) [Co (Ox ) (OH) ]–
2 2
x + 2(–2) + 2(–1) = –1
Þ x = +5
NH3 NH3 NH3 NH3
Co5+ = [Ar] 3d 4
Due to presence of paired electrons, complex is Thus, 4 unpaired electrons.
diamagnetic in nature. x 0
2- (d) [Ti (NH3 ) ]3+
60. (a) [ Ni(CN)4 ] : Number of unpaired electrons = 0 6
x = +3
[Cr(NH3 )6 ] 3+
: Number of unpaired electrons = 3 Ti3+ = [Ar] 3d1
Thus, 1 unpaired electron.
[Fe(H 2O)6 ]2+ : Number of unpaired electrons = 4
Hence, option (c) is the correct answer.
[ Ni(H2O)6 ]2+ : Number of unpaired electrons = 2 To find unpaired electrons let us calculate the
oxidation states of elements in each complex and
61. (d) d 4 in high spin octahedral complex then write the electronic configuration for that
eg – oxidation state to find the number of unpaired
electrons in it.
t2g
64. (c) Out of the given ligands water, ammonia,
CFSE = [0.6 × 1] + [–0.4 × 3] = – 0.6 D 0
cyanide and oxalate, maximum splitting will occur
62. (b) Since Cr 3+ in the complex has unpaired in case of cyanide (CN–) i.e. the magnitude of Do
electrons in the d orbital, hence will be coloured will be maximum in case of [Co(CN)6]3–.
Ti = [Ar]3d 2 4s2 ; Ti4 + = 3d 0
Cr = [Ar] 3d 5 4s1; Cr3+ = 3d 3
EBD_8336
238 CHEMISTRY
[Cr(NH3)6]3+ Cr3+(24 –3 = 21)
In octahedral field the crystal field splitting of d-
orbitals of a metal ion depends upon the field 4p
3d 4s
produced by the ligands.
65. (b) Lesser is the number of unpaired electrons
d 2sp 3 ® (inner octahedral
smaller will be the paramagnetic behaviour. As complex & paramagnetic)
Cr2+, Mn2+, Fe2+ & Ni2+ contains. 2+ 2+
[Ni(NH3)6] Ni (28 – 2 = 26)
Cr2+ (3d 4) =
3d 4s 4p
= 4 unpaired e–.
sp 3d 2 ® (outer octahedral
complex & paramagnetic)
Mn2+ (3d 5) =
[Zn(NH3)6]2+ Zn 2+(30 – 2 = 28)
= 5 unpaired e–.
3d 4s 4p
Fe2+ (3d 6) =
sp3d2 ® (outer octahedral
= 4 unpaired e–. complex & diamagnetic)
68. (b) 28Ni :

Ni2+ (3d 8) =
3d 4s 4p
= 2 unpaired e–.
As Ni2+ has minimum no. of unpaired e– thus
this is least paramagnetic. Ni in [Ni (CO)4] :
66. (b) m = n(n + 2) [Ni]

sp3 Hybridisation
3.83 = n(n + 2)
Remember CO is a strong ligand
on solving n = 3
Ni 2+ :
As per magnetic moment, it has three unpaired 4s 4p
3d
electron.
Cr3+ will have configuration as =
Ni 2 + in [Ni(CN) 4 ]2-
1s2 2s2 2p6 3s2 3p6 3d 3
dsp 2 Hybridisation
dxy dyz dzx Remember CN– is also a strong ligand
Ni 2+ in [ NiCl 4 ]2 -
So 3dxy1 3dyz1 3dxz1
67. (c) [Co(NH3)6]3+ Co3+(27 –3 = 24)

3d 4s 4p sp3 Hybridisation
Cl– is a weak ligand, hence no pairing of electrons
takes place
d 2sp 3 ®(inner octahedral
complex & diamagnetic)
69. (b) CN– is a strong field ligand as it is a [Fe(CN)6]–4
psuedohalide ion. × × × × × ×
× × × × × ×
Psuedohalide ions are strong coordinating ligands 3d 4s 4p
and hence have the tendency to form s-bond (from
the pseudo halide to the metal) and p-bond (from ––– diamagnetic
the metal to pseudo halide). [Cr(NH3)6]+3
70. (b) Since H 2 O is a weak ligand, it will not cause × × × × × ×

× × × × × ×
pairing of electrons in the metal ion Mn 2+. Thus 3d 4s 4p
electronic configuration of the metal (Mn2+) in
the complex will be ––– Paramagnetic
73. (b) Copper sulphate react with KCN to give
Mn 2+ :1s 2 2s 2 p6 3s 2 3 p 6 3d 5 white ppt of Cu(CN)2 and cyanogen gas. The
i.e. 5 unpaired electrons. insoluble copper cyanide dissolve in excess of
71. (d) Co here is in +3 oxidation state KCN and give soluble potassium cuprocyanide
CuSO 4 + 2 KCN ¾
¾® K 2 SO 4 + Cu (CN ) 2
Co
® 2CuCN + CN - CN
2Cu(CN) 2 ¾¾
insoluble cyanogen
Co3+
CuCN + 3KCN ¾¾
® K 3 [Cu(CN) 4 ]
Soluble
Unpaired electrons = 4 and sp3d 2 hybridisation
and octahedral shape. 74. (a) (CO) carbonyl group being a strong ligand
72. (d) Cr 3+ has 4sº 3d 3 electronic configuration paired all electrons present in d orbital of Ni.
with 3 unpaired electrons, hence paramagnetic.
In [Ni(CO)4 ] complex, Ni will have 3d10
In other cases, pairing of d-electrons take place
configuration. It has tetrahedral geometry but
in presence of strong field ligands such as CO
diamagnetic as there are no unpaired electrons.
or CN–.
In Cr(CO)6 molecule 12 electrons are contributed 75. (b) As in [NiCl4]–2, chloride ion being a weak
by CO group and it contain no odd electron ligand is not able to pair up the d–e–s.
[Cr(CO)6] 76. (d) In [Cr (NH3)6]Br3, Cr is in +3 oxidation state etc.

3d 4s 4p
× × × × × ×
× × × × × × Cr
24
3d 4s 4p
––– diamagnetic d2sp 3 hybridized
[Fe(CO)5] 4p
3d 4s
× × × × × Cr +3
× × × × ×
3d 4s 4p Its ion is octahedral in nature. Due to the
––– diamagnetic presence of three unpaired electrons it is
paramagnetic.
EBD_8336
240 CHEMISTRY
77. (b)
No. of
Atom/Ion Configuration Magnetic
unpaired
Complex nature
electrons
3d 4s 4p
2+ 8
Ni (d ) 2
2–
[NiCl4]
2
sp3
2–
[Ni(CN)4] 0
Rearrangement dsp
2
8 2
Ni (d s ) 2
[Ni(CO)4]
0
Rearrangement
sp3
78. (d) In the formation of a coordinate bond, the 83. (a) As + ve charge on the central metal atom
ligands donate a pair of electrons to the metal increases, the less readily the metal can donate
atom. Futher nitrogen and oxygen has great electron density into the p* orbitals of CO ligand
tendency to donate the pair of electrons in most to weaken the C – O bond. Hence, the C – O
of the compounds. Therefore, both nitrogen bond would be strongest in [Mn(CO)6]+.
and oxygen are common donor atoms in ligands.
79. (a) According to VSEPR theory, a molecule with 84. (a) Triethoxyaluminium has no Al – C linkage
six bond pairs must be octahedral. O - CH 2 CH 3
80. (b) [Fe(CO)5] Al O - CH CH2 3
EAN = Z – O.N. + 2(C.N.) O - CH 2 CH 3
= 26 – 0 + 2(5)
85. (a) The number of carbon atom found in p bonded
= 26 + 10 organometallic compounds is indicated by the greek
= 36 latter 'h' with a number. The prefixes h2, h5 and h6
Only one central metal atom/ion is present and indicate that 2, 5 and 6 carbon atom are bound to
it follows EAN rule, so it is mononuclear. the metal in the compound.(CH3)4Sn does not
81. (a) Grignard's reagent (RMgX) is a s-bonded involve any pi (p) bond formation. (CH3)4Sn is a s
organometallic compound. bonded organometallic compound.
82. (c) [Fe(CO)4]2– 86. (d) In metal carbonyl complexes, s and p both
Since metal atom is carrying maximum –ve
bonds are present because of synergic bonding.
charge therefore, it would show maximum
synergic bonding as a resultant C—O bond Thus, [Co(CO)5(NH3)]2+ has s and p bonding.
length would be maximum. 87. (a) Organometallic compounds are those
compounds in which there is a bond which
M–C p bond in metal carbonyl which is formed involve metal-carbon bond. In [Ni(CO)4] there
by the donatio of an electron pair from a filled d-
orbital of metal into the vacant anti bonding p- are bond involving Ni – C.
orbtial of CO, strengthen the M–C s bond. This is In chlorophyll, there are 4 bonds between Mg – N.
called synergic effect.
Haloalkanes and Haloarenes 241
24 Haloalkanes and
Haloarenes
2020 2019 2018 2017 2016

elimination/
Preparation and
dehydration 1 A
properties of
reaction
haloalkanes
Wurtz reaction 1 A
conversion(halogen
1 A
ation/reduction)
Preparation and
elimination/substit
properties of 1 A
ution/addition
haloarenes
optical activity in
1 D
biphenyls
Topic 1: Preparation and Properties of 4. Two possible stereo-structures of

Haloalkanes CH3CHOH.COOH, which are optically active, are
called. [2015 RS]
1. Elimination reaction of 2-Bromo-pentane to form
(a) Diastereomers (b) Atropisomers
pent-2-ene is: [2020]
(c) Enantiomers (d) Mesomers
(A) b-Elimination reaction 5. Which of the following compounds will undergo
(B) Follows Zaitsev rule racemisation when solution of KOH hydrolyses?
(C) Dehydrohalogenation reaction [2014]
CH2Cl
(D) Dehydration reaction
(i)
(a) (A), (C), (D) (b) (B), (C), (D)
(c) (A), (B), (D) (d) (A), (B), (C) (ii) CH3CH2CH2Cl
2. Which of the following alkane cannot be made CH3
in good yield by Wurtz reaction? [2020] |
(a) 2,3-Dimethylbutane (b) n-Heptane (iii) H3C - C H - CH2Cl
(c) n-Butane (d) n-Hexane
3. In an SN1 reaction on chiral centres there is : CH3
[2015 RS] C
(a) 100 % racemization Cl
(iv) H
(b) inversion more than retention leading to C2H5
partial racemization
(c) 100 % retention (a) (i) and (ii) (b) (ii) and (iv)
(d) 100 % inversion (c) (iii) and (iv) (d) (i) and (iv)
EBD_8336
242 CHEMISTRY
6. Which of the following acids does not exhibit (a) CH3 – CH2 – CH2Br
optical isomerism ? [2012]
(b) CH3 - CH - CH 2 Br
(a) Maleic acid (b) a -amino acids |
(c) Lactic acid (d) Tartaric acid CH3
7. Consider the reactions : [2011 M]
(i) C H OH
2 5 ¾¾
(CH 3 ) 2 CH - CH 2 Br ¾¾¾ ® (CH 3 ) 2 CH3
|
(CH3)2 CH - CH2OC2H5 + HBr CH3 - C - CH 2 Br
(c)
|
C 2 H 5O -
(ii) (CH3 )2 CH - CH 2 Br ¾¾¾¾¾ ® (CH 3 )2 CH
3
(CH3)2 CH - CH2OC2H5 + Br -
(d) CH3CH2Br
The mechanisms of reactions (i) and (ii) are 11. How many stereoisomers does this molecule
respectively : have ? [2008]
(a) SN1 and SN2 (b) SN1 and SN1 CH3CH = CHCH 2CHBrCH 3
(c) SN2 and SN2 (d) SN2 and SN1
(a) 4 (b) 6
8. Which one is a nucleophilic substitution
reaction among the following ? [2011] (c) 8 (d) 2
12. If there is no rotation of plane polarised light by
(a) CH3 – CH = CH2 + H2O ¾®
a compound in a specific solvent, though to be
CH3 – CH – CH3 chiral, it may mean that [2007]
OH (a) the compound is certainly meso

(b) there is no compound in the solvent
(b) RCHO + R ¢MgX ¾® R – CH – R¢
(c) the compound may be a racemic mixture
OH
(d) the compound is certainly achiral.
CH 3
13. CH3 – CHCl – CH2 – CH3 has a chiral centre.
(c) CH3 – CH 2–CH–CH 2Br ¾® Which one of the following represents its
R-configuration? [2007]
CH3
CH 3– CH 2–CH–CH 2NH 2 C2 H 5 C2 H5
| |
(d) CH3CHO + HCN ¾¾ ® CH3CH (OH) CN (a) H - C - CH3 (b) Cl - C - CH3
| |
9. Which of the following reactions is an example Cl H
of nucleophilic substitution reaction? [2009]
(a) 2 RX + 2 Na ® R – R + 2 NaX CH3 C2 H 5
(b) RX + H2 ® RH + HX | |
(c) H - C - Cl (d) H3C - C - Cl
(c) RX + Mg ® RMgX | |
(d) RX + KOH ® ROH + KX C2 H5 H
10. In an SN2 substitution reaction of the type
14. For (i) I–, (ii) Cl–, (iii) Br–, the increasing order of
- DMF -
[2008] nucleophilicity would be [2007]
R - Br + Cl ¾¾¾ ® R - Cl + Br
which one of the following has the highest –
(a) Cl < Br < I – – (b) I < Cl < Br–
– –
reactivity rate ? (c) Br– < Cl– < I– (d) I– < Br– < Cl–
15. Which of the following is not chiral ? [2006] CH3 CH3

(a) 2, 3- Dibromopentane H OH HO H
(c) and
(b) 3-Bromopentane HO H HO H
(c) 2-Hydroxypropanoic acid CH3 CH3
(d) 2-Butanol CH3 CH3
16. The chirality of the compound [2005] H OH H OH
(d) and
Br HO H H OH
CH3 CH3
C 21. Reactivityorder of halides for dehydrohalogenation
H is
is [2002]
H3C Cl
(a) R – F > R – Cl > R – Br > R –I
(a) R (b) S (b) R –I > R – Br > R – Cl > R – F
(c) E (d) Z (c) R –I > R – Cl > R – Br > R – F
17. Which of the following undergoes nucleophilic (d) R – F > R –I > R – Br > R – Cl
substitution exclusively by SN1 mechanism?
NaCN Ni / H
[2005] 22. CH 3 CH 2 Cl ¾¾ ¾
¾® X ¾¾ ¾
¾2®Y
(a) Ethyl chloride Acetic

Y ¾¾ ¾
¾® Z
(b) Isopropyl chloride anhydride
(c) Chlorobenzene Z in the above reaction sequence is [2002]
(d) Benzyl chloride (a) CH3CH2CH2NHCOCH3
18. The molecular formula of diphenylmethane, (b) CH3CH2CH2NH2
CH2 , is C13H12. (c) CH3CH2CH2CONHCH3
How many structural isomers are possible when (d) CH3CH2CH2CONHCOCH3
one of the hydrogens is replaced by a chlorine 23. When CH3CH2CHCl2 is treated with NaNH2,
atom? [2004] the product formed is [2002]
(a) 6 (b) 4 (a) CH3 — CH = CH2
(c) 8 (d) 7
(b) CH 3 — C º CH
19. Which of the following is least reactive in a
nucleophilic substitution reaction. [2004] NH2
(c) CH3CH2CH
(a) (CH 3 )3 C - Cl (b) CH 2 = CHCl
NH2
(c) CH 3CH 2Cl (d) CH 2 = CHCH 2 Cl Cl
20. Which of the following pairs of compounds are (d) CH3CH2CH
enantiomers? [2003] NH2
CH3 CH3 24. An organic compound A (C4H9Cl) on reaction
HO H HO H with Na/diethyl ether gives a hydrocarbon which
(a) and on monochlorination gives only one chloro
H OH HO H derivative, then A is [2001]
CH3 CH3
(a) tert-butyl chloride
CH3 CH3 (b) sec-butyl chloride
(b) H OH HO H (c) isobutyl chloride
and
HO H H HO (d) n-butyl chloride
CH3 CH3
EBD_8336
244 CHEMISTRY
25. 33. An important chemical method to resolve a racemic

CH3 - CH2 - CH - CH3 obtained by chlorination
| mixture makes use of the formation of [1994]
Cl
(a) a meso compound (b) enantiomers
of n-butane, will be [2001]
(c) diasteromers (d) racemates
(a) l-form (b) d-form
34. The process of separation of a racemic
(c) Meso form (d) Racemic mixture modification into d and l-enantiomers is called
26. Which is a chiral molecule? [1999] [1994]
(a) 2, 2-dimethylbutanoic acid (a) Resolution
(b) 4-methylpentanoic acid (b) Dehydration
(c) 3-methylpentanoic acid (c) Revolution
(d) 3,3-dimethylbutanoic acid (d) Dehydrohalogenation
27. 2-Bromopentane is heated with potassium 35. When chlorine is passed through propene at
ethoxide in ethanol. The major product obtained 400°C, which of the following is formed ? [1993]
is [1998] (a) PVC
(a) 2-ethoxypentane (b) pentene-1 (b) Allyl chloride
(c) trans-2-pentene (d) cis-pentene-2 (c) Alkyl chloride
28. Which of the following compounds is not chiral? (d) 1, 2-Dichloroethane
[1998] 36. Which of the following is an optically active
(a) DCH2CH2CH2Cl (b) CH3CH2CHDCl compound ? [1988]
(c) CH3CHDCH2Cl (d) CH3CHClCH2D (a) 1-Butanol (b) 1-Propanol
29. Which one of the following compounds is (c) 2-Chlorobutane (d) 4-Hydroxyheptane
resistant to nucleophilic attack by hydroxyl ions? Topic 2: Preparation and Properties of
[1998] Haloarenes
(a) Methyl acetate (b) Acetonitrile 37. The hydrolysis reaction that takes place at the
(c) Diethyl ether (d) Acetamide slowest rate, among the following is
30. The reaction: [NEET Odisha 2019]
CH3 (CH2)5 H H (CH2)5 CH3 aq. NaOH
OH
– (a) CH2Cl ¾¾¾® CH2OH
C – Br ¾® HO – C
H3C CH3
is described as [1997] aq. NaOH –+
(b) Cl ¾¾¾® ONa
(a) SE2 (b) SN1
(c) SN0 (d) SN2 CH3 CH3
31. Which of the following will exhibit chirality?
[1996] aq. NaOH
(a) 2-Methylhexane (b) 3-Methylhexane (c) H3C – CH2 – Cl ¾¾¾® H3C – CH2 – OH
(c) Neopentane (d) Isopentane
32. Zerevitinov’s determination of active hydrogen aq. NaOH
in a compound is based upon its reaction (d) H2C = CH – CH2Cl ¾¾¾®
with [1994] H2C = CH – CH2OH
(a) Na (b) CH3MgI
(c) Zn (d) Al.
38. The compound C7H8 undergoes the following 41. In which of the following compounds, the C - Cl
reactions: [2018] bond ionisation shall give most stable carbonium
C7 H8 ¾¾¾¾
3Cl / D
2 ® A ¾¾¾¾ Br /Fe
2 Zn /HCl
® B ¾¾¾¾® C
ion? [2015]
The product 'C' is H
(a) m-bromotoluene CH — Cl
(b) o-bromotoluene
(c) p-bromotoluene H3C
(d) 3-bromo-2,4,6-trichlorotoluene C — Cl
(a) H3C (b)
39. For the following reactions : [2016] CH3
(1) CH3CH2CH2Br + KOH ®
CH3CH=CH2+KBr + H2O H H
C — Cl H 3C
H3C CH3 H3C CH3 (c) O 2NH2C H (d) C — Cl
H 3C
(2) + KOH ¾® + KBr
42. What products are formed when the following
Br OH compounds is treated with Br2 in the presence
Br of FeBr 3? [2014]
(3) + Br2 ¾®
CH3
Br
Which of the following statements is correct ?
(a) (1) and (2) are elimination reactions and (3)
is addition reaction CH3
(b) (1) is elimination, (2) is substitution and (3)
is addition reaction CH3 CH3
(c) (1) is elimination, (2) an d (3) are
substitution reactions Br
(a) and
(d) (1) is substitution, (2) and (3) are addition
reactions CH3 CH3
40. Which of the following biphenyls is optically Br
active ? [2016]
CH3 CH3
(a) O2N
Br Br
(b) and
CH3 CH3
I
Br Br CH3 CH3
Br
(b) (c) and
I I CH3 CH3
I Br
(c) CH3 CH3
I (d) and
CH 3 CH3 Br CH3
(d) Br
CH 3
EBD_8336
246 CHEMISTRY
43. Which of the following compounds undergoes (I) (II) (III) (IV)
nucleophilic substitution reaction most easily ?
(a) I < II < IV < III (b) II < III < I < IV
[2011 M]
(c) IV < III < I < II (d) III < II < I < IV
Cl 47. Benzene reacts with CH3Cl in the presence of
Cl
anhydrous AlCl3 to form: [2009]
(a) (b) (a) chlorobenzene (b) benzylchloride
NO2 (c) xylene (d) toluene
CH3 48. The replacement of chlorine of chlorobenzene
to give phenol requires drastic conditions, but
the chlorine of 2,4-dinitrochlorobenzene is
Cl
readily replaced since, [1997]
Cl
(a) nitro groups make the aromatic ring electron
(c) (d)
rich at ortho/para positions
(b) nitro groups withdraw electrons from the
OCH3
meta position of the aromatic ring
44. The reaction of toluene with Cl2 in presence of (c) nitro groups donate electrons at meta
FeCl3 gives 'X' and reaction in presence of light position
gives ‘Y’. Thus, ‘X’ and ‘Y’ are : [2010] (d) nitro groups withdraw electrons from
(a) X = Benzal chloride, Y = o – Chlorotoluene ortho/para positions of the aromatic ring
(b) X = m – Chlorotoluene, Y = p –Chlorotoluene 49. Benzene reacts with n-propyl chloride in the
presence of anhydrous AlCl3 to give [1993]
(c) X = o –and p – Chlorotoluene,
(a) 3 – Propyl – 1 – chlorobenzene
Y = Trichloromethyl – benzene
(b) n-Propylbenzene
(d) X = Benzyl chloride, Y = m – Chlorotoluene
(c) No reaction
45. Which one is most reactive towards SN 1 reaction ?
(d) Isopropylbenzene.
(a) C6 H5CH(C6 H5 )Br [2010]
50. Chlorobenzene reacts with Mg in dry ether to
(b) C6 H5CH(CH3 )Br give a compound (A) which further reacts with
ethanol to yield [1993]
(c) C6 H5C(CH3 )(C6 H5 )Br (a) Phenol (b) Benzene
(d) C6 H5CH 2 Br (c) Ethylbenzene (d) Phenyl ether.
51. Which chloro derivative of benzene among the
46. The correct order of increasing reactivity of
following would undergo hydrolysis most
C – X bond towards nucleophile in the following
readily with aqueous sodium hydroxide to
compounds is: [2010]
furnish the corresponding hydroxy derivative?
X X [1989]
NO2
NO2
(CH3)3 C – X, (CH3)2CH – X
(a) O2 N Cl
NO2
NO2
Cl
(b) O2N Cl
(d) Cl C Cl
(c) Me2N Cl CH2Cl

53. Which of the following is responsible for
(d) C6H5Cl. depletion of the ozone layer in the upper strata
of the atmosphere? [2004]
Topic 3: Some Important Polyhalogen
(a) Polyhalogens (b) Ferrocene
Compo unds
(c) Fullerenes (d) Freons
52. Trichloroacetaldehyde, CCl3CHO reacts with
chlorobenzene in presence of sulphuric acid 54. Chloropicrin is obtained by the reaction of
and produces: [2009] [2004]
Cl (a) steam on carbon tetrachloride
(b) nitric acid on chlorobenzene
(c) chlorine on picric acid
(d) nitric acid on chloroform
(a) Cl C Cl 55. Industrial preparation of chloroform employs
acetone and [1993]
H
(a) Phosgene
OH (b) Calcium hypochlorite
(c) Chlorine gas
(b) Cl C Cl (d) Sodium chloride.
Cl 56. Phosgene is a common name for [1988]
(a) phosphoryl chloride
(b) Thionyl chloride
(c) Cl CH Cl
(c) Carbon dioxide and phosphine
CCl3 (d) Carbonyl chloride.
ANSWER KEY
1 (d) 7 (a) 13 (b) 19 (b) 25 (d) 31 (b) 37 (b) 43 (a) 49 (d) 55 (b)
2 (b) 8 (c) 14 (a) 20 (b) 26 (c) 32 (b) 38 (a) 44 (c) 50 (b) 56 (d)
3 (b) 9 (d) 15 (b) 21 (b) 27 (c) 33 (c) 39 (b) 45 (c) 51 (a)
4 (c) 10 (d) 16 (a) 22 (a) 28 (a) 34 (a) 40 (b) 46 (a) 52 (c)
5 (N) 11 (a) 17 (d) 23 (b) 29 (c) 35 (b) 41 (b) 47 (d) 53 (d)
6 (a) 12 (a) 18 (b) 24 (a) 30 (d) 36 (c) 42 (c) 48 (d) 54 (d)
EBD_8336
248 CHEMISTRY
Hints & Solutions

1. (d) If 50% attack below and above the plane of
carbocation take place than 100% racemization
1 2 3 4 5
Elimination occurs but it may not be highly probable.
C H3 - C H - CH 2 - C H 2 - C H3 ¾¾¾¾¾®
| i.e. if inversion occurs more than retention
Br leading to partial racemization.
2-Bromo-pentane
4. (c) H
CH3 - CH = CH - CH 2 - CH 3
Mechanism : C COOH
CH3
a b OH
CH3 – CH – CH – CH2 – CH3 Four different Substituent, only one chiral centre.
Hence only enantiomers are possible.
Br H
5. (N) The compound in option (iv) will undergo
Base SN1 reaction with KOH solution. Hence, only this
CH3 – CH = CH – CH2 – CH3 compound will undergo partial racemisation.
Compounds given in other options are not chiral.
It is an b elimination reaction as b hydrogen is 6. (a) H H
abstracted and results more substituted alkene, C—
—C
which follows Zaitsev’s rule. HOOC COOH
Since ‘H’ and ‘Br’ are removed, it is dehydro- (cis)
halogenation. maleic acid
2. (b) Wurtz reaction is used to prepare HOOC H
symmetrical alkanes like R1 – R1, as C—
—C
H COOH
(Trans)
Dry ether
R1 - X + 2Na + X - R1 ¾¾¾¾
® R1 - R1 + 2NaX
It shows geometrical isomerism but does not
If R1 and R2 are different, then mixture of alkanes show optical isomerism.
may be obtained as 7. (a) First reaction is SN1 reaction because
Dry ether C2H5OH is used as solvent which is a weak
R1 - X + 2Na + R 2 - X ¾¾¾¾
®
nucleophile.
R1 - R1 + R1 - R 2 + R 2 - R 2 + 2NaX Second reaction is SN2 reaction because C2H5O–
Hence, n-heptane cannot be made in good yield is a strong nucleophile.
using Wurtz reaction, since it is unsymmetrical
alkene. A strong nucleophile favours the SN2 reaction and
a weak nucleophile favours the SN1 reaction.
3. (b) In SN1 reaction, carbocation a planar
species as intermediate is formed. 8. (c) Nucleophilic substitution reactions are the
R1 most common reactions of alkyl halides.
Nu
Å Because of high electronegativities of the halogen
C R3
atom, the carbon halogen (C – X) is highly
Nu polarised covalent bond. Thus, the carbon atom of
R2
the C – X bond becomes a good site for attack by
So attack from below or above the plane can
nucleophiles (electron rich species).
take place.
9. (d) In nucleophilic substitution, a nucleophile 2

provides an electron pair to the substrate and C2H5
the leaving group departs with an electron pair. 3
13. (b) Cl — C — CH3
Nu: + R—X ¾® R—Nu + X: 1
10. (d) SN2 mechanism is followed in case of H
4
primary and secondary halides i.e., SN2 reaction
R-configuration
is favoured by small groups on the carbon atom
attached to halogens so reactivity order is: 14. (a) Nucleophilicity increases down the periodic
table : I - > Br - > Cl - > F-
CH3 CH2 Br > CH3 CH2 CH2 Br >
CH3 Nucleophilicity governs the kinetics of a reaction
| while basicitydetermines its thermodynamics.
CH3– CH – CH2Br > CH3 – C – Br
| | Since, electronegativity decreases down the group
CH3 CH3 (or electropositivity increases), nucleophilicity
also increases down the group. But the order of
i.e. option (d) is correct. basicity is:
11. (a) In the molecule I– < Br– < Cl– < F–
CH3 CH = CH CH 2 CH- CH 3, 15. (b)

|
Br | | | | |
(a) C – C*– C*– C – C – [Chiral]
the number of stereoisomers is given by sum of | | | | |
geometrical isomers (because of presence of C = C) Br Br
and optical isomers (because of presence of chiral | | | | |
carbon atom). (b) – C – C – C – C – C – [Not chiral]
| | | | |
Number of geometrical isomers = 2 (one C = C is Br
present).
Number of optical isomers = 2 (one chiral carbon OH
| |
atom). *
(c) – C – C – COOH [Chiral]
Total number of stereoisomers = 2 + 2 = 4 | |
12. (a) Compounds which do not show optical OH
activity inspite of the presence of chiral carbon | | | |
*
atoms are called meso-compounds. (d) – C – C – C – C – [Chiral]
| | | |
The absence of optical activity in these compound * marked are chiral carbons.
is due to the presence of a plane of symmetry in 16. (a) Clockwise rotation.
their molecules. e.g. meso-tartaric acid is optically
1 Br
inactive. H 4
COOH C
H3C Cl 2
H OH 3
(Plane of symmetry) Hence configuration is R.
H OH If the eye travel in a clockwise direction, the
configuration is (R) as the order of priority is
COOH Br > Cl > CH3 > H.
EBD_8336
250 CHEMISTRY
17. (d) SN1 reaction is favoured by heavy groups

on the carbon atom attached to halogen i.e CH3 CH3
Benzyl > allyl > tertiary > secondary > primary H OH HO H
> alkyl halides Å and
HO H H OH
CH2Cl CH2
– Cl CH3
¾® CH3
21. (b) The order of atomic size of halogens

(Benzyl cation)
decrease in the order I > Br > Cl > F
Obtained from SN1 path.
This molecule is resonance stabilised. i.e on moving down a group atomic size increases.
18. (b) In diphenylmethane monochlorination at Further the bond length of C-X bond decreases
following positions will produce structured in the order
isomers C – I > C – Br > C – Cl > C – F
and hence the bond dissociation energy
CH2 decreases in the order
R – F > R – Cl > R – Br > R – I
1
4 hence R – I being a weakest bond break most
2 3 easily. Hence R – I is most reactive.
22. (a)
Cl CH2
NaCN Ni/H
® CH3CH 2CN ¾¾¾¾
CH3CH 2 Cl ¾¾¾¾ 2®
(1) (X)
CH2 ®
CH 3 CH 2 CH 2 NH 2 ¾¾¾¾¾¾
(CH 3CO) 2 O
(Y)
Cl
(2)
CH3CH 2 CH 2 NHCOCH 3
(Z)
CH2
NaNH 2
Cl 23. (b) CH 3 — CH 2 — CHCl 2 ¾¾ ¾¾®
D
(3)
Cl CH 3 — CH = CHCl ¾¾ ¾¾
NaNH
2 ® CH — C º CH
3
D Final Product
CH2
(4) CH3 CH3

19. (b) H 2 C = CHCl is capable of showing 24. (a) CH3 – C – Cl + 2Na + Cl – C – CH3
resonance which develops a partial double bond, CH3 CH3
character to C–Cl bond, thereby making it less t-Butyl chloride
¾¾®
Wurtz
reactive towards nucleophilic substitution.

Rxn
_
H 2 C==CH –Cl H 2C – CH=Cl + CH3CH3 CH3CH3
¾¾®
20. (b) Compound which are mirror image of each CH3 – C – C –CH2Cl Mono
CH3– C – C – CH3
other and are not superimposable are termed as CH3CH3 Clorination CH3 CH3
enantiomers.
hn
25. (d) Cl2 ¾¾® Cl + Cl
• • 30. (d) When (–) 2-bromooctane is allowed to react
with sodium hydroxide under given conditions,
Cl / hn where second order kinetics is followed, the
CH3 — CH2 — CH2 — CH3¾¾2¾¾®
product obtained is (+) 2-octanol.
CH3 CH3 C6H13 H C6H13 C6H13
–
OH
H C Br ¾® HO -----C -----Br ® HO C H + Br–
H — C — Cl + Cl — C — H
CH3 CH3 CH3
C2H5 C2H5 (–) 2-Bromooctane Transition state (+) 2–octanol
d l In this reaction Walden Inversion takes place so
Racemic mixture it is an example of SN2-reaction.
50% d form + 50% l form
31. (b) H 3C — CH 2 — *CH — CH 2 — CH 2 — CH3
|
Chlorination of alkane takes place via free radical
CH3
formation. Cl· may attack on either side and gives
a racemic mixture. 3-Methylhexane
Due to presence of four different groups on
26. (c) Chiral molecules are those molecules which
have atleast one asymmetric carbon atom (a carbon,(C*) it is chiral
carbon atom attached to 4 different groups). This 32. (b) Number of active hydrogen in a compound
is true in case of 3-methylpentanoic acid. corresponds to the number of moles of CH4
H evolved per mole of the compound.
|
CH MgI
C2H5 – C - CH2 COOH -OH, - NH2 , - SH, - OH or - C º CH ¾¾¾¾
3
® CH 4 (2CH 4 from
|
CH3
® CH 4 ( 2CH 4 from - NH 2 )
27. (c) Potassium ethoxide is a strong base, and 2-
bromopentane is a 2º bromide, so elimination 33. (c) Racemic mixtures are resolved by the
formation of Diastereomers.
reaction predominates
OC H - Enantiomers have same physical and chemical
CH 3 CH (Br )CH 2 CH 2 CH 3 ¾¾ ¾
2 ¾
5®
properties except rotation of plane polarized light.
CH3CH = CHCH 2CH3 + CH 2 = CHCH2CH 2CH3 Diasteromers have different physical and chemical
Pentene - 2(major) trans Pentene -1(min or) cis properties.
Since, trans- alkene is more stable than cis, thus 34. (a) Resolution.
trans-pentene -2 is the main product.
28. (a) Due to absence of a chiral 35. (b) At high temp. i.e., 400°C substitution occurs
C-atom. D — CH 2 — CH 2 — CH 2 Cl in preference to addition.
molecule is not a chiral molecule.
Cl , 400°C
29. (c) The compound is diethyl ether (CH3CH2)2O CH 3 CH = CH 2 ¾¾2¾ ¾¾®
which is resistant to nucleophilic attack by - HCl
hydroxyl ion due to absence of double or triple ClCH 2 CH = CH 2
bond, whereas all other compounds given are
unsaturated. H
|
O 36. (c) H3C - CH 2 - C*- CH3
||
|
C2 H5 OC2 H5 CH3 - C - OCH3
Cl
ether Methyl acetate
The compound containing a chiral carbon atom
O i.e., (a carbon atom which is attached to four
||
CH3 - C º N CH3 - C - NH 2 different substituents is known as a chiral carbon
Acetonitrile acetamide atom) is optically active.
EBD_8336
252 CHEMISTRY
37. (b) Aryl halides do not give substitution

Biphenyl compounds are devoid of individual
reactions due to partial double bond chiral carbon atoms, but o-substituted biphenyl
character between carbon and halogen. show optical isomerism. This is due to the fact
CH3 CCl3 that, both the rings are not in the same plane because
of steric hindrance of the groups present in o-
38. (a) 3Cl Br position. Also, these groups restrict the rotation
¾¾®
D
2
¾¾®
2
Fe around the single bond and hence they must exist
in two non-super imposable mirror images of each
CCl3 CH3 other.
Zn 41. (b)
¾¾®
HCl 42. (c) Methyl group is ortho para directing but
Br Br due to steric hindrance effect, generated by two
m-Bromotoluene CH3 groups substitution will not take place on
39. (b) (1) CH3CH2CH2–Br + KOH position (I). Hence, only two products are
® CH3CH=CH2 + KBr + H2O possible.
This is dehydrohalogenation reaction which is
CH3
an example of elimination reaction.
(2) III I
H3C CH3 H3C CH3

C + KOH ® C + KBr II CH3
i.e. CH3 CH3
Br OH
Replacement of Br – by OH– is substitution Br2
reaction thus, it is a nucleophilic substitution ¾¾®
FeBr3
reaction. CH3 CH3
Br Br
(3) + Br2 ® (A)
CH3
Br Br
Above reaction involves addition of Br 2 across
+
double bond. Thus, it is called addition reaction.
40. (b) CH3
In option (a), there is no chiral carbon.
43. (a) To compare the rates of substitution, in
In option (c), there exist a center of symmetry. chlorobenzene, electron-withdrawing group, and
In option (d), there exist a plane of symmetry. chlorobenzene having electron-releasing group,
we compare the structures carbanion I (from
In option (d), both the rings are not in the same chlorobenzene), II (from chlorobenzene
plane and the rotation is restricted around the containing electron-withdrawing group) and III
single bond. (from chlorobenzene containing electron-
releasing group).
Br Br
Z Cl Z Cl
– –
I I I II G
Restricted rotation
G withdraws electrons, neutralises (disperses) – 45. (c) SN1 reactions involve the formation of
ve charge of the ring, stabilises carbanion, carbocations, hence higher the stability of
facilitates SN reaction (activation effect) intermediate carbocation, more will be reactivity
Z Cl of the parent alkyl halide. The tertiary carbocation
formed from (c) is stabilized by two phenyl groups
– and one methyl group, hence most stable.
46. (a) Tertiary alkyl halide is most reactive towards
III G nucleophilic substitution because the
corresponding carbocation (3°) is most stable.
G releases electrons, intensifies –ve charge,
Aryl halide is least reactive due to partial double
destabilizes carbanion, retards SN reaction
bond character of the C – Cl bond.
(deactivation)
NO2 is activating group and CH3 and OCH3 are Presence of — NO 2 groups in ortho and para
deactiving group. positions increases the reactivity of the – Cl
towards nucleophiles.
Hence, the correct order of nucleophilic
substitution reaction is : (CH3)3 – C – X > (CH3)2 – CH – X >
III IV
Cl Cl Cl
X
Cl
X
> > > NO2
>
NO2 CH3 OCH3 NO2
II I
In SN reactions, a carbanion is formed as an or I < II < IV < III
intermediate, so any substituent that increases the
stability of carbanion and hence the transition state CH3
leading to its formation will enhance the S N
reactions. Anhyd.
47. (d) + CH3Cl ¾¾® +HCl
AlCl3
44. (c)
CH3 CH3 CH3 Toluene
Cl Cl Friedel Craft's reaction

¾¾ 2¾® +
FeCl3 48. (d) —NO2 group is electron attracting group,
so it is able to deactivate the benzene ring.
Cl
CH3 Cl
Cl , hv NO2
¾¾2¾¾
®
CH2Cl CHCl2 CCl3 NO2

Hence, withdrawl of electrons from ortho & para
Cl2, hv Cl2, hv
¾¾¾¾ ® ¾¾¾¾ ® position cause easy removal of –Cl atom due to
development of +ve charge on o- and p – positions.
EBD_8336
254 CHEMISTRY
Anhyd. produce free atomic chlorine which results in

49. (d) C 6H6 + CH 3CH 2CH 2CI ¾¾¾¾ ®
AlCl3 decomposition of ozone.
CH 3 Chlorofluorocarbons are chemically inert and hence

| do not react with any substance with which they
C6 H5 - CH - CH 3 come in contact and therefore, float through the
atmosphere and as a result enter the stratosphere.
Isopropyl benzene
54. (d) Chloropicrin is nitrochloroform. It is obtained
Mg
50. (b) C6 H5 Cl ¾¾¾¾
dry ether
® C6 H5 MgCl by the nitration of chloroform with HNO3.
HNO
(A) HCCl 3 ¾¾ ¾
¾3 ® O NCCl
2 3
Chloroform Chloropicrin
CH 3CH 2OH Chloropicrin is poisonous and used as an
® C6 H 6 + CH3CH 2OMgCl
¾¾¾¾¾¾
insecticide and a war gas.
55. (b) By distilling ethanol or acetone with a paste
51. (a) Cl in 2, 4, 6-trinitrochlorobenzene is activated of bleach in g powder (laboratory and
by three NO2 groups at o- and p-positions and commercial method).
hence, undergoes hydrolysis most readily.
CaOCl 2 + H 2 O ¾
¾® Ca (OH ) 2 + Cl 2
52. (c)
Cl2, so obtained acts as a mild oxidising as well
Cl Cl as chlorinating agent
conc. H SO
Cl 3C–C=O + 2 4
¾¾¾¾® Cl2C–CH
Cl
(i) CH 3COCH 3 + 3Cl 2
H Cl Cl
DDT ¾¾® CCl 3 .CO.CH 3 + 3HCl
(Chlorination)
53. (d) Chlorofluorocarbons, e.g. CF2Cl2, CHF2Cl2,
(ii) 2CCl3 .CO.CH 3 + Ca (OH) 2 ¾¾®
HCF2 CHCl 2 . These are non-inflammable,
colourless and stable upto 550ºC. These are 2CHCl 3 + (CH 3COO) 2 Ca
emitted as propellants in aerosol spray, (Hydrolysis)
refrigerators, fire fighting reagents etc. They 56. (d) Carbonyl chloride (COCl2).
absorb UV-rays in the stratosphere and
Alcohols, Phenols and Ethers 255
25 Alcohols, Phenols
and Ethers
2020 2019 2018 2017 2016

conversion reaction
Preparation and
with Na/PCl 5/ether 1 A
properties of alcohols
formation
preparation of
1 A
phenols
Reimer- Tieman
1 A
reaction
Preparation and haloform reaction 1 A
properties of phenols conversion(reaction
1 D
with AlCl 3/ozonolysis)
cis trans diol 1 A

acidity order 1 D
cleavage with HI 1 A 1 A
protonation of ether 1 A
Preparation and
properties of ether Williamson synthesis 1 A
substitution reactions 1 D
(c) C2H5OH, C2H5ONa, C2H5Cl

Topic 1: Preparation and Properties
of Alcohols (d) C2H5Cl, C2H6, C2H5OH
3. How many isomers of C5H11 OH will be primary
1. When vapours of a secondary alcohol is passed alcohols ? [1992]
over heated copper at 573 K, the product formed (a) 5 (b) 4
is [NEET Odisha 2019] (c) 2 (d) 3.
(a) an alkene (b) a carboxylic acid 4. Which of the following reaction (s) can be used
(c) an aldehyde (d) a ketone for the preparation of alkyl halides ? [2015 RS]
2. The compound A on treatment with Na gives B, (I) CH3CH2OH + HCl ¾anh.ZnCl
and with PCl5 gives C. B and C react together to ¾ ¾ ¾2¾ ®
give diethyl ether. A, B and C are in the order (II) CH3CH2OH + HCl ¾ ¾
®
(a) C2H5OH, C2H6, C2H5Cl [2018] (III) (CH3)3COH + HCl ¾ ¾
®
anh.ZnCl2
(b) C2H5OH, C2H5Cl, C2H5ONa (IV) (CH3)2CHOH + HCl ¾¾¾¾¾ ®
EBD_8336
256 CHEMISTRY
(a) (I), (III) and (IV) only (a) CH 3CH (OH)CH 3

(b) (I) and (II) only (b) CH 3CH 2 CH(OH )CH 3
(c) (IV) only
(d) (III) and (IV) only (c) CH 3OH
5. Number of isomeric alcohols of molecular (d) CH 3CH 2OH
formula C6H14O which give positive iodoform 12. n-Propyl alcohol and isopropyl alcohol can be
test is [NEET Kar. 2013] chemically distinguished by which reagent?
(a) two (b) three (a) PCl5 [2002]
(c) four (d) five
(b) Reduction
6. In the following sequence of reactions [2012]
(c) Oxidation with potassium dichromate
KCN 3 ® H O+ (d) Ozonolysis
CH3 - Br ¾¾¾® A ¾¾¾¾
13. Which of the following is correct ? [2001]
LiAlH 4
B ¾¾¾¾ ® C, the end product (C) is : (a) On reduction of any aldehyde, secondary
ether alcohol is formed
(a) Acetone (b) Methane (b) Reaction of vegetable oil with H2SO4 gives
(c) Acetaldehyde (d) Ethyl alcohol glycerine
7. When glycerol is treated with excess of HI, it
(c) Sucrose on reaction with NaCl gives invert
produces: [2010]
(a) glycerol triiodide (b) 2–iodopropane sugar
(c) allyl iodide (d) propene (d) Alcoholic iodine gives iodoform with
8. Consider the following reaction, [2009] NaOH
PBr alc.KOH 14. Propan - 1- ol may be prepared by the reaction
3 ® X ¾¾¾¾® Y
ethanol ¾¾¾ of propene with [2000]
(i) H 2SO 4 room temperature
¾¾¾¾¾¾¾¾¾¾¾¾¾
(ii) H 2O, heat
® Z; (a) H3BO3
(b) H2SO4/H2O
the product Z is:
(c) B2H6, NaOH–H2O2
(a) CH3CH2 – O – CH2 – CH3 O
(b) CH3 – CH2 – O – SO3H ||
(d) CH 3 C - O - O - H
(c) CH3CH2OH
15. Reaction of CH — CH with RMgX leads to
(d) CH2 = CH2 2 2
9. H2COH · CH2OH on heating with periodic acid O

gives: [2009] formation of [1998]
(a) RCHOHR (b) RCHOHCH3
CHO
(a) 2 HCOOH (b) | R
CHO (c) RCH2CH2OH (d) CHCH2OH
H R
(c) 2 C=O (d) 2 CO2 16. The stablest among the following is [1994]
H (a) CH3CH(OH)2 (b) ClCH2CH(OH)2
10. Ethylene oxide when treated with Grignard
(c) (CH3)2 C (OH)2 (d) CCl3 CH (OH)2.
reagent yields [2006]
17. Which one of the following on oxidation gives a
(a) Tertiary alcohol
ketone ? [1993]
(b) Cyclopropyl alcohol
(a) Primary alcohol (b) Secondary alcohol
(c) Primary alcohol (c) Tertiary alcohol (d) All of these
(d) Secondary alcohol 18. What is formed when a primary alcohol
11. Which of the following will not form a yellow undergoes catalytic dehydrogenation ? [1993]
precipitate on heating with an alkaline solution (a) Aldehyde (b) Ketone
of iodine? [2004] (c) Alkene (d) Acid
19. Methanol is industrially prepared by [1992] CH3

(a) Oxidation of CH4 by steam at 900°C
(b) Reduction of HCHO using LiAIH4 H3C – C – O – O – H
(c) Reaction HCHO with a solution of NaOH (b)
(d) Reduction of CO using H2 and
ZnO – Cr2O3.
20. HBr reacts fastest with [1992]
(a) 2-Methylpropan-1-ol CH3
(b) 2-Methylpropan-2-ol O – O – CH
(c) propan-2-ol CH3
(d) propan-1-ol. (c)
21. The compound which reacts fastest with Lucas
reagent at room temperature is [1989] CH2 – O – O – H
(a) Butan-1-ol
(b) Butan-2-ol HC
CH3
(c) 2-Methyl propan-1-ol
(d) 2-Methylpropan-2-ol (d)
22. Propene, CH 3CH = CH 2 can be converted into
1-propanol by oxidation. Indicate which set of 25. In the reaction [2018]
reagents amongst the following is ideal to effect OH O– Na+
the above conversion ? [1989]
(a) KMnO4 (alkaline) CHO
+ CHCl3+ NaOH ¾®
(b) Osmium tetraoxide (OsO4/CH2Cl2)
(c) B2H6 and alk. H2O2 The electrophile involved is
(d) O3/Zn Å
23. Lucas reagent is [1988] (a) Dichloromethyl cation ( C HCl2 )

(a) Conc. HCl and anhydrous ZnCl2 Å
(b) Formyl cation ( C HO )

(b) Conc. HNO3 and hydrous ZnCl2
(c) Conc. HCl and hydrous ZnCl2 (c) Dichlorocarbene (: CCl 2 )
(d) Conc. HNO3 and anhydrous ZnCl2 !
(d) Dichloromethyl anion ( CHCl 2 )
Topic 2: Preparation and 26. Compound A, C8H10O, is found to react with
Properties of Phenols NaOI (produced by reacting Y with NaOH) and
24. The structure of intermediate A in the following yields a yellow precipitate with characteristic
reaction, is: [2019] smell.
CH3 A and Y are respectively [2018]
CH OH
O (a) H3C CH2 – OH and I2
CH3
O2
¾® AH
+
¾®
H2O
+H C3 CH3 (b) CH2 – CH2 – OH and I2
CH3 CH3
O CH (c) CH3 OH and I2
CH3
(a)
(d) CH – CH3 and I2
OH
EBD_8336
258 CHEMISTRY
27. Identify the major products P, Q and R in the (a) Acetone

following sequence of reactions: [2018] (b) Ozone
Anhydrous (c) MnO2
AlCl3
+ CH3CH2CH2Cl ¾ ¾ ¾ ¾ ® (d) Aluminium isopropxide
(i) O 30. Reaction of phenol with chloroform in presence
P ¾¾¾
2
¾
+ ®Q+R
(ii) H3O /D of dilute sodium hydroxide finally introduces
P Q R which one of the following functional group ?
CH2CH2CH3 CHO [2015 RS]
(a) –CH2Cl (b) –COOH
(a) , , (c) –CHCl2 (d) –CHO
31. Which of the following is not the product of
CH3CH2 – OH
CH2CH2CH3 CHO COOH dehydration of OH ? [2015 RS]
(b) , ,
(a) (b)
OH
CH(CH3)2
(c) , , (c) (d)
CH3 – CO – CH3 32. Among the following sets of reactants which

one produces anisole? [2014]
CH(CH3)2 OH
(a) CH3CHO; RMgX
(d) , , (b) C6H5OH; NaOH ; CH3I
CH3CH(OH)CH3 (c) C6H5OH; neutral FeCl3
28. Which one is the most acidic compound ? (d) C6H5–CH3; CH3COCl; AlCl3
[2017] 33. Which of the following will not be soluble in
sodium hydrogen carbonate? [2014]
OH OH
(a) 2, 4, 6-trinitrophenol
(b) Benzoic acid
(a) (b)
(c) o-Nitrophenol
(d) Benzenesulphonic acid
NO2
34. Phenol is distilled with Zn dust followed by
Friedel Crafts alkylation with propyl chloride in
OH OH
the presence of AlCl3 to give a compound (B).
O2N NO2 (B) is oxidised in the presence of air to form the
(c) (d) compound (C). The structural formula of (C) is
[NEET Kar. 2013]
NO2 CH3
COOH COOH
29. Which of the following reagents would OH
distinguish cis-cyclopentane-1,2-diol from the (a) (b)
trans-isomer? [2016]
H3 C (a) Benzaldehyde
C O O H (b) Salicylaldehyde
H 3C (c) Salicylic acid
(c) (d) Benzoic acid
40. The correct order of acidic strength for following
compounds will be [2001]
CH3 OH OH OH
H3C C O O H
(d) OH
CH3 NO2
35. Which one of the following compounds has the I II III
most acidic nature? [2010] (a) III > I > II (b) I > III > II
(c) II > III > I (d) I > II > III
CH2OH OH 41. The ionization constant of phenol is higher than
(a) (b)
that of ethanol because : [2000]
(a) Phenoxide ion is bulkier than ethoxide
OH (b) Phenoxide ion is stronger base than
(c)
ethoxide
OH (c) Phenoxide ion is stabilized through
delocalization
CH (d) Phenoxide ion is less stable than ethoxide
(d) 42. Consider the following phenols :
36. Among the following four compounds [2010] OH OH OH OH
(i) phenol (ii) methylphenol
(iii) meta-nitrophenol (iv) para-nitrophenol
the acidity order is : NO2
(a) ii > i > iii > iv (b) iv > iii > i > ii CH3 NO2
(c) iii > iv > i > ii (d) i > iv > iii > ii I II III IV
37. Consider the following reaction: [2009] The decreasing order of acidity of the above
Zn dust CH Cl phenols is [1999]
Phenol ¾¾¾¾
® X ¾¾¾¾¾¾¾
3 ®Y
Anhydrous AlCl3
(a) III > IV > II > I (b) II > I > IV > III
Alkaline KMnO
¾¾¾¾¾¾¾ 4®Z
(c) I > IV > II > III (d) III > IV > I > II
The product Z is:
43. 1-Phenylethanol can be prepared by the reaction
(a) benzaldehyde (b) benzoic acid
of benzaldehyde with [1997]
(c) benzene (d) toluene
38. Which one of the following compounds is most (a) Ethyl iodide and magnesium
acidic? [2005] (b) Methyl iodide and magnesium
OH (c) Methyl bromide and aluminium bromide
(a) Cl–CH2–CH2–OH (b) (d) Methyl bromide
44. Correct increasing order of acidity is as follows:
OH OH [1994]
(c) (d) (a) H2O, C2H2, H2CO3, Phenol
NO2 CH3 (b) C2H2, H2O, H2CO3, Phenol
39. When phenol is treated with CHCl3 and NaOH, (c) Phenol, C2H2, H2CO3, H2O
the product formed is [2002] (d) C2H2, H2O, Phenol, H2CO3
EBD_8336
260 CHEMISTRY
45. Increasing order of acid strength among OH

p-methoxyphenol, p-methylphenol and
p-nitrophenol is [1993]
(d) + CH3I
(a) p-Nitrophenol, p-Methoxyphenol,
p-Methylphenol
(b) p-Methylphenol, p-Methoxyphenol, 50. The major products C and D formed in the
p-Nitrophenol following reaction respectively are
(c) p-Nitrophenol, p-Methylphenol, [NEET Odisha 2019]
p-Methoxyphenol.
excess HI
(d) p-Methoxyphenol, p-Methylphenol, H3C – CH2 – CH2 – O – C(CH3)3 ¾¾¾¾
D
® C+ D
p-Nitrophenol (a) H3C – CH2 – CH2 – OH and HO – C(CH3)3
46. When phenol is treated with excess bromine (b) H3C – CH2 – CH2 – I and I – C(CH3)3
water. It gives [1992] (c) H3C – CH2 – CH2 – OH and I – C(CH3)3
(a) m-Bromophenol
(d) H3C – CH2 – CH2 – I and HO – C(CH3)3
(b) o-and p-Bromophenols
51. The compound that is most difficult to protonate
(c) 2,4-Dibromophenol
(d) 2,4, 6-Tribromophenol. is : [2019]
47. Which one of the following compounds will be O
(a) H H
most readily attacked by an electrophile ? [1989]
(a) Chlorobenzene (b) Benzene O
(b) H3C H
(c) Phenol (d) Toluene
48. When phenol is heated with CHCl3 and aqueous O
KOH then salicyladehyde is produced. This (c) H3C CH3
reaction is known as [1988, 89]
O
(a) Rosenmund’s reaction (d) Ph H
(b) Reimer-Tiemann reaction
52. The heating of phenyl-methyl ethers with HI
(c) Friedel-Crafts reaction produces [2017]
(d) Sommelet reaction (a) Iodobenzene (b) Phenol
(c) Benzene (d) Ethyl chlorides
Topic 3: Preparation and Properties
53. Identify A and predict the type of reaction
of Ethers
OCH3 [2017]
49. Anisole on cleavage with HI gives [2020]
NaNH
I ¾¾®
2
A
Br
(a) OCH3
+ CH3OH
NH2
OH (a) and elimination addition
reaction
(b) + C2H5I OCH3
I Br
(b) and cine substitution reaction
(c) + C2H5OH OCH3
(c) and cine substitution reaction
OCH3 (c) CH3 - CH- CH2 - O - CH3

|
CH3
(d) and substitution reaction (d) CH3 – CH2 – CH2 – CH2 – O – CH3
NH2 58. In the reaction: [2007]
54. The reaction CH3
|
NaOH – Me Heated
O Na Me–1
+
OH ¾¾® ¾® O CH3 - CH - CH 2 - O - CH 2 - CH3 + HI ¾ ¾ ¾ ¾®
Which of the following compounds will be
Can be classified as :- [2016] formed?
(a) Williamson ether synthesis reaction (a) CH3 - CH - CH3 + CH3CH 2 OH
(b) Alcohol formation reaction |
CH3
(c) Dehydration reaction (b) CH3 - CH - CH 2 OH + CH 3CH 3
(d) Williamson alcohol synthesis reaction |
55. The reaction CH3
CH3 CH3 CH3
|
CH3–C–ONa + CH3CH2Cl–—®CH3–C–O–CH2–CH3 (c) CH3 - CH - CH 2 OH + CH3 - CH 2 - I
–NaCl
CH3 CH3 CH3
is called : [2015] |
(d) CH3 - CH - CH 2 - I + CH3CH 2OH
(a) Williamson continuous etherification process
59. The major organic product in the reaction,
(b) Etard reaction
CH3 — O — CH(CH3)2 + HI ® Product is
(c) Gatterman - Koch reaction [2006]
(d) Williamson Synthesis (a) ICH2OCH(CH3)2
56. Identify Z in the sequence of reactions: (b) CH 3 O C(CH 3 ) 2
[2014] |
HBr/ H 2 O 2 C 2 H 5 ONa
I
CH 3 CH 2 CH=CH 2 ¾ ¾ ¾ ¾ ¾
® Y ¾¾ ¾ ¾® Z (c) CH3I + (CH3)2CHOH
(a) CH3—(CH2)3 —O—CH2CH3 (d) CH3OH + (CH3)2CHI
(b) (CH3)2 CH2—O—CH2CH3 60. Ethanol and dimethyl ether form a pair of
(c) CH3(CH2)4—O—CH3 functional isomers. The boiling point of ethanol
is higher than that of dimethyl ether, due to the
(d) CH3CH2—CH(CH3)—O—CH2CH3 presence of [1993]
57. Among the following ethers, which one will (a) H-bonding in ethanol
produce methyl alcohol on treatment with hot (b) H-bonding in dimethyl ether
concentrated HI? [NEET 2013] (c) CH3 group in ethanol
(a) CH3 - CH 2 - CH - O - CH 3 (d) CH3 group in dimethyl ether
|
CH 3 61. Which one is formed when sodium phenoxide is
heated with ethyl iodide ? [1988]
CH3 (a) Phenetole
(b) CH3 - C - O - CH3 (b) Ethyl phenyl alcohol
(c) Phenol
CH3
(d) None of these
EBD_8336
262 CHEMISTRY
ANSW E R K E Y
1 (d ) 8 (c) 15 (c) 22 (c) 2 9 (a) 3 6 (b ) 43 (b ) 50 (b ) 57 (b )
2 (c) 9 (c) 16 (d ) 23 (a) 3 0 (d ) 3 7 (b ) 44 (d ) 51 (d ) 58 (c)
3 (b ) 10 (c) 17 (b ) 24 (b ) 3 1 (b ) 3 8 (c) 45 (d ) 52 (b ) 59 (c)
4 (a) 11 (c) 18 (a) 25 (c) 3 2 (b ) 3 9 (b ) 46 (d ) 53 (d ) 60 (a)
5 (c) 12 (c) 19 (d ) 26 (d ) 3 3 (c) 4 0 (a) 47 (c) 54 (a) 61 (a)
6 (d ) 13 (d ) 20 (b ) 27 (c) 3 4 (c) 4 1 (c) 48 (b ) 55 (d )
7 (b ) 14 (c) 21 (d ) 28 (c) 3 5 (b ) 4 2 (a) 49 (d ) 56 (a)
Hints & Solutions

OH O Å
| P R — O— ZnCl2 ® R Å + [HOZnCl2 ]d
-
Cu |
1. (d) R — CH — R ¾¾¾ ® R — C —R
300°C
(Secondary (Ketone) H
Alcohol)
(I)
Na – Carbocation is formed as intermediate in the
2. (c) C2H5OH ¾¾® C2H5O Na+
(A) (B) SN mechanism which these reaction undergoes.
1
(III) Tertiary carbocation easily formed due to
PCl5 the stability.
OH
C2H5Cl |
(C) CH3 — C — CH3 ¾¾
®
– SN2 |
C2H5O Na+ + C2H5Cl ¾¾® C2H5OC2H5
CH3
(B) (C)
Å
So, the correct option is (c) CH3 — C — CH 3 + H 2 O
3. (b) Four primary alcohols of C 5H11 OH are |
possible. These are: CH3
(i) CH 3CH 2 CH 2 CH 2 CH 2 OH (IV) In the presence of ZnCl2, 2° carbocation is
(ii) CH3CH 2—CH—CH2OH formed from (CH3 ) 2 — C— OH
|
H
CH3 Å
(iii) CH3—CH—CH 2CH2OH i.e., CH3 — C H— CH3
CH3 ZnCl2 is a lewis acid and interact with alcohol.

In the absence of ZnCl2 formation of primary
CH3 carbocation is difficult.
(iv) CH3—C—CH2OH 5. (c) Compound containing CH3 CH(OH) or
CH3CO–group give positive iodoform test.
CH3 OH
4. (a) |
CH3 CH— CH 2 CH 2 CH 2 CH 3
Å
CH 3 — CH 2OH + ZnCl 2 ® R — O— ZnCl 2 OH
| |
H CH3 — CH — CH CH 2CH 3 ,
(R = CH3 — CH 2 —) (I) |
CH3
OH 11. (c) CH 3OH does not have -CH(OH )CH 3

|
CH3 — CH — CH 2 — CH — CH 3 , group hence it will not form yellow precipitate
| with an alkaline solution of iodine (haloform
CH3
OH CH3 reaction).
| | 12. (c) Primary alcohol on oxidation give aldehyde
CH3 — CH — C — CH 3
| which on further oxidation give carboxylic acid
CH3 whereas secondary alcohols give ketone.
KCN 3 ® H O+
6. (d) CH3 - Br ¾¾¾® CH3 - CN ¾¾¾¾ CH 3CH 2 CH 2 OH ¾¾®
¾
[O]
(A)
n - propyl alcohal
LiAlH
4 ® CH - CH - OH
CH3 - COOH ¾¾¾¾ 3 2 [O]
CH 3 CH 2 CHO ¾¾®
¾ CH 3 CH 2 COOH
(B) (C)
Ethyl alcohol H3C [O] H 3C
7. (b) Glycerol when treated with excess HI CH – OH ¾® C=O
isopropyl alcohal Ketone
produces 2–iodopropane
CH 2 OH CH 2 I CH 2 13. (d) C 2 H 5 OH + 4 I 2 + 6 NaOH ¾
¾®
-I CHI 3 ¯+ HCOONa + 5NaI + 5H 2 O
CHOH + 3HI ¾ ¾
® CHI ¾ ¾2¾
® CH Iodoform
CH 2 OH CH 2 I CH 2 I 14. (c)
B H
CH3 CH3 CH3 CH3– CH=CH2 ¾¾2 ¾6 ® CH3–CH2–CH2–OH
| | | NaOH / H 2O 2 Propanol
+HI –I +HI
¾¾¾
® CHI ¾¾¾
2 ® CH ¾¾¾
® CHI 15. (c) We know that
| || |
CH2 I CH2 CH2 H2C – CH2 + RMgX ¾® CH2 – CH2
\ Correct choice : (b) O OMgX R
8. (c)
HO CH2– CH2
CH3 CH2 OH ¾¾¾
3 PBr
® CH3CH2 Br ¾¾¾¾® CH2 = CH 2
alc.KOH ¾¾®
–Mg(OH)X
OH R
¬¾¾
H 2SO 4
16. (d) Due to –I-effect of the three C–Cl-bonding
HO
HO between Cl and C-atom of the OH group, CCl3
CH3 CH 2 OH ¬¾¾
22 ¾ CH – CH – HSO
3 2 4
heat
CH (OH)2 is most stable.
9. (c) 1, 2 – Diols, when treated with an aqueous
solution of periodic acid give aldehyde or 17. (b) Secondary alcohols on oxidation give
ketones ketones.
CH2OH HIO4 R R
| ¾¾® CH2O +CH2O [O]
CH2OH CHOH ¾¾® C=O
R R
A 1° alcohol on reaction with periodic acid gives Isopropyl Ketone
CH 2O. Since in glycol, both the OH groups are alcohol
primary hence, 2 molecules of CH 2O is formed as
product.
Primary alcohols form aldehydes.
10. (c) Ethylene oxide when treated with Grignard
Reagent gives primary alcohol.
18. (a) 1° Alcohols on catalytic dehydrogenation
CH 2 CH 2 – OMgX
give aldehydes.
| O + R–MgX ¾® | + H 2O
CH 2 CH 2 – R Cu
RCH2OH ¾¾® RCHO + H2
300°C
X 1° alcohol Aldehyde
¾® R – CH2– CH –2 OH + Mg
OH
EBD_8336
264 CHEMISTRY
19. (d) Water gas is mixed with half of its volume of –

hydrogen.The mixture is compressed to 25. (c) CHCl3 + NaOH ¾® CCl3 + H2O
¾®
approximately 200 – 300 atmospheres. It is then – Cl (a-elimination)
passed over a catalyst (ZnO + Cr 2O3) at 300°C. : CCl2 dichlorocarbene
Methyl alcohol vapours are formed which are (electrophile)
condensed 26. (d) Haloform reaction is shown by compound
ZnO+ Cr O having
CO + 2H 2 ¾¾¾¾¾®
2 3 CH3OH
300°C
Compressed gas Methyl alcohol CH3 – C – or CH 3 – CH –
20. (b) Since 2-methylpropan-2-ol generates 3° || | Group
carbocation, therefore, it reacts fastest with HBr. O OH
NaOI
¾¾¾¾®
Greater the stability of the intermediate CH – CH3 or
carbocation, more reactive is the alcohol. | NaOH + I 2
OH
– +
21. (d) The rates of reaction of different alcohols C – ONa + CHI3
with lucas reagent follows the order. || Yellow
3° alcohol > 2° alcohol > 1° alcohol O ppt.
Since carbocations are formed as 27. (c) Mechanism :
intermediate, more stable the carbocation, higher AlCl
CH 3 – CH 2 – CH 2 – Cl ¾¾¾®
3
will be the reactivity of the parent compound + –
(alcohol). 2-Methylpropan-2-ol generates a 3º CH3 – CH 2 – CH 2 + AlCl4
carbocation, so it will react fastest; other three 1° Carbocation
generates either 1º or 2º carbocations.
CH3 – CH – CH 3
CH3 CH3 CH3 + –
| + | - | ESR H
H Å Br ¬¾¾¾ C 3 – CH – CH3
CH3 - C - OH ¾¾¾ ® CH3 - C ¾¾¾® CH3 - C - Br shift
| | | 2° Carbocation
CH3 CH3 CH3 (P)
2-Methylpropan-2-ol CH3
22. (c) KMnO4 (alkaline) and OsO4 / CH2Cl2 are CH3 – CH – CH3 CH3–C– O– O–H
used for hydroxylation of double bond while O3
O +
/Zn is used for ozonolysis. Therefore, the right ¾¾®
D
2 H3O
option is (c), i.e., D
BH3 in THF Cumene Cumene
3CH 3CH = CH 2 ¾¾¾¾¾¾ ® (CH 3CH 2CH 2 )3 B (P) hydroperoxide
3H2O2
¾¾¾¾® 3CH 3CH 2CH 2OH + H3BO3 OH
NaOH O
1-propanol
23. (a) Lucas reagent is conc. HCl + anhyd. ZnCl2. + CH3 – C– CH3
CH3 Phenol Acetone

CH3 (Q) (R)
–
CH H3C–C– O–O–H
CH3 28. (c) Electron withdrawing – NO2 group has very
O
strong –I and –R effects so, compound 3 will be
24. (b) ¾¾
2¾
® most acidic.
Cumene OH CH3
Cumene
hydroperoxide 29. (a) +O C ¾¾®
–H2O
OH CH3
OH O cis-cyclopenta-1, acetone
|| 2-diol
H+ O CH3
¾¾¾
® + H3C CH3 C
H2 O
O CH3
cyclic ketal
Trans isomer can not react with acetone to form

34. (c)
cyclic ketal. OH
d-
AlCl3
30. (d) CHCl3 + NaOH ƒ : CCl3 + H 2 O Zn
D CH 3CH 2CH 2Cl
d- d-
: CCl3 ¾¾
® : CCl2 + Cl CH3
O
–
O
– C O O H CH3 CH CH3
Cl CH3
Cl C O2
– Cl + H O ¾
+ :C ¾® 2 –
¾®
Cl – OH
– –
O O
C=O – CCl2 35. (b) Phenol is most acidic because its conjugate
OH
H
¾ ¾®
H
base is stabilised due to resonance, while the
– 2HCl
rest three compounds are alcohols, hence, their
Therefore, functional group – CHO is introduced. corrosponding conjugate bases do not exhibit
resonance.
31. (b)
OH OH
36. (b) >

OH Å
+H ¾® O—H
Å NO2
H NO2
¯
H—CH2 (iv) (iii)
H CH3 (– I and – M effects, (only – I effect)
Å
(d) both increase acidity)
¾¾® H H
) ¾ OH OH
(a ¾(c)
¾
¾
®
® > > CH3
(i) (ii)
(+ I effect of CH3 group decreases
acidity)
The intermediate is a 3° carbocation, which is \ Correct choice : (b)
very stable. Hence, rearrangement will not take
place and product mentioned in option (b) will OH
not form.
32. (b) Phenols react with alkyl halides in alkaline Zn CH Cl
medium to form ethers. Therefore, 37. (b) ¾® ¾ ¾3 ®
anhy
AlCl3
OH OCH3 Phenol X
(i) NaOH CH3 COOH

¾¾¾®
(ii) CH3I
alc.
33. (c) o-nitrophenol will not be soluble in NaHCO3. ¾¾®
KMnO 4
Due to intramolecular hydrogen bonding,
hydrogen on OH is strongly bound. So, it cannot Y Z
be have as an acid and can not react with sodium
bicarbonate.
EBD_8336
266 CHEMISTRY
38. (c) Phenols are more acidic than alcohols as Dry ether
43. (b) CH 3 I + Mg ¾ CH 3 MgI
they are resonance stabilised whereas alcohols ¾ ¾ ¾ ®
are not. C6H5

Further –NO2 is an electron withdrawing group CH3MgI + C O ¾®
which increases acidic character and facilitates H
release of proton, whereas –CH3 is an electron C6H5
donating group which decrea ses acidic CH O MgI
character, thus removal of H+ becomes difficult. CH3
OH OH C6H5
H O
CHO CHOH ¬¾¾
2 ¾
CHCl CH3 - Mg ( OH ) I
39. (b) ¾¾®
3
(1-Phenyl ethanol)
NaOH
(Riemer Tiemann reaction) Salicylaldehyde 44. (d) Such questions can be solved by considering
the relative basic character of their conjugated bases
which for H2O, C2H2, H2CO3 and C6H5OH are
If CCI4 is used in place of CHCl3, then the -
product is salicylic acid.

-
OH, HC º C : , HCO 3 , C 6 H 5 O - -
More the possibility for the dispersal of the

40. (a) Electron releasing group (–CH3)decreases negative charge, weaker will be the base. Thus
acidity while electron withdrawing group the relative basic character of the four bases is
(–NO2)increases acidity. HCO 3 < C 6 H 5 O < OH < HC º C
- - - -
41. (c) The acidic nature of phenol is due to the Equivalent Non-equivalent Oxygen can accommodate
formation of stable phenoxide ion in solution resonating structures (–) charge easily
C 6 H5 O
C6 H 5OH + H 2 O -
+ H 3O +
Due to resonance
Phenoxide ion Thus, the acidic character of the four
The phenoxide ion is stable due to resonance. corresponding acids wil be
–
O O O HC º CH < H 2O < C6 H5OH < H 2CO3
•• 45. (d) Electron-donating groups (– OCH3, – CH3
etc.) tend to decrease and electron withdrawing
•• groups (–NO2) tend to increase the acidic
character of phenols. Since –OCH3 is a more
powerful electron-donating group than –CH3
OH O– O group, therefore, p-methylphenol is slightly
d
–
d
–
more acidic than p-methoxyphenol while
••
p-nitrophenol is the strongest acid. Thus,
op t i o n ( d) , i . e . p - m e t h ox yp h en ol ,
d
–
p-methylphenol, p-nitrophenol is correct.

The negative charge is delocalized in the 46. (d) Wit h Br 2 wa ter, phen ol gi ves 2, 4,
benzene ring which is a stabilizing factor in the 6- tribromophenol.
phenoxide ion and increase acidity of phenol, OH
wheras no resonance is possible in alkoxide ions
(RO–) derived from alcohol. The negative charge + 3Br2 (excess)
is localized on oxygen atom. Thus, alcohols are
less acidic. OH
42. (a) Electron withdrawing group (–NO 2 ) Br Br
H2O
increases the acidity while electron releasing ¾® + 3HBr
group (–CH3, –H) decreases acidity. Also effect
will be more if functional group is present at para Br
position than ortho and meta position. 2, 4, 6 Tribromophenol
O – CH3 OH
When phenol is treated Br2/CS2 monobromination
takes place.
HI
47. (c) Due to strong electron-donating effect of the ¾® + CH3I
OH group, the electron density in phenol is much
higher than that in toluene, benzene and 53. (d)
chlorobenzene and hence phenol is readily
OC3H OC3H OC3H
attacked by the electrophile.
OH OH H
NH
CHCl2 ¾®
2
¾®
48. (b) Br Br
+ CHCl ¾® 3 Benzyne
OH OH OC3H
CH(OH)2 CHO
2KOH N2H
¾¾® ¾¾®
–H O
OC3H a (Less stable)
2
Reimer-Tiemann reaction. NH OC3H

¾®
2 OC3H
49. (d)
b
H + N2H
¾¾®
OCH3 HO – CH3 NH2 NH2
(More stable)
+d –d
I
+ H H–I
¾¾® ¾¾®
SN 2 More stable as –ve charge is close to electron
withdrawing group.
OH Also, incoming nucleophile gets attached on
same 'C' on which 'Br' (Leaving group) was
+ CH3I present.
\ not a cine substitution reaction.
HI 54. (a) This is an example of Williamson ether
50. (b) H3C – CH2 – CH2 – O – C(CH3)3 ¾¾
D
® synthesis reaction in which sodium alkoxide
reacts with alkyl halide and gives ether.
55. (d) Williamson synthesis is one of the best
methods for the preparation of symmetrical and
unsymmetrical ethers. In this method, an alkyl
halide is allowed to react with sodium alkoxide.
56. (a)
:
:O–H
HBr/H O
51. (d) In lone pair of e–s present on CH3 CH2 CH ¾¾¾¾®
CH2 (Peroxide
2 2
effect)
oxygen atom is involved in delocalisation. CH3 CH2 CH2 CH2

Therefore, it is most difficult to protonate the (Y)
¾¾®
phenol amongst the given compounds, due to Br

C2H5Na
less availability of e–s.
CH3 (CH2)3 O CH2 CH3
52. (b) When Ar – O – R ethers are reacted with HI,
(Z)
they are cleaved at weaker O – R bond to give
phenol and alkyl iodide.
EBD_8336
268 CHEMISTRY
57. (b) The reaction will proceed via SN1 mechanism

D
because alkyl group attached is 3°. CH3 - CH - CH2 - O - CH2 - CH3 + HI ¾¾
®
|
CH3 CH3 CH3
| | H
HI
CH3 - C- O - CH3 ¾® CH3 - C- O ® CH3OH
| Sn1 | + CH3 CH3
CH3 CH3 |
CH3 - CH - CH 2 OH + CH3CH 2 I
CH3 CH3
|+ – | 59. (c) In case of unsymmetrical ethers, the site of
I
+ CH3 - C ¾® CH3 - C- I cleavage depends on the nature of alkyl group
| |
CH3 CH3 e.g.,
(Highly stable) 373K
CH3O - CH(CH 3 )2 + HI ¾¾¾® CH 3I + (CH 3 )2 CHOH
Methyl Isopropyl
When tertiary alkyl group is attached then it forms iodide alcohol
alkyl iodide because of the stability of tertiary The alkyl halide is always formed from the
carbocation. smaller alkyl group.
58. (c) In the cleavage of mixed ethers with two 60. (a) Due to H-bonding, the boiling point of
different alkyl groups, the alcohol and alkyl ethanol is much higher than that of the isomeric
iodide that form depend on the nature of alkyl diethyl ether.
group. When primary or secondary alkyl groups D
61. (a) C 6 H 5 ONa + C 2 H 5 I ¾¾® C6 H 5OC 2 H 5
are present, it is the lower alkyl group that forms
Phenetole
alkyl iodide therefore
+ NaI
Aldehydes, Ketones, and Carboxylic acids 269
26 Aldehydes, Ketones,
and Carboxylic Acids
2020 2019 2018 2017 2016

Methods of preparation of
1 D
preparation of benzaldehyde
reaction with
1 A
Grignard reagent
cross aldol /aldol
1 A 1 D
condensation
Properties of carbonyl conversion(semicar
compounds bazone/aldol 1 D
condensation)
keto enol
1 A
tautomerism
reaction with amine 1 E
Preparation and reaction with
1 A
properties of ammonia
carboxylic acids physical properties 1 A
Topic 1: Methods of Preparation of

CCl2 Cl
Carbonyl Compounds
1. Identify compound X in the following sequence (c) (d)

of reactions [2020]
CHO
2. Reaction by which Benzaldehyde cannot be
prepared : [NEET 2013]
Cl /hv H O
¾¾®
2
X ¾¾®
2
COCI
373K
(a) + H2 in presence of Pd - BaSO4
CH2Cl CHCl2
(b) + CO + HCl in presence of
(a) (b)
anhydrous AlCl3
EBD_8336
270 CHEMISTRY
COOH (a) oxidation of primary alcohols
(c) + Zn/Hg and conc. HCl (b) hydrolysis of esters
(c) oxidation of tertiary alcohols
CH3 (d) reaction of acid halides with alcohols
(d) + CrO2Cl 2 in CS2 followed by 9. Pinacolone is [1994]
(a) 2, 3-Dimethyl-2, 3-butanediol
H3O+
(b) 3, 3-Dimethyl-2-butanone
3. Consider the following reaction :
(c) 1-Phenyl-2-Propanone
COCl
H (d) 1,1-Diphenyl-2-ethandiol.
¾¾¾®
2
'A'
Pd-BaSO4
Topic 2: Properties of Carbonyl Compounds
The product ‘A’ is : [2012 M]
10. Reaction between acetone and methyl-
(a) C6H5CHO (b) C6H5OH
magnesium chloride followed by hydrolysis will
(c) C6H5COCH3 (d) C6H5Cl give : [2020]
4. Which of the following reactions will not result (a) Sec. butyl alcohol (b) Tert. butyl alcohol
in the formation of carbon-carbon bonds?
(c) Isobutyl alcohol (d) Isopropyl alcohol
(a) Reimer-Tiemann reaction [2010]
11. Reaction between benzaldehyde and
(b) Cannizaro reaction
acetophenone in presence of dilute NaOH is
(c) Wurtz reaction known as [2020]
(d) Friedel-Crafts acylation (a) Cannizzaro's reaction
5. Which one of the following can be oxidised to
(b) Cross Cannizzaro's reaction
the corresponding carbonyl compound? [2004]
(c) Cross Aldol condensation
(a) 2-hydroxypropane
(d) Aldol condensation
(b) Ortho-nitrophenol
(c) Phenol 12. Consider the reactions :- [2017]
(d) 2-methyl-2 hydroxypropane +
[Ag(NH3)2]
Cu
6. In the following reaction, product 'P' is [2002] X ¾¾®573K
A ¾¾¾¾®
–
Silver mirror
(C2H6O) OH D observed
H
R - C - Cl ¾¾¾
2® P –
OH D
|| Pd - BaSO 4 ¾¾¾¾¾¾¾®
O Y
O
(a) RCH2OH (b) RCOOH NH2 – NH – C – NH2
Z
(c) RCHO (d) RCH3
7. The catalyst used in Rosenmund's reduction is Identify A, X, Y and Z
[2000] (a) A-Methoxymethane, X-Ethanol,
(a) HgSO4 (b) Pd/BaSO4 Y-Ethanoic acid, Z-Semicarbazide.
(c) anhydrous AlCl3 (d) anhydrous ZnCl2 (b) A - Ethanal, X-Ethanol, Y - But - 2-enal,
8. Ketones Z-Semicarbazone
(c) A-Ethanol, X-Acetaldehyde, Y - Butanone,
[ R — C — R1 , where R = R1 = alkyl groups]
|| Z-Hydrazone
O (d) A-Methoxymethane, X-Ethanoic acid,
can be obtained in one step by [1998] Y-Acetate ion, Z-hydrazine.
13. Of the following, which is the product formed when 16. An organic compound 'X' having molecular
cyclohexanone undergoes aldol condensation formula C5H10O yields phenyl hydrazone and
followed by heating ? [2017] gives negative response to the Iodoform test
and Tollen's test. It produces n-pentane on
(a) reduction. 'X' could be :- [2015]
(a) 2-pentanone (b) 3-pentanone
(c) n-amyl alcohol (d) pentanal
O
17. Treatment of cyclopentanone =O with
(b)
methyl lithium gives which of the following
species? [2015]
OH (a) Cyclopentanonyl cation
(b) Cyclopentanonyl radical
(c) (c) Cyclopentanonyl biradical
(d) Cyclopentanonyl anion
OH OH 18. The enolic form of ethyl acetoacetate as below
has: [2015]
OH H H2
H3C C O H3C C O
(d) C C C C
OH OC2H5 O OC2H5
OH (a) 16 sigma bonds and 1 pi - bond
14. The correct statement regarding a carbonyl (b) 9 sigma bonds and 2 pi - bonds
compoun d with a hydrogen atom on its (c) 9 sigma bonds and 1 pi - bond
alphacarbon, is : [2016] (d) 18 sigma bonds and 2 pi - bonds
(a) a carbonyl compound with a hydrogen atom 19. Reaction of a carbonyl compound with one of
on its alpha-carbon never equilibrates with the following reagents involves nucleophilic
its corresponding enol. addition followed by elimination of water. The
(b) a carbonyl compound with a hydrgen atom reagent is : [2015 RS]
on its alpha-carbon rapidly equilibrates (a) a Grignard reagent
with its corresponding enol and this (b) hydrazine in presence of feebly acidic solution
process is known as aldehyde-ketone (c) hydrocyanic acid
equilibration. (d) sodium hydrogen sulphite
(c) a carbonyl compound with a hydrogen atom 20. Which one is most reactive towards Nucleophilic
on its alpha-carbon rapidly equilibrates addition reaction? [2014]
with its corresponding enol and this
process is known as carbonylation. CHO COCH3
(a) (b)
(d) a carbonyl compound with a hydrogen atom
on its alpha-carbon rapidly equilibrates with its
corresponding enol and this process is known CHO CHO
as keto-enol tautomerism.
15. The product formed by the reaction of an (c) (d)
aldehyde with a primary amine is [2016]
(a) Schiff base (b) Ketone NO2
CH3
(c) Carboxylic acid (d) Aromatic acid
EBD_8336
272 CHEMISTRY
21. The order of stability of the following tautomeric OH
compounds is : [NEET 2013] (c) (CH3)2C
OH O OC2H5
| || OC2H5
CH 2 = C - CH 2 - C - CH 3 (d) (CH3)2C
I OC2H5
O O 24. CH 3 CHO and C 6 H5 CH 2 CHO can be
|| ||
distinguished chemically by : [2012]
CH3 - C- CH 2 - C- CH 3
(a) Benedict test (b) Iodoform test
II
(c) Tollen’s reagent test (d) Fehling solution test
OH O 25. Consider the reaction :
| ||
CH 3 - C = CH - C - CH 3
RCHO + NH2NH2 ® RCH = N – NH2
III What sort of reaction is it ? [2012 M]
(a) III > II > I (b) II > I > III (a) Electrophilic addition – elimination reaction
(c) II > III > I (d) I > II > III (b) Free radical addition – elimination reaction
22. Predict the product in the given reaction. [2012] (c) Electrophilic substitution – elimination
CHO reaction
(d) Nucleophilic addition – elimination reaction
50 % KOH
¾¾¾® 26. Which of the following compounds will give a
yellow precipitate with iodine and alkali?
Cl
[2012 M]
CH2OH CH2COO– (a) Acetophenone (c) Methyl acetate
(a) +
(b) Acetamide (d) 2-Hydroxypropane
Cl Cl 27. Clemmensen reduction of a ketone is carried out in
the presence of which of the following? [2011]
CH2OH OH (a) Glycol with KOH
(b) +
(b) Zn-Hg with HCl
OH (c) Li Al H4
OH
– (d) H2 and Pt as catalyst
CH2OH COO
(c) + 28. The order of reactivity of phenyl magnesium
bromide (PhMgBr) with the following compounds
Cl Cl [2011 M]
CH2OH COO– H3C H3C Ph

(d) + C=O, C=O and C=O
H H3C Ph
OH OH I II III
23. Acetone is treated with excess of ethanol in the (a) III > II > I (b) II > I > III
presence of hydrochloric acid. The product (c) I > III > II (d) I > II > III
obtained is : [2012]
O 29. Following compounds are given:
(1) CH3CH2OH (2) CH3COCH3
(a) CH3CH2CH2 C CH3
O
(3) CH 3 - CHOH (4) CH3OH
(b) CH3CH2CH2 C CH 2CH 2CH 3 CH 3
Which of the above compound(s), on being 33. Reduction of aldehydes and ketones into
warmed with iodine solution and NaOH, will give hydrocarbons using zinc amalgam and conc. HCl
iodoform? [2010] is called [2007]
(a) (1) and (2) (b) (1), (3) and (4) (a) Cope reduction
(c) only (2) (d) (1), (2) and (3) (b) Dow reduction
30. Which one of the following compounds will be (c) Wolff-Kishner reduction
most readily dehydrated? [2010]
(d) Clemmensen reduction.
OH 34. Which one of the following on treatment with
50% aqueous sodium hydroxide yields the
(a)
H3C corresponding alcohol and acid? [2007]
O
O (a) C6H5CHO (b) CH3CH2CH2CHO
O
(b) ||
H3C (c) CH 3 - C - CH 3 (d) C6H5CH2CHO
OH
O 35. The product formed in Aldol condensation is
[2007]
(c) (a) A beta-hydroxy aldehyde or a beta-hydroxy
H3 C
OH ketone
(b) An alpha-hydroxy aldehyde or ketone
O OH
(c) An alpha, beta unsaturated ester
(d) A beta-hydroxy acid
(d)
H3C 36. Consider the following compounds. [2007]
31. Acetophenone when reacted with a base, (i) C6H5COCl
C2H5ONa, yields a stable compound which has
the structure. [2008] (ii) O2N COCl
C = CH – C
(a)
CH3 O (iii) H3C COCl
CH – CH2C
(b)
CH3 O (iv) OHC COCl
CH3CH3
The correct decreasing order of their reactivity
C–C towards hydrolysis is
(c)
(a) (i) > (ii) > (iii) > (iv) (b) (iv) > (ii) > (i) > (iii)
OH OH
(c) (ii) > (iv) > (i) > (iii) (d) (ii) > (iv) > (iii) > (i)
CH – CH 37. A carbonyl compound reacts with hydrogen
(d) cyanide to form cyanohydrin which on
OH OH hydrolysis forms a racemic mixture of a-hydroxy
32. A strong base can abstract an a -hydrogen acid. The carbonyl compound is [2006]
from : [2008] (a) Acetone (b) Diethyl ketone
(a) alkene (b) amine (c) Formaldehyde (d) Acetaldehyde
(c) ketone (d) alkane
EBD_8336
274 CHEMISTRY
38. Nucleophilic addition reaction will be most 41. In the reaction
favoured in [2006] CH 3CHO + HCN ® CH 3CH (OH) CN
(a) (CH3)2C = O H.OH
(b) CH3CH2CHO ¾¾ ¾® CH 3 CH (OH )COOH
(c) CH3CHO an asymmetric centre is generated. The acid
O obtained would be [2003]
||
(d) CH 3 — CH 2 — CH 2C — CH 3 (a) 20 % D + 80 % L-isomer
(b) D-isomer
39. A and B in the following reactions are [2003]
(c) L-isomer
OH (d) 50% D + 50% L-isomer
HCN/ B
R–C–R' ¾¾® A ¾® R– C 42. Which of the following is correct? [2001]
KCN
R' CH2NH2
O (a) Diastase is an enzyme
CN (b) Acetophenone is an ether
(a) A = RR'C , B = LiAlH4 (c) Cycloheptane is an aromatic compound
OH
OH (d) All the above
(b) A = RR'C , B = NH3 43. Which of the following is incorrect? [2001]
COOH (a) NaHSO3 is used in detection of carbonyl
CN compound
(c) A = RR'C , B = H 3O Å (b) FeCl3 is used in detection of phenolic group
OH
(c) Tollens’ reagent is used in detection of
(d) A = RR'CH2CN, B = NaOH
unsaturation
40. When m-chlorobenzaldehyde is treated with 50%
(d) Fehling solution is used in detection of
KOH solution, the product(s) obtained is (are)
glucose
[2003]
44. Polarization of electrons in acrolein may be
OH OH written as: [2000]
δ– δ+
CH CH (a) CH2 =CH — CH= O
(a)
δ+ δ–
(b) CH 2 = CH—CH=O
OH OH
δ+ δ-
COO –
CH2OH (c) CH 2 = CH — CH= O
+ δ- δ+
(d) CH 2 = C H — CH = O
(b)
OH OH 45. During reduction of aldehydes with hydrazine
and potassium hydroxide, the first is the
COO– CH2OH formation of : [2000]
(c) + (a) R — CH == N — NH2
(b) R — C ºº N
Cl Cl (c) R — C — NH 2
||
OH OH O
(d) R — CH == NH
CH CH
(d) 46. Iodoform test is not given by [1999]
(a) 2-Pentanone (b) Ethanol
Cl Cl (c) Ethanal (d) 3-Pentanone
47. Reaction of phenylacetylene with dil. H2SO4 and 55. Which of the following compound will undergo
HgSO4 gives [1999] self aldol condensation in the presence of cold
(a) Acetophenone (b) 2-Phenylethanol dilute alkali ? [1994]
(c) Phenylacetaldehyde (d) Phenylacetic acid (a) CH2 == CH — CHO (b) CH == C — CHO
48. The cyanohydrin of a compound on hydrolysis (c) C6H5CHO (d) CH3CH2CHO.
gives an optically active a-hydroxy acid. The
56. Acetaldehyde reacts with [1991]
compound is [1999]
(a) Diethyl ketone (b) Formaldehyde (a) Electrophiles only
(c) Acetaldehyde (d) Acetone (b) Nucleophiles only
49. Phenylmethyl ketone can be converted into (c) Free radicals only
ethylbezene in one step by which of the (d) Both electrophiles and nucleophiles.
following reagents? [1999]
57. The reagent (s) which can be used to distinguish
(a) LiAlH4 (b) Zn-Hg/HCl
acetophenone from benzophenone is (are)
(c) NaBH4 (d) CH3MgI
50. (CH3 ) 3 C—CHO does not undergo Aldol (a) 2,4- Dinitrophenylhydrazine [1990]
condensation due to [1996] (b) Aqueous solution of NaHSO3
(a) three electron donating methyl groups (c) Benedict reagent
(b) cleavage taking place between —C— CHO (d) I2 and NaOH.
bond
(c) absence of alpha hydrogen atom in the CH 2 O
molecule 58. O CH 2
(d) bulky (CH3)3 C—group CH 2 O
51. Decreasing order of reactivity towards
nucleophilic addition to carbonyl group among The above shown polymer is obtained when a
cyclopentanone, 3-pentanone and n-pentanal is carbonyl compound is allowed to stand. It is a
[1996] white solid. The polymer is [1989]
(a) 3-pentanone, cyclopentanone, n-pentanal (a) Trioxane (b) Formose
(b) n-pentanal, 3-pentanone, cyclopentanone (c) Paraformaldehyde (d) Metaldehyde.
(c) n-pentanal, cyclopentanone, 3-pentanone
59. CH 3
(d) cyclopentanone, 3-pentanone, n-pentanal
52. Acetone reacts with iodine (I2) to form iodoform
in the presence of [1995]
(a) CaCO3 (b) NaOH CH 3
CH 3
(c) KOH (d) MgCO3
53. Benzaldehyde reacts with ethanoic KCN to give The above compound describes a condensation
(a) C6H5CHOHCN [1994] polymer which can be obtained in two ways :
(b) C6H5CHOHCOC6H5 either treating 3 molecules of acetone
(c) C6H5CHOHCOOH (CH3 COCH3) with conc. H2SO4 or passing
(d) C6H5CHOHCHOHC6H5 propyne (CH3 C º CH) through a red hot tube.
54. Aldehydes and ketones will not form crystalline The polymer is [1989]
derivatives with [1994] (a) Phorone
(a) Sodium bisulphite (b) Mesityl oxide
(b) Phenylhydrazine (c) Deacetonyl alcohol
(c) Semicarbazide hydrochloride
(d) Mesitylene.
(d) Dihydrogen sodium phosphate.
EBD_8336
276 CHEMISTRY
HCl O
60. 3CH3COCH3 ¾¾¾¾
®
-3H 2O
(A)
(CH 3 )2 C = CH - CO - CH = C(CH 3 ) 2 (b) NH
(B)
This polymer (B) is obtained when acetone is O
saturated with hydrogen chloride gas, B can be COOH
(a) phorone (b) formose [1989] (c)
(c) diacetone alcohol (d) mesityl oxide. NH2
61. If formaldehyde and KOH are heated, then we NH2
get [1988] (d)
(a) Methane (b) Methyl alcohol NH2
(c) Ethyl formate (d) Acetylene.
65. Carboxylic acids have higher boiling points than
62. Formalin is an aqueous solution of [1988] aldehydes, ketones and even alcohols of
(a) Fluorescein (b) Formic acid comparable molecular mass. It is due to their
(c) Formaldehyde (d) Furfuraldehyde. [2018]
(a) Formation of intramolecular H-bonding
Carboxylic Acids (b) Formation of carboxylate ion
(c) Formation of intermolecular H-bonding
63. The reaction that does not give benzoic acid as (d) More extensive association of carboxylic
the major product is [NEET Odisha 2019] acid via van der Waals force of attraction
CH2OH 66. Which one of the following esters gets
KMnO /H + hydrolysed most easily under alkaline conditions?
(a) ¾¾¾¾¾®
4
[2015 RS]
CH2OH OCOCH3
(a)
(b) K Cr O
¾¾¾¾®
2 2 7
O 2N
OCOCH 3
COCH3
(i) NaOCl
(c) ¾¾¾¾¾
+®
(b)
(ii) H 3 O H 3CO
CH2OH PCC
OCOCH3
¾¾¾¾¾¾®
(d) Pyridinium (c)
chlorochromate
64. The major product of the following reaction is : OCOCH3

COOH (d)
strong heating Cl
+ NH3 ¾¾¾¾¾ ®
67. The correct order of decreasing acid strength of
COOH
trichloroacetic acid (A), trifluoroacetic acid (B),
COOH acetic acid (C) and formic acid (D) is : [2012]
(a) [2019] (a) B > A > D > C (b) B > D > C > A
CONH (c) A > B > C > D (d) A > C > B > D
68. Match the compounds given in List-I with
COOH
List-II and select the suitable option using the
code given below : [2011 M]
List I List-II (c)
OCH2CH3
(A) Benzaldehyde (i) Phenolphthalein
(B) Phthalic anhydride (ii) Benzoin COOC2H5
condensation
(C) Phenyl benzoate (iii) Oil of wintergreen (d)
(D) Methyl salicylate (iv) Fries Br
rearrangement 71. Given are cyclohexanol (I) acetic acid (II),
Code : 2, 4, 6 – trinitrophenol (III) and phenol (IV). In
(A) (B) (C) (D) these, the order of decreasing acidic character
will be : [2010]
(a) (iv) (i) (iii) (ii)
(a) III > II > IV > I (b) II > III > I > IV
(b) (iv) (ii) (iii) (i) (c) II > III > IV > I (d) III > IV > II > I
(c) (ii) (iii) (iv) (i) 72. Among the given compounds, the most
(d) (ii) (i) (iv) (iii) susceptible to nucleophilic attack at the carbonyl
69. An organic compound ‘A’ on treatment with NH3 group is: [2010]
gives ‘B’ which on heating gives ‘C’, ‘C’ when (a) CH3COOCH3 (b) CH3CONH2
treated with Br2 in the presence of KOH produces (b) CH3COOCOCH3 (d) CH3COCl
ethylamine. Compound ‘A’ is: [2011 M] 73. Propionic acid with Br 2|P yields a dibromo
(a) CH3COOH product. Its structure would be: [2009]
(b) CH3 CH2 CH2 COOH Br
|
(c) CH3 – CHCOOH (a) H– C – CH2COOH
|
CH3
Br
(d) CH3CH2COOH (b) CH2Br – CH2 – COBr
70. In a set of reactions, ethylbenzene yielded a
product D. [2010] Br
|
KMnO4 Br2
(c) CH3– C – COOH
CH2CH3 ¾¾¾¾ ® B ¾¾¾® |
KOH FeCl3
Br
(d) CH2 Br – CHBr – COOH
C H OH
2 5 74. The relative reactivities of acyl compounds
C ¾¾¾¾¾
+
®D
H towards nucleophilic substitution are in the order
of : [2008]
CH2 – CH – COOC 2H5
(a) (a) Acyl chloride > Acid anhydride > Ester
Br > Amide
Br (b) Ester > Acyl chloride > Amide
> Acid anhydride
(c) Acid anhydride > Amide > Ester
(b)
> Acyl chloride
Br
(d) Acyl chloride > Ester > Acid anhydride
CH2 COOC2H5
> Amide
EBD_8336
278 CHEMISTRY
75. Which of the following represents the correct 79. The –OH group of an alcohol or the –COOH
order of the acidity in the given compounds? group of a carboxylic acid can be replaced by
[2007] –Cl using [2004]
(a) FCH2COOH > CH3COOH > BrCH2COOH (a) Phosphorus pentachloride
> ClCH2COOH (b) Hypochlorous acid
(b) BrCH2COOH > ClCH2COOH > FCH2COOH (c) Chlorine
(d) Hydrochloric acid
> CH3COOH
80. In a set of the given reactions, acetic acid yielded
(c) FCH2COOH > ClCH2COOH > BrCH2COOH
a product C.
> CH3COOH
C H
(d) CH3 COOH > BrCH2COOH > ClCH2COOH CH3COOH + PCl5 ¾¾
® A ¾¾¾®
6 6 B
Anh.AlCl3
> FCH2COOH
C2H 5MgBr
76. Self condensation of two moles of ethyl acetate ¾¾¾¾¾¾ ®C
Ether
in presence of sodium ethoxide yields [2006] Product C would be - [2003]
(a) acetoacetic ester (b) methyl acetoacetate
(c) ethyl propionate (d) ethyl butyrate C2 H 5
|
77. In a set of reactions propionic acid yielded a (a) CH 3 - C (OH)C 6 H 5
compound D. [2006]
SOCl2 NH3 (b) CH3CH(OH)C2H5
CH3CH2COOH ¾¾¾¾ ® B ¾¾¾ ®C
(c) CH3COC6H5
KOH
¾¾¾® D (d) CH3CH(OH)C6H5
Br2
The structure of D would be 81. MgBr
(a) CH3CH2CONH2 (b) CH3CH2NHCH3
(c) CH3CH2NH2 (d) CH3CH2CH2NH2
( i ) CO
78. In a set of reactions acetic acid yielded a ¾¾¾¾
2®
P
product D. ( ii ) H 3O Å
SOCl Benzene
CH3COOH ¾¾¾¾
2
® A ¾¾¾¾¾® B In the above reaction product 'P' is [2002]
Anhy.AlCl3
HCN H.OH
CHO COOH
¾¾¾® C ¾¾¾® D
The structure of D would be: [2005] (a) (b)
COOH
CH2 – C – CH3 OH
(a) O
OH (c) (d) C 6H 5 – C – C 6H5
CN
82. Benzoic acid may be converted to ethyl benzoate
C – CH3 by reaction with : [2000]
(b)
OH (a) Sodium ethoxide (b) Ethyl chloride
(c) Dry HCl—C2H5OH (d) Ethanol
OH 83. Acetaldehyde reacts with semicarbazide and
CH2 – C – CH3 forms semicarbazone. Its structure is [1999]
(c)
CN (a) CH3CH = NNHCON = CHCH3
(b) CH3CH = NNHCONH2
OH (c) CH 3 CH = N — N — CONH 2
|
C – COOH OH
(d)
CH3 (d) CH3CH = N—CONHNH2
84. Aspirin is an acetylation product of [1998] 91. An ester is boiled with KOH. The product is cooled
(a) o-Hydroxybenzoic acid and acidified with concentrated HCl. A white
(b) o-Dihydroxybenzene crystalline acid separates. The ester is [1994]
(c) m-Hydroxybenzoic acid (a) Methyl acetate (b) Ethyl acetate
(d) p-Dihydroxybenzene (c) Ethyl formate (d) Ethyl benzoate
85. An ester (A) with molecular fomula, C9H10O2 92. Sodium formate on heating yields [1993]
was treated with excess of CH3MgBr and the (a) Oxalic acid and H2
complex so formed was treated with H2SO4 to (b) Sodium oxalate and H2
give an olefin (B). Ozonolysis of (B) gave a ketone (c) CO2 and NaOH
with molecular formula C8H8O which shows +ve (d) Sodium oxalate.
iodoform test. The structure of (A) is [1998] 93. Among acetic acid, phenol and n-hexanol, which
(a) C6H5COOC2H5 of the following compounds will react with
(b) C2H5COOC6H5 NaHCO3 solution to give sodium salt and carbon
(c) H3COCH2COC6H5 dioxide? [1993]
(d) p – H3CO – C6 H 4 – COCH3 (a) Acetic acid
86. Which one of the following esters cannot (b) n-Hexanol
undergo Claisen self-condensation? [1998] (c) acetic acid and phenol
(a) CH 3 - CH 2 - CH 2 - CH 2 - COOC 2 H 5 (d) Phenol.
(b) C6H5COOC2H5 94. (CH3)2 C = CHCOCH3 can be oxidized to
(c) C6H5CH2COOC2H5 (CH3)2C = CHCOOH by [1993]
(d) C6H11CH2COOC2H5 (a) Chromic acid (b) NaOI
87. Consider the following transformations : (c) Cu at 300°C (d) KMnO4.
CaCO 3 heat I 95. In which of the following, the number of carbon
CH3COOH¾¾ ¾ ¾® B ¾¾®
¾® A ¾¾ 2
C atoms does not remain same when carboxylic
NaOH
acid is obtained by oxidation [1992]
The molecular formula of C is [1996]
(a) CH 3COCH 3 (b) CCl 3CH 2CHO
OH
| (c) CH 3CH 2 CH 2OH (d) CH 3CH 2CHO.
(a) CH 3 - C - CH 3 (b) ICH2 — COCH3
| 96. Benzoic acid gives benzene on being heated with
I X and phenol gives benzene on being heated
(c) CHI3 (d) CH3I with Y. Therefore X and Y are respectively [1992]
88. Formic acid is obtained when [1994] (a) Soda-lime and copper
(a) Calcium acetate is heated with conc. H2SO4 (b) Zn dust and NaOH
(b) Calcium formate is heated with calcium acetate (c) Zn dust and soda-lime
(c) Glycerol is heated with oxalic acid at 373 K (d) Soda-lime and zinc dust.
(d) Acetaldehyde is oxidised with K2Cr2O7 and 97. The compound formed when malonic ester is
H2SO4. heated with urea is [1989]
89. The preparation of ethyl acetoacetate involves (a) Cinnamic acid (b) Butyric acid
(a) Wittig reaction [1994] (c) Barbituric acid (d) Crotonic acid.
(b) Cannizzaro’s reaction 98. Which of the following is the correct decreasing
(c) Reformatsky reaction order of acidic strength of [1988]
(d) Claisen condensation. (i) methanoic acid (ii) ethanoic acid
90. Schotten-Baumann reaction is a reaction of (iii) propanoic acid (iv) butanoic acid.
phenols with [1994] (a) (i) > (ii) > (iii) > (iv) (b) (ii) > (iii) > (ii) > (i)
(a) Benzoyl chloride and sodium hydroxide (c) (i) > (iv) > (iii) > (ii) (d) (iv) > (i) > (iii) > (ii)
(b) Acetyl chloride and sodium hydroxide 99. Among the following the strongest acid is [1988]
(c) Salicylic acid and conc. H2SO4 (a) CH3COOH (b) CH2ClCH2COOH
(d) Acetyl chloride and conc H2SO4 (c) CH2ClCOOH (d) CH3CH2COOH
EBD_8336
280 CHEMISTRY
ANSWER KEY
1 (b) 11 (c) 21 (a) 31 (a) 41 (d) 51 (c) 61 (b) 71 (a) 81 (b) 91 (d)
2 (c) 12 (b) 22 (c) 32 (c) 42 (a) 52 (b) 62 (c) 72 (d) 82 (c) 92 (b)
3 (a) 13 (a) 23 (d) 33 (d) 43 (c) 53 (b) 63 (d) 73 (c) 83 (b) 93 (a)
4 (b) 14 (d) 24 (b) 34 (a) 44 (c) 54 (d) 64 (b) 74 (a) 84 (a) 94 (b)
5 (a) 15 (a) 25 (d) 35 (a) 45 (a) 55 (d) 65 (c) 75 (c) 85 (a) 95 (a)
6 (c) 16 (b) 26 (a, d) 36 (c) 46 (d) 56 (b) 66 (a 76 (a) 86 (b) 96 (d)
7 (b) 17 (d) 27 (b) 37 (d) 47 (a) 57 (d) 67 (a) 77 (c) 87 (c) 97 (c)
8 (c) 18 (d) 28 (d) 38 (c) 48 (c) 58 (a) 68 (d) 78 (d) 88 (c) 98 (a)
9 (b) 19 (b) 29 (d) 39 (a) 49 (b) 59 (d) 69 (d) 79 (a) 89 (d) 99 (c)
10 (b) 20 (d) 30 (d) 40 (c) 50 (c) 60 (a) 70 (d) 80 (a) 90 (a)
Hints & Solutions

OH
1. (b) O
||
CH3 CHCl2 CH – OH H C H ¾¾¾¾
NaOH
® CH3OH + HCOONa
(b)
Cannizzaro reaction
Cl 2/hv H2 O
Na
373 K (c) 2CH3Cl ¾¾¾¾® CH3 – CH3
dry ether
(X)
Wurtz reaction
–H 2 O
COCH3
CHO
CH COCl
(d) ¾¾¾¾¾
3 ®
anh.AlCl3
Friedel-Craft acylation
In presence of sunlight chlorination takes place at Note that, no new C–C bond is formed in Cannizzaro
the side chain by free radical mechanism. reaction.
5. (a) Among the given options, only (a) can be
2. (c) Zn/Hg and conc. HCl reduce carboxyl oxidized to ketone.
group to meth ylene group (Clemmensen OH O
reduction). | ||
O O oxidation
H3C – CH – CH3 ¾¾¾¾® H3C – C – CH3
C Cl CH 2-hydroxypropane Acetone
3. (a) H2
¾¾¾®
Pd–BaSO4
Carbonyl compounds (aldehydes and ketones) are
It is Rosenmund reaction. obtained by the oxidation of 1° and 2° alcohols
4. (b) respectively.
OH OH
CHO H
CHCl3 6. (c) R — C — Cl ¾¾®
¾2
R — C — H + HCl
(a) ¾¾¾¾ ® Pd – BaSO4
NaOH O O
Riemer-Tiemann reaction ‘P’
7. (b) Catalyst used in Rosenmund reduction is Pd/ Cu
CH 3 - CH 2 OH ¾¾¾® CH3 - CHO
BaSO4. Rosenmund Reduction is used for 573K
(X) (A)
+
reduction of acid chloride. éë Ag(NH3 )2 ùû OH –
O O ¾¾¾¾¾¾¾® silver mirror observed
D
Pd / BaSO4
R C Cl ¾¾¾ ¾¾® R C H
8. (c) By oxidation of tertiary alcohol with stronger
oxidising agents ketones may be formed along
with carboxylic acid.
4[O]
CH3COCH3+CO2+2H2O
OH
(CH3)3 COH | D
8[O] CH3 - CH - CH 2 - CHO
CH3COOH+2CO2+3H2O 3-Hydroxybutanal
9. (b) Pinacolone is 3,3-dimethyl-2-butanone.
CH3 - CH = CH - CHO
CH3 (Y)
But-2-enal
CH3 – C – C – CH3 O
CH3O CH3 - CH = N - NH - C - NH 2
10. (b) (Z)
d– Semicarbazone
O d– d+ O MgBr 13. (a)
CH3–MgBr O
CH3–C–CH3 ¾¾¾ ¾¾ ® CH3–C–CH3 O
d+ H
Acetone CH3 (i) OH
+H
||
¾®
Hydrolysis (ii) D
OH O
14. (d) Keto-enol tautomerism is possible only in
CH3–C–CH3 those aldehydes and ketones which have at least
one a-hydrogen atom, which can convert the
CH3 ketonic group to the enolic group. e.g.
(tert- Butyl alcohol)
O O
11. (c) || ||
O O CH3 — C — CH2 — C CH3
dil. OH –
C–H+ C – CH3 ¾ ¾¾¾®
Cross Aldol
Ketonic form
reaction OH O
OH H O | ||
CH 3 — C CH — C — CH 3
||
C–C–C enolic form

15. (a) Schiff base is formed when 1° amine reacts
H H O with aldehydes.
–H2O R R
CH = CH – C H+
C = O + R' — NH 2 ¾¾¾ ® C = N – R'
In the presence of dil. NaOH, C6H5CHO and H H
Aldehyde + primary amine Schiff base
C6H5COCH3 will react to undergo cross-aldol
condensation. 16. (b) H3C—CH2— C—CH2—CH3
12. (b) Since 'A' gives positive silver mirror test O
therefore, it must be an aldehyde of does not give iodoform test due to absence of
a-Hydroxyketone. Also, reaction with OH– i.e.,
O
aldol condensation (by assuming alkali to be dilute)
indicates that 'A' is aldehyde as aldol reaction of (CH3—C—) group. It also does not give
ketones is reversible and carried out in special
Tollen’s test.
apparatus. It indicates that 'A' is an aldehyde.
EBD_8336
282 CHEMISTRY
On reduction, it gives n-pentane 21. (a) Enolic form predominates in compounds
reduction containing two carbonyl groups separated by a
H3C—CH2—C—CH2—CH3 ¾¾¾¾ ¾® – CH2 group. This is due to following two factors.
Zn-Hg/HCl
or NH 2-NH 2/OH
– (i) Presence of conjugation which increases
O stability.
CH 3—CH 2—CH2—CH 2—CH 3 (ii) Formation of intramolecular hydrogen
n-pentane
bond between enolic hydroxyl group and
17. (d) – second carbonyl group which leads to
O O
CH3 stablisation of the molecule. Hence, the cor-
–
rect answer is III > II > I.
Å
+ CH3 Li ® 22. (c) Cannizzaro reaction - when an aldehyde
containing no a – H undergo reaction in presence
Cylopentanoyl anion of 50% KOH. It disproportionates to form a molecule
of carboxylic acid and a molecule of alcohol.
Reactions involving methyl lithium require and an O
hydrous condtions, because the compound is highly
CH2–OH
reactive towards water. Methyl lithium is stable CHO C–O
as a solution in ether.
50 % KOH +
18. (d) Enolic form of ethyl acetoacetate has 18 ¾¾¾®
sigma and 2 pi-bonds as shown below: Cl
Cl Cl
H H 23. (d) Anhydrous alcohols add to the carbonyl
s s s group of aldehydes in the presence of anhydrous
s s s
H C C p C s
C p
O hydrogen chloride to form acetals via hemiacetals.
s s H H
s OC2H5
H Os H s s
s
Os C s C H C H OH
s s CH3 C 2 5
CH3 ¾¾¾® CH3 C CH3
H H
O O OH
||
1 HÅ Hemiacetal
19. (b) R — C— R + NH 2 — NH 2 ¾¾¾®
NH2 OC2H5
OH N C H OH
2 5
¾¾¾® CH3 C CH3
1 H2O
R—C—R ¾¾¾¾¾ ® R—C—R¢
Elimination
OC2H5
NH—NH2 Acetal
(Addition) 24. (b) CH 3 CHO gives Iodoform test but
While in all other cases no elimination take place. C6H5CH2CHO does not give Iodoform test due
20. (d) Any substituent in the carbonyl compound to absence of methyl group.
that increases the positive charge on the carbonyl
carbon will increase reactivity towards nucleophilic 25. (d) R – CH = O + H2N – NH2 ®
addition. R – CH = N – NH2
—NO2 shows –M effect hence Such reactions take place in slightly acidic
medium and involve nucleophilic addition of the
CHO ammonia derivative.
26. (a, d) The compounds with CH3 – C – group
is most reactive towards nucleophilic ||
addition reaction. O
or CH3 — CH — group give iodoform test.
NO 2 |
OH
Hence, Acetophenone Thus, two molecules of acetophenone condense
to form a b-hydroxy ketone which gets dehydrated
CH3 C and 2-Hydroxypropane in the presence of acid upon heating to form a,
b-unsaturated compound.
O i.e., option (a) is correct.
CH3 CH CH3 32. (c) A strong base (OH–) abstract an a – H atom
both give a yellow from ketone which is acidic in nature.
OH
The acidity of a-hydrogen atom in ketone is due
precipitate of CHI3 (iodoform) with iodine and
to resonance stabilization of enolate anoin.
alkali.
27. (b) Clemmensen reduction is
Zn-Hg / conc. HCl
Zn–Hg/HCl 33. (d) C = O ¾¾¾¾¾ ¾¾® CH2 + H2O
C = O ¾¾¾¾® CH 2
Clemmensen reduction
28. (d) The reactivity of the carbonyl group
towards the nucleophilic addition reactions e.g.
depend upon the magnitude of the positive CH3 Zn-Hg / CH3
charge on the carbonyl carbon atom (electronic conc. HCl
C = O ¾¾¾ ¾® CH2 + H2O
factor) and also on the crowding around the
CH3 CH3
carboxyl carbon atom in the transition state
(steric factor). Both these factors predict the Clemmensen reduction is complementary to wolf-
following order kishner reduction, which also convert aldehyde and
H3C H3C Ph ketones to hydrocarbons. Clemmensen reduction
C=O> C=O> C=O carried out in strongly acidic conditions and wolf
H H3C Ph kishner reduction carried out in strongly basic
(due to steric crowding). conditions.
29. (d) Among the given compounds only CH3OH 34. (a) Aldehydes containing no a-hydrogen
does not give iodoform reaction. atom on warming with 50% NaOH or KOH
30. (d) The intermediate is carbocation which is undergo disproportionation i.e. self oxidation -
destabilised by C = O group (present on a-
reduction known as Cannizzaro’s reaction.
carbon to the –OH group) in the first three cases.
In (d), a–hydrogen is more acidic which can be 50% NaOH
removed as water. Moreover, the positive charge 2 C6 H5 CHO + NaOH ¾¾¾¾¾®
on the intermediate carbocation is relatively C6 H5COONa + C6 H5CH 2 OH
away from the C = O group.
O O 35. (a) Aldehydes and ketones having at least one
a-hydrogen atom in presence of dilute alkali give
OH -
31. (a) C6H5 – C + H.CH 2– C ¾¾¾® b-hydroxy aldehyde or b-hydroxy ketone.
O
CH3 C6H5 ||
CH 3 - C + HCH 2 CHO
OH O |
+
H
H Heat Acetaldehyde
C6H5 – C – CH 2– C ¾¾¾¾®
H O 2 OH
|
CH3 dil.NaOH
6 5 ¾¾¾¾¾
® CH3 - C - CH 2 - CHO
O |
H
Aldol
C6H5 – C = CH – C– C6H5
D
¾¾
® CH3 - CH = CH.CHO
CH3 - H 2O Crotonaldehyde
EBD_8336
284 CHEMISTRY
36. (c) The degree of hydrolysis increases as the
magnitude of positive charge on carbonyl group H H
| |
increases. Electron withdrawing group increases 41. (d) CH 3 - C = O + HCN ® CH 3 - C - OH
the positive charge and electron releasing group |
decreases the positive charge. Among these NO2 CN
&-CHO are electron withdrawing group from H H
which-NO2 exhibit more –I effect than –CHO. On | |
H + / H 2O
the other hand-CH3 is a electron releasing group ¾¾ ¾ ¾
¾® OH - C - CH 3 + CH 3 - C - OH
| |
therefore the order of reactivity towards COOH COOH
hydrolysis is 50% L - Lactic 50% D-Lactic
acid acid
COCl COCl COCl COCl 42. (a) Acetophenone is a ketone, cyclopentane
doesn’t contain (4n + 2)p electron hence is not
> > > aromatic. Diastase is an enzyme used in the
preparation of Maltose (Malt sugar,
NO2 CHO CH3 C12H22O11) through hydrolysis of starch.
37. (d) Out of given compound only acetaldehyde 43. (c) Tollen's reagent is used to detect aldehydic
can form optical active hydroxy acid as it contains group. Tollen's reagent is an ammonical solution
one asymmetric carbon atom as marked below : of silver nitrate. When aldehyde is added to
Tollen's reagent, silver oxide is reduced to metallic
O OH silver which deposits as mirror.
|| |
HCN
CH3 - C - H ¾¾¾® CH3 - C - CN RCHO + Ag2O ¾¾ ® RCOOH + 2Ag
|
H 44. (c) In CH 2 = CH — CHO due to – M effect of
OH — CHO group, polarization of electron takes
hydrolysis
| place as follows:
¾¾¾¾¾
® CH3 - C*- H + –
| CH 2 = CH — C = O « CH 2 — CH = C — O
| |
COOH H H
38. (c) Aldehydes are more reactive than ketones due Hence, partial polarization is represented as
to +I effect of –CH3 group. There are two –CH3 d+ d-
group in acetone which reduces +ve charge density C H 2 = CH — CH = O
on carbon atom of carbonyl group. More hindered 45. (a)
carbonyl group too becomes less reactive. So, in O
the given case CH3CHO is the right choice.
R C H + NH2 NH2 ¾® R C N NH2
O OH H
|| |
HCN Aldehyde Hydrazine Aldehyde hydrazone
39. (a) R– C –R ¢ ¾¾¾® R — C — CN
KCN | 46. (d) Iodoform test is exhibited by ethyl alcohol
R ¢ (A) acetaldehyde, acetone, methyl ketones and those
OH alcohols which possess CH3CH(OH)-group. As
| 3-pentanone does not contain CH3 CO-group
Reduction by
¾¾¾¾¾¾
® R– C – CH 2 NH 2 therefore it does not give iodoform test.
LiAlH 4 (B) |
R¢ 47. (a)
40. (c) It is a simple Cannizzaro reaction. OH O
– C CH C CH2 C CH3
CHO COO CH2OH
H SO /HgSO 4
2 4
50% KOH ¾¾¾¾¾®
2 +
Cl Cl Cl enol form Keto form
OH In benzoin condensation potassium cyanide act as

O
a catalyst. Chiral catalyst can make benzoins with
48. (c) CH3 C H + HCN CH3 C H stereoselectivity with a significant enantiomeric
excess.
CN
CH3 CH COOH ¬¾ ¾¾
¾¾
Hydrolysis 54. (d) Dihydrogen sodium phosphate (NaH2PO4)
does not have a lone pair of electrons on the P
OH atom hence, can not act as a nucleophile and hence,
2-Hydroxy propanol does not react with aldehydes and ketones.
(As it has a chiral C-atom thus, it is optically active) 55. (d) Aldehydes which contain an a -hydrogen on
a saturated carbon, undergo aldol condensation.
O
H CH3
C–CH3 CH2–CH3 | |
CH3CH 2 – C = O + H - H C - CHO
Zn-Hg/HCl propanol a
49. (b) ¾¾¾¾®
CH3 CH3
Phenyl methyl ethyl OH - b| a|
ketone benzene ¾¾¾® CH3 CH 2 - C - C HCHO
|
This reaction is known as Clemmensen's reduction. OH
50. (c) Aldol condensation is given by the 3-hydroxy-2-methyl pentanal
compounds which contain a-hydrogen atom. As 56. (b) Acetaldehyde reacts only with nucleophiles.
the given compound does not contain a Since, the mobile p-electrons of carbon–oxygen
hydrogen atom. Hence, it does not undergo aldol double bond are strongly pulled towards oxygen,
condensation. carbonyl carbon is electron-deficient and
51. (c) More is the electron - deficiency of the carbonyl oxygen is electron-rich. Thus, the
carbonyl carbon, greater will be the reactivity of electron deficient (acidic) carbonyl carbon is
the carbonyl compounds towards nucleophilic most susceptible to attack by electron rich
addition. nucleophilic reagents, that is, by base. Hence,
O the typical reaction of aldehydes and ketones is
CH3CH2CH 2CHO > > CH3CH2COCH2CH3 nucleophilic addition.
O OH
–
52. (b) CH 3 COCH 3 + 3I 2 + 4 NaOH ¾¾® C = O + Nu C C
Acetone Nu Nu
CHI 3 + 3NaI + CH 3COONa + 3H 2 O 57. (d) I2 and NaOH react with acetophenone
Iodoform (C6H5COCH3) to give yellow ppt. of CHI3 but
Thus, acetone reacts with iodine to form benzophenone (C6H5COC6H5 ) does not and
iodoform in the presence of NaOH. hence, can be used to distinguish between them.
53. (b) When benzaldehyde is refluxed with aqueous 58. (a) CH2
alcoholic potassium cyanide, two molecules of On keeping O O
3 HCHO
benzaldehyde condense together to form benzoin CH2
aq. solution CH2
H O O
KCN (alc) Trioxane
—C +C— ¾¾¾® (meta formaldehyde)
D
O H 59. (d) Acetone forms mesitylene (1,3,5-trimethyl
benzene) on distillation with conc. H2SO4.
H O
60. (a) When 3 molecules are combined in presence
—C—C— of dry HCl gas they condense to form phorone.
OH
EBD_8336
286 CHEMISTRY
CH3 CH3 65. (c) Carboxylic acids have higher boiling points
C = O + H2 CHCOCH H2 + O = C than aldehydes, ketones and even alcohols of
CH3 CH3 comparable molecular mass.
CH 3 CH 3 This is due to more extensive association through
HCl
¾¾® C = CH COCH = C intermolecular H-bonding.
–2H 2O
CH 3 CH 3
Phorone O ¼¼¼H O
R C C R
Two molecules of acetone condense to form O H ¼¼¼O
mesityl oxide.
66. (a) Among the substituent attached to the
CH3
C = O + H 2 CHCOCH 3 ¾® benzene ring, –NO2 group is the most electron
CH3 withdrawing, thus withdraws electron density
CH3
from carbonyl carbon thus facilitate the attack
C == CH.CO.CH3
CH3 –
of OH ion.
61. (b) Aldehydes containing no a-hydrogen atom O O
on warming with 50% NaOH or KOH undergo . . || ||
O – C – CH3 O – C – CH3
..
disproportionation i.e. self oxidation - reduction
known as Cannizzaro’s reaction.
50%NaOH
2 HCHO + ¾¾¾¾¾
® HCOONa + CH 3OH
62. (c) Formalin is an aqueous solution (40%) of N N
– – –
formaldehyde. O O O O
63. (d) (–R effect of –NO 2 group)
CH2 CHO 67. (a) CF3 COOH > CCl3 COOH > HCOOH >
OH ¾¾¾¾®
PCC CH3COOH (Ka order)
Pyridinium
chlorochromate The halogenated fatty acids are much stronger
PCC is a mild oxidizing agent which oxidises acids than the parent fatty acid and moreover
primary alcohol to aldehyde. the acidity among the halogenated fatty acid
COOH increases almost proportionely with the increase
64. (b) + NH3 ¾¾® in electronegativity of the halogen present.
COOH Further, formic acid having no alkyl group is more
Å acidic than acetic acid.
COONH4 CONH2
D
Å ¾¾¾¾ ® 68. (d)
-2H 2O
COONH4 CONH2
KCN
(a) 2C6H5CHO ¾¾¾¾¾®
H O, C H OH 2 2 5
O
Strong C OH
Heating
¾¾¾® NH KCN
C6H5 – CH – C – C6H5
–NH3 C H O C H OH
O O
(Benzoin)
(b) O O OH
71. (a) N6O2
+
O ¾®
H
O NO2 > CH3COOH >
H O H
NO2
(II) (III)
OH OH
OH OH OH OH
Phenolphthalein
(c) The fries rearrangement enables the >
preparation of acylphenols. The reaction is
catalysed by Bronsted or lewis acid such as (IV) (I)
AlCl3. Explanation: Presence of three — NO2 groups
O OH O OH in o–, p– positions to phenolic groups (in III)
makes phenol strongly acidic because its
O R AlCl R corresponding phenate ion (conjugate base) is
¾¾ ®
3
highly stabilised due to resonance. Conjugate
base of CH3 COOH, II (i.e. CH3 COO – ) is
resonance hybrid of two equivalent structures.
R O The conjugate base of phenol, IV is stabilized
Fries rearrangement
due to resonance (note that here all resonating
COOCH3
structures are not equivalent). The conjugate
OH base of cyclohexanol, I does not exhibit
(d) (Oil of wintergreen) resonance, hence not formed.
72. (d) Cl– is the weakest base and hence better
69. (d) Since, C when heated with Br2 in presence leaving group.
of KOH produces ethylamine, hence it must be 73. (c) This reaction is an example of Hell - Volhard
propanamide and hence the organic compound Zelinsky reaction. In this reaction acids
(A) will be propanoic acid. The reactions follows:
NH
containing a – H on treatment with X2 /P give
CH3 - CH 2 - COOH ¾¾¾
3
® di-halo substituted acid.
(A)
- + Br /P
D CH3 – CH 2 COOH ¾¾¾
2 ® CH - CBr - COOH
CH3 - CH 2 - CO O N H 4 ¾¾
® 3 2
(B) Hell-volhard-zelinsky reaction:
KOH + Br Carboxylic acids having an a-hydrogen are
CH 3 - CH 2 - CONH 2 ¾¾¾¾¾
2
®
Hoffmann halogenated at the a-position on treatment with
(C) bromamide chlorine or bromine in the presence of small amount
reaction
of red phosphoms to give a-halocarboxylic acids.
CH3 - CH 2 - NH 2 The reaction fails to accomplish the fluorination
(Ethylamine)
and iodination of carboxylic acids.
CH2 – CH3 COOH
74. (a) The more the basic character of the leaving
( KMnO4 )®
¾¾¾¾¾ group, the lesser is the reactivity. The basic
70. (d) KOH
character follows the order:
(B) NH2– > OR– > RCOO – > Cl–
COOH COOC2H5 Hence, the relative reactivities of acyl
Br C H OH
compounds towards nucleophilic substitution
¾®
2
¾¾¾¾®
2 5
+ follow the order Acyl halides > Acid anhydride
FeCl3 H
Br Br > Ester > Amide.
(C) (D)
EBD_8336
288 CHEMISTRY
75. (c) Electron withdrawing substituents (like 79. (a) Among the given options, only PCl5 can
halogen, – NO2, – C6H5 etc.) would disperse convert an alcoholic group as well as a carboxyl
the negative charge and hence stabilise the group to chloride.
carboxylate ion and thus increase acidity of the PCl
5® RCH Cl
RCH 2 OH ¾¾¾
parent acid. On the other hand, electron-releasing 2
substituents would intensify the negative PCl
5 ® RCOCl
RCOOH ¾¾¾
charge, destabilise the carboxylate ion and thus
decrease acidity of the parent acid. Other than PCl5 or PCl3, SOCl2 also can be used.
Electronegativity decreases in order SOCl2 is preferred because the other two products
F > Cl > Br in this case are gaseous and escape the reaction
and hence –I effect also decreases in the same mixture. This makes the purification of the
order, therefore the correct option is products easier.
RCOOH + SOCl2(l) ® RCOCl + SO2(g) + HCl(g)
[FCH2COOH > ClCH2COOH >
BrCH2COOH > CH3COOH] 80. (a) CH3COOH + PCl5 ® CH3COCl
76. (a) It is an example of Claisen condensation. The COCH3
product is acetoacetic ester.
O O C H
¾¾¾¾¾
6 6
¾
® MgBrC2H 5
|| || Anhyd AlCl3
CH 3 C - OC 2 H 5 + H - CH 2 - C - OC 2 H 5 ¾
¾® Friedel Craft
reaction
O O [B]
|| ||
CH 3 - C - CH 2 - C - OC 2 H 5
(ethyl acetoacetate ) OH
OMgBr
C 2 H5 – C – CH3
77. (c) CH 3 CH 2 COOH ¾SOCl
¾¾ ¾ 2® C 2 H 5 – C – CH3
NH H+
CH 3 CH 2 COCl ¾¾¾
3®
ether
KOH hydrolysis [C]
CH3 CH 2 CONH 2 ¾¾¾® CH3CH 2 NH 2
Br2
81. (b) Grignard reagent forms addition product with
SOCl bubbled carbondioxide which on hydrolysis with
78. (d) CH 3COOH ¾ ¾¾2® CH 3 - COCl HCl yields benzoic acid.
Friedel Craft C6 H 6 / AlCl3
reaction O
MgBr C OMgBr
+
(i) CO H O
¾¾®
2
¾¾®
3
HCN
¬¾¾
¾¾¾®
O
H2O
(hydrolysis of cyano group) C O H
+ Mg(OH)Br
'P'
Benzoic acid
82. (c) 86. (b) The ester having a-hydrogen atom show
Claisen condensation reaction. We know that
COOH COOC2H5 ethyl benzoate (C6 H5 COOC 2 H5 ) does not
contain a-hydrogen. Therefore, C6H5COOC2H5
HCl does not undergo Claisen self condensation.
+ C2H5OH ¾®
dry
+ H2O
Ethanol 87. (c) CH3COOH + CaCO3 ¾® (CH3COO)2Ca
CH 3
This process is known as esterification. ¾¾¾®
Heat
CH 3
> CO ¾¾¾¾¾
I2 + NaOH
®
O CHI3 + NaI + CH3COONa + 3H2O
83. (b) CH3 —C == O + H2N—NH—C—NH2 88. (c) When glycerol is heated with oxalic acid
following reaction occurs.
H CH2OH HOOC CH2OC.COOH
O | |
100 -110°C
|
(–H2O) CHOH + HOOC ¾¾¾¾¾
® CHOH
- H2O
¾ ¾ ® CH3—CH == N—NH—C—NH2 | oxalic |
acetaldehyde semicarbazone CH 2OH acid CH2OH
CH2 CHO CH2OH
OH | |
- CO H O
COOH ¾¾¾®
2 CHOH ¾¾¾
2 ® CHOH + HCOOH
| | Formic acid
84. (a) + ClCOCH3 CH 2OH CH2OH
89. (d) In Claisen condensation intermolecular
o-hydroxy benzoic acid acetyl chloride
(Salicylic acid) condensation of esters containing a-hydrogen
OCOCH3 atom in presence of strong base form b-keto ester.
COOH CH3COO C2H5 + H.CH2.CO.OC2H5
Pyridine
¾¾¾® ethyl acetate
O
C2H5ONa
Aspirin CH3C. CH2COOC2 H5+ C2H5OH
CH COO C H + H.CH .CO.OC H
85. (a) Ethyl acetoacetate
OMgBr (b-ketoester)
| OH
CH MgBr
C6 H5COOC2 H5 ¾¾¾¾¾
3
® C6 H5 - C - OC2 H5
( A) |
CH 90. (a) aq. NaOH
3 + C6H5COCl
O O.COC6H5
||
- Mg(OC2 H5 )Br Excess
¾¾¾¾¾¾¾
® C6 H5 - C - CH3 ¾¾¾¾
®
CH3MgBr
OMgBr CH3
HO phenyl benzoate
C6 H5 C CH3 ¾®
2
C6 H5 C CH3
The function of NaOH is
CH3 OH (i) To convert phenol to more stronger nucleophile
CH3 PhO –
| (ii) To neutralize the acid formed
Conc. H 2SO 4
¾¾¾¾¾¾
® C 6 H5 — C = CH 2
D 91. (d) Methyl acetate and ethyl acetate on
'B' hydrolysis give CH3COOH which is a liquid.
Ozonolysis
¾¾¾¾¾ ® C 6 H 5 COCH 3 + HCHO Similarly ethyl formate on hydrolysis will give
formic acid which is also a liquid. Only ethyl
3I + 4 NaOH
C6 H 5 COCH 3 ¾¾¾¾¾¾
2
® CHI3 benzoate on hydrolysis will give benzoic acid
which is a solid.
EBD_8336
290 CHEMISTRY
D COONa COOC2H5 H2N

92. (b) 2HCOONa ¾¾ ® | + H2 97. (c) CH 2 + CO
360°
COONa COOC2H5 H2 N
sod.oxalate
93. (a) Among acetic acid, phenol and n-hexanol Malonic ester
only CH3 COOH reacts with NaHCO3 to evolve CO - NH
CO2 gas. D
¾¾
® CH 2 CO + 2C2H5OH
CH3COOH + NaHCO3 CO - NH
¾¾ ® CH3COONa + CO2 + H2O Barbituric acid
94. (b) The only reagent suitable for this 98. (a) An electron releasing substituent (+I effect)
conversion is NaOI or NaOH + I2 (iodoform test): intensify the negative charge on the anion
(CH 3 ) 2 C = CHCOCH 3 ¾¾¾®
NaOI resulting in the decrease of stability and thus
decreases the acidity of the acid. Hence, acidic
(CH 3 ) 2 C = CHCOOH + CHI 3 . character decreases as the + I-effect of the alkyl
group increases as
Chromic acid and KMnO4 will cleave the molecule
at the site of double bond while Cu at 300°C cannot CH 3 < CH 3CH 2 < CH 3CH 2CH 2
oxidise COCH3 ¾® COOH.
< CH3CH2CH2CH2
95. (a) Ketones on oxidation give carboxylic acids Hence the order of acidic strength becomes:
with lesser number of carbon atoms, i.e.,
(i) > (ii) > (iii) > (iv)
[O]
CH3COCH3 ¾¾¾
® CH3COOH + CO2 + H2O 99. (c) Chlorine is electron withdrawing group.
Soda - lim e (X) Further Inductive effect is stronger at a-position
96. (d) C6 H 5 COOH ¾¾¾¾¾¾®
than b-position. i.e.,
C6 H6 + Na 2CO3 + H 2 O
a b a
Zn dust (Y) CH 2 ClCOOH > CH 2 ClCH 2COOH
C6 H 5 OH ¾¾¾¾¾® C6 H 6 + ZnO
Amines 291
27 Amines
2020 2019 2018 2017 2016

carbylamine
1 E
reaction
basic strength of
1 A 1 A 1 A
amines
Aliphatic and aromatic
Hoffmann
amines
bromamide 1 A
reaction
electrophillic
1 A
substitution
Topic 1: Aliphatic and Aromatic Amines (b) CH3 — CH — NH — CH — CH3

1. Which of the following amine will give the | |
CH3 CH3
carbylamine test? [2020]
NHCH3 N(CH3)2 CH2CH3
|
(c) CH 3 — CH 2 — N — CH 2CH 3
(a) (b)
NH2
|
NHC2H5 NH3 (d) CH3 — C — CH 2CH 2CH3
|
(c) (d) CH3
3. The correct order of the basic strength of methyl

2. The amine that reacts with Hinsberg’s reagent substituted amines in aqueous solution is :
to give an alkali insoluble product is (a) (CH3)2NH > CH3NH2 > (CH3)3N [2019]
[NEET Odisha 2019]
CH3 (b) (CH3)3N > CH3NH2 > (CH3)2NH
|
(a) CH3 — C — CH — NH 2 (c) (CH3)3N > (CH3)2NH > CH3NH2
| | (d) CH3NH2 > (CH3)2NH>(CH3)3N
CH3 CH3
EBD_8336
292 CHEMISTRY
4. Nitration of aniline in strong acidic medium also (d) Arylamines are generally more basic than
gives m-nitroaniline because [2018] alkylamines, because the n itrogen atom
(a) Inspite of substituents nitro group always in arylamines is sp-hybridized.
goes to only m-position. 8. The electrolytic reduction of nitrobenzene in
(b) In electrophilic substitution reactions, strongly acidic medium produces :- [2015]
amino group is meta directive. (a) Azoxybenzene (b) Azobenzene
(c) In acidic (strong) medium aniline is present (c) Aniline (d) p-Aminophenol
as anilinium ion. 9. The number of structural isomers possible from
(d) In absence of substituents, nitro group the molecular formula C3H9N is : [2015 RS]
always goes to m-position. (a) 4 (b) 5
5. The correct increasing order of basic strength (c) 2 (d) 3
for the following compounds is : [2017] 10. Method by which aniline cannot be prepared is:
[2015 RS]
NH2 NH2 NH2
(a) hydrolysis of phenylisocyanide with acidic
solution
(I) (II) (III)
(b) degradation of benzamide with bromine in
CH3 alkaline solution
NO2
(c) reduction of nitrobenzene with H2/Pd in
(a) III < I < II (b) III < II < I ethanol
(c) II < I < III (d) II < III < I (d) potassium salt of phthalimide treated with
chlorobenzene followed by hydrolysis with
6. Which of the following reactions is appropriate
aqueous NaOH solution.
for converting acetamide to methanamine? [2017]
11. Some reactions of amines are given. Which one
(a) Hoffmann hypobromamide reaction is not correct ? [NEET Kar. 2013]
(b) Stephens reaction (a) (CH3)2NH + NaNO2 + HCl ®
(c) Gabriels phthalimide synthesis (CH3)2 N – N = O
(d) Carbylamine reaction (b) (CH3)2N – + NaNO2 + HCl ®
7. The correct statement regarding the basicity of
arylamines is [2016] (CH3)2N – – N = NCl
(a) Arylamines are generally less basic than
alkylamines because the nitrogen lone-pair (c) CH3CH2NH2 + HNO2 ® CH3CH2OH + N2
electrons are delocalized by interaction (d) CH3NH2 + C6H5SO2Cl ®
with the aromatic ring p electron system. CH3NHSO2C6H5.
(b) Arylamines are generally more basic than 12. In a set of reactions m-bromobenzoic acid gave
alkylamines because the nitrogen lone-pair a product D. Identify the product D. [2011]
electrons are not delocalized by interaction COOH
with the aromatic ring p electron system.
SOCl NH
NaOH
¾¾®
2
B ¾¾®
3
C ¾¾®
Br D
(c) Arylamines are generally more basic than 2
alkylamines because of aryl group. Br
Amines 293
SO2NH2 COOH (4) CH3CH(OH)CH3 (iv) with Lucas

(a) (b) reagent
cloudiness
Br NH2 appears
after 5 minutes
NH2 CONH2 Options :
(c) (d) (1) (2) (3) (4)
(a) (iv) (ii) (iii) (i)
Br Br (b) (ii) (i) (iv) (iii)
(c) (iii) (ii) (i) (iv)
13. Which of the following compounds is most basic? (d) (ii) (iii) (i) (iv)
[2011 M] 16. Predict the product: [2009]
NHCH3+NaNO2+ HCl ¾® Product
(a) O2N NH2 (b) CH2NH2
CH3
(c) N – COCH3 (d) NH2 N NO2
H (a)
14. Which of the following statements about primary
NHCH3 NHCH3
amines is ‘False’ ? [2010]
(a) Alkyl amines are stronger bases than aryl NO
amines (b) +
(b) Alkyl amines react with nitrous acid to
produce alcohols NO
OH
(c) Aryl amines react with nitrous acid to
produce phenols N CH3
(c)
(d) Alkyl amines are stronger bases than ammonia
15. Match the compounds given in List - I with their
characteristic reactions given in List - II. Select CH3
the correct option. [2010] N N=O
(d)
List - I List - II
Compounds Reactions
17. Which of the following is more basic than
(1) CH3CH2CH2CH2NH2 (i) alkaline aniline? [2006]
hydrolysis (a) Triphenylamine (b) p-Nitroaniline
(c) Benzylamine (d) Diphenylamine
(2) CH3C º CH (ii) with KOH
18. The major organic product formed from the
(alcohol) and following reaction : [2005]
CHCl3 produces
O
bad smell (i) CH NH
¾ ¾ ¾ ¾ ¾ ¾ ® ......
3 2
(3) CH3CH2COOCH3 (iii) gives white (ii) LiAlH 4, (iii) H 2O
ppt. with
is
ammonical
AgNO3
EBD_8336
294 CHEMISTRY
O – NHCH3 23. The compound obtained by heating a mixture
(a) of a primary amine and chloroform with ethanolic
potassium hydroxide (KOH) is [1997]
(a) an alkyl cyanide (b) a nitro compound
(b)
(c) an alkyl isocyanide (d) an amide
NCH3
24. When aniline reacts with oil of bitter almonds
H
(C6 H5CHO), condensation takes place and benzal
derivative is formed. This is known as [1995]
H
(a) Million's base (b) Schiff's reagent
NCH3
(c) (c) Schiff's base (d) Benedict's reagent
OH 25. What is the decreasing order of basicity of
primary, secondary and tertiary ethylamines and
H NH3 ? [1994]
NCH3 (a) NH 3 > C 2 H 5 NH 2 > (C 2 H 5 ) 2 NH >
(d)
OH (C 2 H 5 )3 N
19. Electrolytic reduction of nitrobenzene in weakly (b) (C2 H 5 )3 N > (C2 H 5 )2 NH >
acidic medium gives [2005]
C2 H5 NH 2 > NH 3
(a) N-Phenylhydroxylamine
(b) Nitrosobenzene (c) (C2 H 5 )2 NH > C2 H 5 NH 2 >
(c) Aniline (C 2 H 5 )3 N > NH 3
(d) p-Hydroxyaniline (d) (C 2 H 5 ) 2 NH > (C 2 H 5 )3 N >
20. The consituent of the powerful explosive RDX
C 2 H 5 NH 2 > NH 3 .
is formed during the nitration of [2000]
(a) Toluene (b) Phenol 26. Mark the correct statement [1988]
(c) Glycerol (d) Urotropine (a) Methylamine is slightly acidic
21. Which of the following is most basic in nature? (b) Methylamine is less basic than ammonia
(a) NH3 (b) CH3NH2 [2000] (c) Methylamine is a stronger base than ammonia
(c) (CH3)2NH (d) C6H5NHCH3 (d) Methylamine forms salts with alkalies.
22. Aniline is reacted with bromine water and the
Topic 2: Amides, Cyanides and Isocyanides
resulting product is treated with an aqueous
solution of sodium nitrite in presence of dilute 27. The following reaction
hydrochloric acid. The compound so formed is NH2
converted into a tetrafluoroborate which is + Cl
subsequently heated dry. The final product is
O
(a) 1,3, 5-Tribromobenzene [1998]
H
(b) p-Bromofluorobenzene N
NaOH
(c) p-Bromoaniline ¾¾¾®
O
(d) 2,4, 6-Tribromofluorobenzene
O
is known by the name : [2015 RS]
Amines 295
(a) Friedel-Craft's reaction 32. The final product C, obtained in this reaction
(b) Perkin's reaction NH2
(c) Acetylation reaction Ac O Br H O
¾¾®
2
¾¾¾®
A CH 2
B ¾¾®
2
C
(d) Schotten-Baumen reaction COOH
3
+
H
28. On hydrolysis of a “compound”, two compounds
CH3
are obtained. One of which on treatment with sodium
would be [2003]
nitrite and hydrochloric acid gives a product which
does not respond to iodoform test. The second one NHCOCH3 NH2
reduces Tollen’s reagent and Fehling’s solution. The Br COCH3
“compound” is [NEET Kar. 2013] (a) (b)
(a) CH3 CH2 CH2 CON(CH3)2
CH3 CH3
(b) CH3 CH2 CH2 NC
COCH3 NH2
(c) CH3 CH2 CH2 CN Br Br
(d) CH3 CH2 CH2 ON = O (c) (d)
29. An organic compound (C3H9N) (A), when treated
with nitrous acid, gave an alcohol and N2 gas was CH3 CH3
evolved. (A) on warming with CHCl3 and caustic C N
potash gave (C) which on reduction gave
isopropylmethylamine. Predict the structure of (A). H OÅ
33. + CH3MgBr ¾¾¾¾
3 ®P
CH3
(a) CH NH2 [2012 M] OCH3
CH3
Product 'P' in the above reaction is [2002]
(b) CH3CH2 NH CH3 OH O
(c) CH3 N CH3
CH – CH3 C – CH3
CH3
(a) (b)
(d) CH3CH2 CH2 NH2
OCH3 OCH3
30. Acetamide is treated with the following reagents
separately. Which one of these would yield CHO COOH
methylamine? [2010]
(a) NaOH – Br2
(b) Sodalime (c) (d)
(c) Hot conc. H2SO4 OCH3 OCH3
(d) PCl5 34. Intermediates formed during reaction of
31. Which one of the following on reduction with R C NH 2 with Br2 and KOH are [2001]
lithium aluminium hydride yields a secondary ||
O
amine? [2007]
(a) Methyl isocyanide (a) RNHBr and RCONHBr
(b) Acetamide (b) RNHCOBr and RNCO
(c) Methyl cyanide (c) RCONHBr and RNCO
(d) Nitroethane. (d) RCONBr2
EBD_8336
296 CHEMISTRY
35. An isocyanide is prepared by [1999] 39. Acetamide and ethylamine can be distinguished
(a) Friedel-Crafts reaction by reacting with [1994]
(b) Perkin reaction (a) Aqueous HCl and heat
(c) Carbylamine reaction (b) Aqueous NaOH and heat
(d) Wurtz reaction (c) Acidified KMnO4
36. Consider the following sequence of reactions :
(d) Bromine water.
Reduction HNO
® [B] ¾¾¾¾
Compound[A] ¾¾¾¾¾ 2®
40. For carbylamine reaction, we need hot alcoholic
CH3CH 2OH KOH and [1992]
The compound [A] is [1996] (a) Any primary amine and chloroform
(a) CH3CH2CN (b) CH3NO2 (b) Chloroform and silver powder
(c) CH3NC (d) CH3CN (c) A primary amine and an alkyl halide
37. Aniline is an activated system for electrophilic
(d) A monoalkylamine and trichloromethane.
substitution. The compound formed on heating
aniline with acetic anhydride is [1996] 41. Indicate which nitrogen compound amongst the
following would undergo Hoffmann reaction
NH2 (i.e., reaction with Br2 and strong KOH) to
furnish the primary amine (R – NH2) [1989]
(a) (a) RCONHCH3 (b) RCOONH4
COCH3
(c) RCONH2 (d) R – CO – NHOH.
NH2
Topic 3: Nitrocompounds, Alkyl Nitrites and
Diazonium Salts
(b)
42. In the following reaction, the product (A) [2014]
COCH3 +
NºNCl
–
NH2
NH2
+ H +
is :
(c) ¾¾® (A)
Yellow dye
COCH3
NHCOCH3
(d) (a) N=N–NH
NH2
38. Which is formed, when acetonitrile is hydrolysed
partially with cold concentrated HCl? [1995] (b) N=N
(a) Acetic acid NH2
(b) Acetamide
(c) N=N
(c) Methyl cyanide
(d) Acetic anhydrides
(d) N=N NH2
Amines 297
43. Which of the following will be most stable 47. Aniline in a set of the following reactions yielded
diazonium salt RN2+X– ? [2014] a coloured product ‘Y’ [2002, 2010]
(a) CH3 N2+X– (b) C6H5N2+X– NH2
(c) CH3CH2N2+X– (d) C6H5CH2N2+X– NaNO /HC1

¾¾¾¾¾¾
2 ®X
(273-278K)
44. In the reaction
NO2 NO2 N, N-dimethylaniline
¾¾¾¾¾¾¾¾® Y
A
The structure of ‘Y’ would be ;
¾®
Br Br
CH3
(a) N=N N
ÅN2C I –
CH3
A is : [NEET 2013]
(a) Cu2Cl2 (b) H3PO2 and H2O CH3 CH3
(c) H+/H2O (d) HgSO4/H2SO4 (b) HN NH NH

45. Nitrobenzene on reaction with conc.
HNO3/H2SO4 at 80 - 100°C forms which one of
(c) H C N=N NH2
the following products ? [NEET 2013] 3
(a) 1, 3 - Dinitrobenzene
CH3 CH3
(b) 1, 4 - Dinitrobenzene
(c) 1, 2, 4 - Trinitrobenzene (d) HN N=N NH
(d) 1, 2 - Dinitrobenzene
48. Nitrobenzene can be prepared from benzene by
46. What is the product obtained in the following using a mixture of conc. HNO3 and conc. H2SO4;
reaction : [2011] in the mixture, nitric acid acts as a/an: [2009]
NO2 (a) acid (b) base
Zn ........... ?
¾¾®
NH Cl (c) catalyst (d) reducing agent
4
49. Aniline in a set of reactions yielded a product D.
NHOH NH2
NaNO CuCN
(a) ¾¾¾®
HCl
2
A ¾¾¾® B
N H HNO
¾¾¾®
2
C ¾¾¾®
2
D
(b) N Ni
The structure of the product D would be: [2005]
O
– (a) C6H5NHOH (b) C6H5NHCH2CH3
N=N (c) C6H5CH2NH2 (d) C6H5CH2OH

(c) + 50. Aniline when diazotized in cold and when
treated with dimethyl aniline gives a coloured
NH 2 product. Its structure would be [2004]
(d)
(a) CH3NH N=N NHCH3
EBD_8336
298 CHEMISTRY
(a) Formaldehyde
(b) CH3 N=N NH2 (b) Trichloromethane
(c) Nitrobenzene
(d) Toluene
(c) (CH3)2N N=N 52. Which of the following reagents will convert
p-methylbenzenediazonium chloride into
p-cresol?
(d) (CH3)2N NH (a) Cu powder (b) H2O [1999]
(c) H3PO2 (d) C6H5OH
51. reduction
[A] ¾¾¾¾® [B] ¾¾¾¾¾¾
3 ®
CHCl +KOH [2000] 53. Diazo coupling is useful to prepare some [1994]
reduction (a) Pesticides (b) dyes
[C] ¾¾¾¾® N-Methylaniline, A is
(c) proteins (d) vitamins
ANSW E R KE Y
1 (d) 7 (a) 13 (b ) 19 (c) 25 (d ) 31 (a) 37 (d ) 43 (b ) 49 (d )
2 (b) 8 (d ) 14 (c) 20 (d ) 26 (c) 32 (d ) 38 (b ) 44 (b ) 50 (c)
3 (a) 9 (a) 15 (d ) 21 (c) 27 (d ) 33 (b ) 39 (b ) 45 (a) 51 (c)
4 (c) 10 (d ) 16 (d ) 22 (d ) 28 (b ) 34 (c) 40 (a) 46 (a) 52 (b )
5 (c) 11 (b ) 17 (c) 23 (c) 29 (a) 35 (c) 41 (c) 47 (a) 53 (b )
6 (a) 12 (c) 18 (b ) 24 (c) 30 (a) 36 (d ) 42 (d ) 48 (b )
Hints & Solutions

1. (d) Aliphatic and aromatic primary amines give In acidic medium aniline is protonated to form
carbylamine reaction. Since aniline is primary anilinium ion which is meta-directing.
aromatic amine, it gives carbylamine test. 5. (c) – NO2 group has strong – R effect and –
2. (b) Hinsberg’s reagent is used to distinguish CH3 shows +R effect.
1°, 2° and 3° amine. Primary amines react with \ Order of basic strength is
Hinsberg’s reagent to give precipitate. which is
soluble in alkali while secondary amines give a NH2 NH2 NH2
product which is insoluble in alkali. Tertiary
amines do not react with Hinsberg’s reagent. < <
3. (a) Account for the inductive effect, solvation
effect (H-bonding.) and steric hinderance for NO2 CH3
basic character in aqueous solutions O
(CH3)2 NH > CH3 NH2 > (CH3)3 N 6. D
(a) CH3 - C - NH 2 + Br2 + 4NaOH ¾¾ ®
4. (c) acetamide
+ + CH3 – NH2 + 2NaBr + Na2CO3 + 3H2O
NH2 NH3 NH3
methanamine
+
H+
¾¾¾¾®
NO2
¾¾¾®
It is called Hoffmann Bromamide reaction.
nitrating
mixture NO2
Amines 299
Hoffmann bromamide reaction: Reaction of an O

acid amide with bromine in an aqueous or ethanolic
solution of sodium hydroxide to form a primary COOH C – Cl
amine, with one carbon atom less, is known as
Hoffmann bromamide reaction. SOCl NH
2
12. (c) ¾¾® ¾¾®
3
7. (a) Arylamines are generally less basic than Br Br

alkylamines due to following factors:
(i) Due to resonance in aromatic amines. O NH2
C NH2
(ii) Lower stability of anilinium ion.
NaOH
8. (d) ¾¾¾®
+Br2
NO2 HN—OH Br Br
Electrolytic
reduction 13. (b)
¾¾¾¾¾® CH2–NH2 compound is most basic
(Strongly acidic
medium)
Phenyl due to localized lone pair of electron on nitrogen
nitrobenzene hydroxylamine
atom while other compounds have delocalized
lone pair of electron.
NH2
14. (c) Aryl amines react with nitrous acid to
rearrangement produce diazonium salt and not phenol.
¾¾¾¾¾®
¾¾¾¾¾®
15. (d) (1) CH3 CH2 – CH2 – CH2 – NH2
(primary amine)
OH
(ii) with KOH (alcohol) and CHCl3 it produces
9. (a) C3H9N bad smell
CH3—CH2—CH2—NH2 (2) CH3C º CH (acidic hydrogen)
CH3 – NH – CH2 – CH3. (iii) gives white ppt with ammonical AgNO3
CH3 — CH — CH 3 , CH 3 —N — CH 3 (3) CH3 CH2 COOCH3 (ester)
| | (i) alkaline hydrolysis
NH2 CH3
(4) CH3 CHOH – CH3 (secondary alcohol)
10. (d) Because arylhalides do not undergo (iv) with Lucas reagent cloudiness appears after
nucleophilic substitution reaction with 5 minutes
potassium phthalimide easily. 16. (d) Secondary amine with (NaNO2 + HCl) gives
11. (b) Secondary amine react with nitrous acid to a nitroso product
give N-Nitrosoamines. CH3
|
NHCH3 NaNO N–N=O
(CH3)2 N + NaNO2 + HCl ¾® ¾¾¾®
HCl
2
CH3 N– Nitroso – N– methylaniline
Primary amine with NaNO 2/HCl produces

N — N = O + NaCl + CH3OH nitrogen gas. tertiary amine form ammonium
salt.
EBD_8336
300 CHEMISTRY
17. (c) Benzylamine is more basic than aniline. The 21. (c) (CH3)2NH is most basic because two electron
reason is that in aniline, the lone pair of nitrogen releasing groups are present on Nitrogen. Also
aromatic amines are less basic than aliphatic amines.
is conjugated with benzene ring so it is not
The basic character of amines follow the order
available readily for others. On the other hand
R2NH > RNH2 > C6H5NHCH3 > NH3
in Benzylamine, nitrogen is not directly attached
with ring so lone pairs are not conjugated with ring. NH2 NH2
18. (b) Br Br
NaNO
O NCH3 22. (d) +3Br2 ¾® ¾¾¾® 2
& dil HCl
CH 3NH 2
¾¾¾®
Br
¾¾¾®
LiAlH4/H2O
2, 4, 6 tribromoaniline
[H]
+ –
NHCH3 N2Cl N2BF4
Br Br Br Br
NaBF4
¾¾¾®
(- NaCl)
19. (c) Electrolytic reduction of Nitrobenzene in
weakly acidic medium give aniline
Br Br
NO2 NH2 Diazonium Diazonium
salt tetra fluro borate
Electrolytic reduction
¾¾¾¾¾¾¾®
(weakly acidic medium) F
Aniline Br Br
D
Nitroalkane in strongly acidic medium gives ¾¾®
-N2
p-hydroxyaniline - BF3
Br
NO2 NHOH 2,4,6 tribromofluorobenzene
electrolytic
¾¾¾¾¾¾¾®
reduction in presence 23. (c) CH 3CH 2 NH 2 + CHCl 3 + 3KOH ¾
¾®
of conc. H2 SO4
CH 3CH 2 NC + 3KCl + 3H 2O
(Strongly acidic medium)
In this reaction, bad smelling compound ethyl
NH2 isocyanide (CH 3CH 2 NC) is produced. This
rearrangement equation is known as carbyl amine reaction.
¾¾¾¾®
24. (c) Benzaldehyde reacts with primary aromatic
amine to form schiff's base
OH
p-Hydroxyaniline C6 H 5CH = O + C 6 H 5 NH 2 ¾
¾®
Benzaldehyde Aniline
20. (d) RDX is prepared by treating urotropine with
fuming nitric acid. When the inner bridge system is C 6 H 5 C H = NC 6 H 5 + H 2 O
destroyed by oxidation and the peripheral nitrogen Benzyliden e aniline
atom are nitrated, it forms cyclonite (or RDX). 25. (d) All aliphatic amines are stronger bases than
N N conc. HNO O2N — N N — NO2 NH3 and among different ethylamines order of
N ¾¾¾¾® 3
basictity is 2° > 3° > 1°. Thus, the correct order
N N is (d) (in polar solvent):
Urotropine
NO2 (C 2 H 5 ) 2 NH > (C 2 H 5 )3 N >
RDX
C 2 H 5 NH 2 > NH 3 .
Amines 301
This anomalous behaviour of tertiary ethyl amine
is due to steric factors i.e., crowding of alkyl NH2
Cl
groups cover nitrogen atom from all sides and +
(d)
thus makes the approach and bonding by a lewis O
acid relatively difficult which results the Schotten-Baumen Reaction
maximum steric strain in tertiary amines. The
electrons are there but the path is blocked NH – C –
resulting the reduction in its basicity. ¾¾®
NaOH O
This comparison is true for amines in a protic 28. (b) Hydrolysis of propyl isocyanide
solvent like water. In gaseous phase, the order of
basicity is: tertiary amine > secondary amine > (CH3CH2CH2NC) gives CH3CH2CH2 NH2 +
primary amine > NH3. HCOOH.
26. (c) Methyl amine is a stronger base than On treatment with NaNO2 and HCl (I) gives
ammonia due to +I effect. The alkyl groups which CH3CH2CH2OH which does not give iodoform
are electron releasing groups increase the test. II (HCOOH) reduces Tollen’s reagent and
electron density around the nitrogen thereby Fehling’s solution.
increasing the availability of the lone pair of H O
electrons to proton or lewis acid and making the CH3CH 2CH 2 NC ¾¾¾
2 ®
Propyl isocyanide
amine more basic
NH3 CH3NH2 CH3CH 2 CH 2 NH 2 + HCOOH
I II
Kb = 1.8 × 10–5 44 × 10–5
27. (d) HNO2
29. (a) CH3 CH NH2 ¾¾®
CH3
(a) AlCl CH3 (A)

¾¾® 3
CH Cl isopropyl amine
3
(Friedel Craft’s CH3 CH OH + N2
Reaction)
H CH3
O O
isopropyl alcohol
C=O
O CHCl / KOH
(b) + A ¾¾¾¾¾®
3
CH3 CH N C
R R
Perkin Reaction CH3
O O isopropyl isocyanide
(C)
Base
Ar OH + HO reduction
C ¾¾¾® CH3 CH NH CH3
¾¾®
R R CH3
O Isopropylmethylamine
OH
+ CH3 – C – Cl ¾® Only primary aliphatic and aromatic amines give
(c)
Acetylation Reaction
carbylamine reaction. Primary amine on reaction
with HNO2 give alcohol
O
NaOH
O – C – CH3 30. (a) CH3CONH2 ¾¾¾¾
® CH3 NH 2
Br2
(Hofmann bromamide reaction)
EBD_8336
302 CHEMISTRY
31. (a) Reduction of alkyl isocyanides in presence
– +
of LiAlH4 yields secondary amines containing K
(iii) R — C — N —Br R — C — N + KBr
methyl as one of the alkyl group.
O O
r LiAlH 4
R - N = C + 4[H] ¾¾¾¾ ® R - NH - CH3 R
2°amine
N ••
••
r LiAlH 4 (iv) O = C R—N=C=O
e.g., CH3 - N = C + 4[H] ¾¾¾¾ ®
•
•
(rearrangement)
CH 3 - NH - CH 3 · ·
(v) R - N =
C=O + 2KOH ® RNH 2 + K 2 CO 3
dimethyl amine
whereas, alkyl cyanides give 1° amine on reduction. 35. (c) Carbylamine reaction :
32. (d) R– NH2+3KOH+CHCl3 ¾¾®
NH2 NHCOCH3 R –N C+3KCl+3H2O
Reduction CH
(CH CO) O
¾
Br
¾¾¾
2
® 36. (d) CH3CN ¾¾¾® 3 CH 2 NH2
¾¾¾¾
3 2
® CH COOH
3 HONO
CH3 CH 2 OH + N 2+ HO2¬
CH3 CH3
(A) 37. (d) Aniline when treated with acetic anhydride
NHCOCH3 NH2 forms acetanilide (nucleophilic substitution)
O
Br +
H /H O Br
¾¾2® NH2 NH – C – CH3
O O
O
CH3 CH3 CH 3–C–O–C–CH 3
¾¾¾¾¾¾® + CH3– C – OH
(B) (C)
CºN
38. (b) Acetonitrile (Methyl cyanide) on treatment
33. (b) + CH3MgBr ¾¾ with conc. HCl give acetamide.
®
Conc .HCl
OCH3 CH 3C º N ¾¾ ¾ ¾
¾® CH 3CONH 2.
Acetonitri le Acetamide
H3C –C = NMgBr H3C –C = NH
39. (b) Acetamide and ethylamine can be
H O+ distinguished by heating with NaOH solution.
¾¾®
3
Acetamide evolves NH3 but ethylamine does not.
OCH3
OCH3 D
COCH3 CH 3CONH 2 + NaOH ¾¾®
H O
+ CH 3COONa + NH 3
¾¾®
3
OCH3 ® No reaction.
CH 3 CH 2 NH 2 + NaOH ¾¾
34. (c) The mechanism of Hoffmann bromamide
40. (a) Any primary amine means both aliphatic as
reaction is
well as aromatic but monoalkylamines means
(i) RCONH 2 + Br2 ® RCONHBr + HBr
only 1° aliphatic amines. Therefore, option (a) is
-
OH
(ii) RCONHBr + HBr ¾¾¾ ® correct while (d) is wrong.
·-·
R — CO N Br + H 2O RNH2 + CHCl3 + 3KOH ¾¾®
RNC + 3KCl + 3H 2 O
isocyanide
Amines 303
41. (c) Only 1° amides (i.e. RCONH2) in the present 46. (a) When nitro compound is reduced with a
case undergo Hofmann bromamide reaction. neutral reducing agent (Zn dust + NH4Cl) the
RCONH2 + Br2 + 4KOH ¾¾ ® corresponding hydroxyl amine is formed
R - NH 2 + 2KBr + K 2CO3 + 2H 2O Zn dust + NH Cl
C6 H 5 NO 2 + 4[H] ¾¾¾¾¾¾¾
4
®
(Hofmann's bromamide reaction) C6 H 5 NHOH
Phenyl hydroxyl amine
NH 2 47. (a)
42. (d) NH2 N = N – Cl
N 2 Cl ¾¾¾¾¾¾®
+
CH3
H N
NaNO2/HCl CH3
¾¾ ¾¾®
(273–278K)
¾¾¾¾¾®
N=N NH 2 (X)
CH3
43. (b) Arene diazonium salts are most stable N=N N
among the given options because of the CH3
dispersal of +ve charge on the benzene ring (Y)
due to resonance. 48. (b) HONO2 + H2SO4
Base Acid
Resonance structures of arene diazonium
® NO +2 + H 2 O + HSO 4-
¾¾
N º ··
Å Å Å
N N= N N= N Nitric acid acts as a base by accepting a proton.
··
··
·· ·· 49. (d)
Å + –
¬¾® ¬¾® NH2 N2 Cl
NaNO
Å ¾¾®
2
HCl
Å
N º ··
Å Å
··
N = ··
N N NºN Arene diazonium salt
¾¾®
Å CuCN
¬¾® ¬¾® ¬¾® Å
5-resonance structures resonance hybrid H2/Ni
44. (b) HNO2

NO2 NO2
¾®
Br +H3PO2+H2O Br Benzyl a lcohol
+H3 PO3 + HCl + N2 NaNO 2 ,HCl

ÅN2Cl
–
50. (c) N H2 ¾¾¾ ¾¾ ¾®
0-5°C
NO 2 N(CH3)2
NO 2
N 2 Cl
HNO / H SO
H+
3 2 4
45. (a) ¾¾¾¾¾¾®
80 -100°C
NO 2
Nitrobenzene 1,3 - Dinitrobenzene N(CH3)2
N=N
EBD_8336
304 CHEMISTRY
51. (c) 53. (b) Azo dyes can be prepared by diazotizing an
NO2 N C aromatic amine and subsequent coupling with a
suitable aromatic phenol or amine
Sn + HCl CHCl +KOH
3
¾¾¾¾®
reduction
¾¾¾¾¾®
Nitrobenzene N =NCl + H N(CH3)2
(A) (B) (C)
NH–CH3
Diazonium chloride N,N-dimethylaniline
Re duction
¬¾ ¾¾ ¾¾
Na/C2H5OH
¾® N=N N(CH3)2
N-methylaniline
p-Dimethyl amino azobenzene
–
N2+ Cl OH p-Dimethyl amino azobenzene is used as a dye
for colouring polishes, wax products and soap.
H O
¾¾¾
2 ®
+ N2+HCl
52. (b)
CH3 CH3
p-cresol
Biomolecules 305
28 Biomolecules
2020 2019 2018 2017 2016

hydrolysis of
1 E
Carbohydrates and sucrose
lipids reducing/non
1 E
reducing sugars
Amino acids and aminoacids/
1 E 1 E 1 E 1 A 1 E
proteins proteins
Nucleic acid and structure of
1 A
enzymes DNA/RNA
Topic 1: Carbohydrates and Lipids (c) CH = NOH (d) CH = NOH

HO – C – H H – C – OH
1. Sucrose on hydrolysis gives: [2020]
(a) a-D-Glucose + b-D-Glucose H – C – OH HO – C – H
(b) a-D-Glucose + b-D-Fructose HO – C – H H – C – OH
(c) a-D-Fructose + b-D-Fructose H – C – OH H – C – OH
(d) a-D-Glucose + b-D-Fructose
CH2OH CH2OH
2. Which one given below is a non-reducing sugar?
4. Which one of the following sets of monosac-
(a) Maltose (b) Lactose [2016]
charides forms sucrose? [2012]
(c) Glucose (d) Sucrose (a) a–D-Galactopyranose and
3. D (+) glucose reacts with hydroxylamine and a–D-Glucopyranose
yields an oxime. The structure of the oxime would (b) a–D-Glucopyranose and
be : [2014] b–D-Fructofuranose
(a) CH = NOH (b) CH = NOH (c) b–D-Glucopyranose and
a–D- Fructofuranose
H – C – OH HO – C – H
(d) a–D-Glucopyranose and
HO – C – H HO – C – H b–D-Fructopyranose
HO – C – H H – C – OH 5. Which one of the following statements is not
true regarding (+) Lactose ? [2011]
H – C – OH H – C – OH (a) On hydrolysis (+) Lactose gives equal
CH2OH CH2OH amount of D(+) glucose and D(+)
galactose.
EBD_8336
306 CHEMISTRY
(b) (+) Lactose is a b-glycoside formed by the 15. Mg is present in which of the following : [2000]
union of a molecule of D(+) glucose and a (a) Starch (b) Chlorophyll
molecule of D(+) galactose. (c) Both (d) None
(c) (+) Lactose is a reducing sugar and does 16. Which of the following is the sweetest sugar?
not exhibit mutarotation. (a) Sucrose (b) Glucose [1999]
(d) (+) Lactose, C12H22 O11 contains 8-OH (c) Fructose (d) Maltose
groups. 17. In cells, the net production of ATP molecules
6. Which one of the following does not exhibit the generated from one glucose molecule is [1999]
phenomenon of mutarotation ? [2010] (a) 46 (b) 32
(a) (+) – Sucrose (b) (+) – Lactose (c) 36 (d) 40
(c) (+) – Maltose (d) (–) – Fructose 18. The number of molecules of ATP produced in
7. Fructose reduces Tollen’s reagent due to [2010] the lipid metabolism of a molecule of palmitic
(a) enolisation of fructose followed by acid is [1998]
conversion to aldehyde by base (a) 130 (b) 36
(b) asymmetric carbons (c) 56 (d) 86
(c) primary alcoholic group 19. Glucose molecule reacts with 'X' number of
(d) secondary alcoholic group molecules of phenylhydrazine to yield osazone.
8. The cell membranes are mainly composed of The value of 'X' is [1998]
(a) fats (b) proteins [2005] (a) four (b) one
(c) phospholipids (d) carbohydrates (c) two (d) three
9. Number of chiral carbons in b – D – (+) – glucose 20. Sucrose in water is dextro-rotatory, [a]D= + 66.4º.
is [2004] When boiled with dilute HCl, the solution
(a) five (b) six becomes leavo-rotatory, [a]D= –20º. In this
(c) three (d) four process, the sucrose molecule breaks into[1996]
10. Glycolysis is [2003] (a) L-glucose + D-fructose
(a) conversion of glucose to haem (b) L-glucose + L-fructose
(b) oxidation of glucose to glutamate (c) D-glucose + D-fructose
(c) conversion of pyruvate to citrate (d) D-glucose + L-fructose
(d) oxidation of glucose to pyruvate 21. The a-D glucose and b-D glucose differ from
11. Phospholipids are esters of glycerol with [2003] each other due to difference in carbon atom with
(a) Three phosphate groups respect to its [1995]
(b) Three carboxylic acid residues (a) Conformation
(c) Two carboxylic acid residues and one (b) Configuration
phosphate group (c) Number of OH groups
(d) One carboxylic acid residue and two (d) Size of hemiacetal ring
phosphate groups 22. On hydrolysis of starch, we finally get [1991]
12. Cellulose is a polymer of [2002] (a) Glucose (b) Fructose
(a) Glucose (b) Fructose (c) Both (a) and (b) (d) Sucrose
(c) Ribose (d) Sucrose
13. Which of the following gives positive Fehling Topic 2: Amino Acids and Proteins
solution test ? [2001] 23. Which of the following is a basic amino acid ?
(a) Protein (b) Sucrose (a) Alanine (b) Tyrosine [2020]
(c) Glucose (d) Fats (c) Lysine (d) Serine
14. Which is correct statement? [2001] 24. Which structure(s) of proteins remain(s) intact
(a) Starch is a polymer of a-glucose during denaturation process?
(b) In cyclic structure of fructose, there are four [NEET Odisha, 2019]
carbons and one oxygen atom (a) Tertiary structure only
(c) Amylose is a component of cellulose (b) Both secondary and tertiary structures
(d) Proteins are composed of only one type of (c) Primary structure only
amino acids (d) Secondary structure only
Biomolecules 307
25. The non-essential amino acid among the H O H
following is: [2019] | | | || | | | | |
(a) valine (b) leucine (d) - N - C- C- C - N - C- C- N- C - C- C-
| | | | | || | |
(c) alanine (d) lysine H O
26. Which of the following compounds can form a 32. The correct statement in respect of protein
zwitterion? [2018] haemoglobin is that it [2004]
(a) Aniline (b) Acetanilide (a) functions as a catalyst for biological reactions
(c) Glycine (d) Benzoic acid (b) maintains blood sugar level
27. Which of the following statements is not (c) acts as an oxygen carrier in the blood
correct : [2017] (d) forms antibodies and offers resistance to
(a) Ovalbumin is a simple food reserve in egg- dieases
white 33. The helical structure of protein is stabilized by
(b) Blood proteins thrombin and fibrinogen are [2004]
involved in blood clotting (a) dipeptide bonds (b) hydrogen bonds
(c) Denaturation makes the proteins more active (c) ether bonds (d) peptide bonds
(d) Insulin maintains sugar level in the blood
34. Which is not a true statement? [2002]
of a human body
(a) a-Carbon of a-amino acid is asymmetric
28. In a protein molecule various amino acids are
linked together by [2016] (b) All proteins are found in L-form
(a) a-glycosidic bond (b) b-glycosidic bond (c) Human body can synthesize all proteins
(c) peptide bond (d) dative bond they need
29. Which of the statements about "Denaturation" (d) At pH = 7 both amino and carboxylic
given below are correct ? [2011 M] groups exist in ionised form
(a) Denaturation of proteins causes loss of O
|| · ·
secondary and tertiary structures of the protein. 35. For - C - N H - (peptide bond) [2001]
(b) Denturation leads to the conversion of Which statement is incorrect about peptide bond?
double strand of DNA into single strand
(a) C — N bond length in proteins is longer
(c) Denaturation affects primary strucrture
than usual bond length of the C — N bond
which gets distorted
(b) Spectroscopic analysis shows planar
(a) (b) and (c) (b) (a) and (c)
(c) (a) and (b) (d) (a), (b) and (c) structure of the — C— NH — group
||
30. Which functional group participates in O
disulphide bond formation in proteins? [2005] (c) C — N bond length in proteins is smaller
(a) Thioester (b) Thioether than usual bond length of the C—N bond
(c) Thiol (d) Thiolactone (d) None of the above
31. Which one of the following structures 36. The number of essential amino acids in man is
represents the peptide chain? [2004] (a) 8 (b) 10 [2000]
H O (c) 18 (d) 20
| | || 37. The dominant cation in the blood plasma
(a) - N - C - N - C - NH - C - NH - (extracellular fluid) is [1999]
|| | |
O H (a) potassium (b) calcium
H H (c) magnesium (d) sodium
| | | | | | | | 38. The reactions of (a) oxygen and (b) carbon
(b) - N - C - C- C- C- N - C- C- C- monoxide with haeme (the prosthetic group of
|| | | | | | | haemoglobin) give [1997]
O (a) only oxygen-haeme complex
H H H O (b) only carbon monoxide-haeme complex
| | | | | | ||
(c) both oxygen-haeme and carbon monoxide-
(c) - N - C- C - N - C - C - N - C - C -
| || | || | haeme complexes but oxygen-haeme
O O complex is more stable
EBD_8336
308 CHEMISTRY
(d) both oxygen-haeme and carbon monoxide- 46. The segment of DNA which acts as the
haeme complexes but carbon monoxide- instrumental manual for the synthesis of the
haeme complex is more stable protein is: [2009]
39. Identify an element amongst the following which (a) ribose (b) gene
is responsible for oxidation of water to O2 in (c) nucleoside (d) nucleotide
biological processes [1997] 47. In DNA, the complimentary bases are:
(a) Fe (b) Mn [1998, 2008]
(c) Mo (d) Cu (a) Adenine and thymine; guanine and cytosine
40. In reference to biological role, Ca2+ ions are (b) Adenine and thymine ; guanine and uracil
important in [1996] (c) Adenine and guanine; thymine and cytosine
(a) triggering the contraction of muscles
(d) Uracil and adenine; cytosine and guanine
(b) generating right electrical potential across
48. RNA and DNA are chiral molecules, their
cell membrane
chirality is due to [2007]
(c) hydrolysis of ATP
(d) defence mechanism (a) chiral bases
41. A reagent suitable for the determination of (b) chiral phosphate ester units
N-terminal residue of a peptide is [1996] (c) D-sugar component
(a) p-Toluenesulphonyl chloride (d) L-sugar component.
(b) 2, 4-Dinitrophenylhydrazine 49. During the process of digestion, the proteins
(c) Carboxypeptidase present in food materials are hydrolysed to
(d) 2, 4-Dinitrofluorobenzene amino acids. The two enzymes involved in the
42. Which of the following protein destroy the process
antigen when it enters in body cell? [1995] Proteins ¾¾¾¾¾Enzyme (A)
® Polypeptides
(a) Antibodies (b) Insulin Enzyme (B)
(c) Chromoprotein (d) Phosphoprotein ¾¾¾¾¾® Amino acids
are respectively [2006]
Topic 3: Nucleic Acid and Enzymes (a) Diastase and Lipase
(b) Pepsin and Trypsin
43. The correct statement regarding RNA and DNA, (c) Invertase and Zymase
respectively is [2016] (d) Amylase and Maltase
(a) The sugar component in RNA is arabinose 50. A sequence of how many nucleotides in
and the sugar component in DNA is messenger RNA makes a codon for an amino
2'-deoxyribose. acid? [2004]
(b) The sugar component in RNA is ribose and the (a) Three (b) Four
sugar component in DNA is 2'-deoxyribose. (c) One (d) Two
(c) The sugar component in RNA is arabinose 51. The enzyme which hydrolyses triglycerides to
(d) The sugar component in RNA is fatty acids and glycerol is called [2004]
2'-deoxyribose and the sugar component (a) Maltase (b) Lipase
in DNA is arabinose (c) Zymase (d) Pepsin
44. In DNA, the linkages between different 52. Chargaff's rule states that in an organism [2003]
nitrogenous bases are: [NEET Kar. 2013] (a) Amounts of all bases are equal
(a) peptide linkage (b) phosphate linkage (b) Amount of adenine (A) is equal to that of
(c) H-bonding (d) glycosidic linkage thymine (T) and the amount of guanine (G)
45. Which one of the following, statements is is equal to that of cytosine (C)
incorrect about enzyme catalysis? [2012] (c) Amount of adenine (A) is equal to that of
(a) Enzymes are mostly proteinous in nature. guanine (G) and the amount of thymine (T)
(b) Enzyme action is specific. is equal to that of cytosine (C)
(c) Enzymes are denaturated by ultraviolet
(d) Amount of adenine (A) is equal to that of
rays and at high temperature.
cytosine (C) and the amount of thymine
(d) Enzymes are least reactive at optimum
(T) is equal to that of guanine (G)
temperature.
Biomolecules 309
53. Enzymes are made up of [2002] Topic 4: Vitamins and Hormones
(a) Edible proteins
(b) Proteins with specific structure 59. Which of the following hormones is produced
(c) Nitrogen containing carbohydrates under the condition of stress which stimulates
(d) Carbohydrates glycogenolysis in the liver of human beings?
54. Which of the following is correct about H- (a) Thyroxin (b) Insulin [2014]
bonding in nu cleotide? [2001] (c) Adrenaline (d) Estradiol
(a) A --- A and T --- T (b) G --- T and A --- C 60. Deficiency of vitamin B1 causes the disease
(c) A --- G and T --- C (d) A --- T and G --- C (a) Convulsions (b) Beri-Beri [2012]
55. Which one of the following chemical units is (c) Cheilosis (d) Sterility
certainly to be found in an enzyme? [1997] 61. Which of the following hormones contains
OH iodine? [2009]
O
H (a) Testosterone (b) Adrenaline
O (c) Thyroxine (d) Insulin
(a) (b) N—C
HO 62. Which one of the following is an amine hormone ?
HO O O (a) Thyroxine (b) Oxypurin [2008]
O (c) Insulin (d) Progesterone
O O R 63. Which of the following is water-soluble? [2007]
(a) Vitamin E (b) Vitamin K
O R (c) Vitamin A (d) Vitamin B
(c) (d) 64. Which one of the following is a peptide
O R
hormone ? [2006]
O (a) Testosterone (b) Thyroxin
56. Chemically considering, digestion is basically (c) Adrenaline (d) Glucagon
[1994] 65. The human body does not produce [2006]
(a) Anabolism (b) Hydrogenation (a) Vitamins (b) Hormones
(c) Hydrolysis (d) Dehydrogenation. (c) Enzymes (d) DNA
57. Enzymes take part in a reaction and [1993] 66. The hormone that helps in the conversion of
(a) decrease the rate of a chemical reaction glucose to glycogen is [2004]
(b) increase the rate of a chemical reaction (a) Cortisone (b) Bile acids
(c) both (a) and (b) (c) Adrenaline (d) Insulin
(d) none of these 67. Vitamin B12 contains [2003]
58. The couplings between base units of DNA is (a) Ca(II) (b) Fe(II)
through : [1992] (c) Co(III) (d) Zn(II)
(a) Hydrogen bonding 68. Which of the following is a steroid hormone?
(b) Electrostatic bonding [1999]
(c) Covalent bonding (a) Cholesterol (b) Adrenaline
(d) van der Waals forces (c) Thyroxine (d) Progesterone
ANSWER KEY
1 (b) 8 (c) 15 (b) 22 (a) 29 (c) 36 (b) 43 (b) 50 (a) 57 (b) 64 (d)
2 (d) 9 (a) 16 (c) 23 (c) 30 (c) 37 (d) 44 (c) 51 (b) 58 (a) 65 (a)
3 (d) 10 (d) 17 (c) 24 (c) 31 (c) 38 (d) 45 (d) 52 (b) 59 (c) 66 (d)
4 (b) 11 (c) 18 (a) 25 (c) 32 (c) 39 (b) 46 (b) 53 (b) 60 (b) 67 (c)
5 (c) 12 (a) 19 (d) 26 (c) 33 (b) 40 (a) 47 (a) 54 (d) 61 (c) 68 (d)
6 (a) 13 (c) 20 (c) 27 (c) 34 (b) 41 (d) 48 (c) 55 (b) 62 (a)
7 (a) 14 (a) 21 (b) 28 (c) 35 (a) 42 (a) 49 (b) 56 (c) 63 (d)
EBD_8336
310 CHEMISTRY
Hints & Solutions

HO
1. (b) Sucrose ¾¾¾¾®
Hydrolysis a-D-Glucose + CH2 OH
b-D-Fructose O CH2 O
¾¾
® + H2O
OH HO
CH2OH O
OH CH2
O O OH OH
H H HOH2C OH OH
H Sucrose
OH H H HO
HO O Sucrose is a disaccharide of a–D-Glucopyranose
CH2OH
and b–D-Fructofuranose.
H OH OH H
The glycoside linkage is between C1 and C2.
a-D-Glucose b-D-Fructose
Sucrose on hydrolysis brings about a change in the 5. (c) All reducing sugar shows mutarotation.
sign of rotation from dextro to laevo and the product
is called as invert sugar. Reducing sugars have hydroxyl group at the
anomeric C1 position. In solution, a carbohydrate
2. (d) Sucrose is non-reducing disaccharide as can open up to its aldehyde form. Hence, it can
the two monosaccharide units are linked through switch configuration between a– and b– forms.
their respective carbonyl groups. 6. (a) Sucrose does not have free — CHO or CO
Only carbonyl group can be reduced as with other
group, hence it does not undergo mutarotation.
carbons, –OH group is attached.
7. (a) Fructose, a ketose as the substrate, under
the alkaline medium of Tollen’s reagent, a part of
fructose is transformed into glucose and
3. (d) Glucose reacts with hydroxyl amine to form
mannose, both aldoses. Then these aldoses give
an oxime.
positive silver mirror test.
CHO CH=N–OH
8. (c) Cell membranes (Plasma membranes) con-
H OH H OH stitutes bilayer of phospholipid with embedded
HO H NH2OH HO H proteins. In humans, lipids accounts for upto
¾¾¾ ®
H OH H OH 79% of cell membrane.
H OH H OH 9. (a)
CH2–OH CH2–OH
HO 1
D(+)glucose C H
2
H OH
4. (b) HO 3
CH2 OH HO H
4 O b – D –(+)– Glucose
O CH2 H OH
O
OH + OH 5
OH H
HO H2C
OH
OH CH2OH
OH OH
a-D-Glucopyranose b-D-Fructofuranose Carbon atoms from C 1 to C 5 are chiral
Biomolecules 311
10. (d) It is a common pathway for both the aerobic ketonic group, the third molecule of
& anaerobic respiration in which 1 glucose phenylhydrazine condenses to glucosazone.
molecule is converted to 2 molecules of pyruvate. Therefore, the value of X is 3
11. (c) Phospholipids are derivatives of glycerol CHO + H2NNHC6H5 CH = NNHC6H5
in which two of the hydroxyl groups are
esterified with fatty acids while the third is CHOH CHOH
esterified with some derivative of phosphoric warm
¾¾®
acid with some alcohol such as choline, (CHOH)3 (CHOH)3
ethanolamine, serine or inositol.
CH2OH CH2OH
R¢¢
Glucose Glucose Phenylhydrozone
O
¾¾®
H2NNHC6H5
O = P – O – CH2 O
OH CH – O – C –R¢ CH = NNHC6H5 CH = NNHC6H5
CH2O – C –R H2NNHC6H5
C = NNHC6H5 C=O
– H2 O
O
12. (a) We know that cellulose (C 6 H12 O 6 ) n is (CHOH)3 (CHOH)3
the chief constituent of cell walls of plants. It is
the most abundant organic substance found in CH2OH CH2OH
nature. It is a polymer of glucose with 3500 Glucosazone keto compound of glucose
phenyl hydrazone
repeating units in a chain.
20. (c) The hydrolysis of sucrose by boiling with
13. (c) Glucose contain aldehyde group. Hence, it
mineral acid or by enzyme invertase or sucrase
gives positive fehling solution test.
produces a mixture of equal molecules of D(+)
14. (a) Starch is also know as amylum which
glucose and D(–) Fructose.
occurs in all green plants. A molecule of starch
(C 6 H10 O5 ) n is built of a large number of HCl
C12 H 22 O11 + H 2 O ¾¾¾
® C6 H12 O6 + C6 H12 O6
a-glucose ring joined through oxygen-atom. sucrose D - glu cos e D - Fructose
15. (b) Chlorophyll contain Mg. [ a D ]=+66.5º [ aD ]=+52.5º [a D ]=-92º
144444244444 3
16. (c) Fructose is the sweetest sugar. Invert sugar,[ a D ]=-20º
17. (c) C 6 H12 O 6 + 6O 2 + 2 ATP ¾ ¾® 21. (b) a-D glucose and b-D glucose are the
6CO 2 + 6H 2O + 38 ATP Molecules isomers which differ in the orientation
Net total number of ATP molecules evolved = (configuration) of H and OH groups around C1
36 molecules. atom.
18. (a) In the lipid metabolism, when palmitic acid
is oxidised, two carbon fragments are removed
H —C1—OH HO —C1—H
sequentially to form acetyl coenzyme. It enters
the citric acid cycle for production of 130 ATP. H —C2—OH H —C2—OH
O O
19. (d) Glucose reacts with one molecule of HO —C3—H HO —C —H
3
phenyl hydrazine to give phenyl hydrazone.

H —C4—OH H —C4—OH
When warmed with excess of phenylhydrazine,
5 5
the secondary alcoholic group adjacent to the H —C H —C
6 6
aldehyde group is oxidised by another molecule CH2OH CH2OH
of phenylhydrazine to a ketonic group. With this a– D - glucose b– D - glucose
EBD_8336
312 CHEMISTRY
22. (a) Manufacture - By hydrolysis of starch with
HO 2CCHC H 2S - SCH 2 CHC O 2 H
hot dil. mineral acids | |
NH 2 NH2
(C6 H10O5 ) n ® (C6 H10O5 )n ® Cystine
Starch Dextrin
31. (c) The bond formed between two amino acids
H O
C12 H 22 O11 ¾¾¾
2 ® 2C H O
6 12 6 by the elimination of a water molecule is called
Maltose Glucose a peptide linkage or bond. The peptide bond is
simply another name for amide bond.
–
23. (c) H2N – (CH2)4 – CH – COO
+ - C OH + H — N— ¾¾
® — C– N— + H2 O
NH3 | | || |
Lysine O H O H
Carboxyl group Amine group of Peptide bond
of one amino acid other amino acid
Since it contains more number of –NH2 groups
as compared to –COOH groups, hence it is basic The product formed by linking amino acid
amino acid. molecules through peptide linkages. —CO—
24. (c) During denaturation primary structure of NH—, is called a peptide.
proteins remain intact while secondary and 32. (c) Haemoglobin acts as an oxygen carrier in
tertiary structures are destroyed. the blood since it reacts with oxygen to form
unstable oxyhaemoglobin which easily breaks
25. (c) Alanine is non-essential amino acid.
to give back haemoglobin and oxygen.
26. (c)
HOOC – CH 2 – NH 2 33. (b) Hydrogen bonding between different units
Glycine is responsible for holding helix in a position.
+
OOC – CH 2 – NH 3 NH group in one unit is linked to carbonyl
Zwitter ion oxygen of the third unit by hydrogen bonding.
27. (c) Due to denaturation of proteins, helix get
uncoiled and protein loses its biological activity. The a-helix structure is formed when the chain of
a-amino acids coils as a right handed screw (called
28. (c) Peptide bond
a-helix) because of the formation of hydrogen
bonds between amide groups of the same peptide
— C — NH —
|| chain.
O 34. (b) All proteins are not found in L-form but
29. (c) When the proteins are subjected to the they may be present in form of D or L
action of heat, mineral acids or alkali, the water 35. (a) Due to resonance C — N bond in protein
soluble form of globular protein changes to water acquires double bond character and is smaller
insoluble fibrous protein. This is called than usual C — N bond.
—
denaturation of proteins. During denaturation, O O
secondary and tertiary structures of protein C NH C NH
Å
destroyed but primary structures remains intact. 36. (b) There are 20 amino acid in man, out of
R -S-S- R which 10 amino acids are essential amino acids.
30. (c) 2R - S - H
Thiol Disulphide
Essential amino acids are supplied to our bodies
Example : by food which we take because they cannot be
[O] synthesised in the body. These are (i) valine (ii)
2HO 2C CHC H 2SH leucine (iii) Isoleucine (iv) Phenylalanine (v)
| [H]
NH2 Threonine (vi) Methionine (vii) Lysine (viii)
Cysteine Tryptophan (ix) Arginine (x) Histidine.
Biomolecules 313
37. (d) Na+, Cl– and HCO3– are the electrolytes

present in blood plasma. Na+ and Cl– helps in H+
maintainence of osmotic pressure and fluid
balance.
O2N NH CHCOOH
38. (d) |
¾® HbCO (stable compound)
Hb + CO ¾ R1 +
carboxy haemoglobin NO2 (DNP derivative)
Hb + O 2
HbO 2 H 2 NCHCOOH + H 2 NCHCOOH
| |
oxyhaemoglobin (unstable). R2 R3
39. (b) Water oxidation is catalyzed by a
(Amino acid mixture)
manganese containing cofactor. Here, cofactor
is a species which increases the activity of an 42. (a) When antigens enter in to the body cells
enzyme. and destroy them, then antibodies being
40. (a) proteins are synthesised in the body and
(a) Ca2+ ions are responsible for triggering combine with antigens and destroy these
contraction of muscles and functions of antigens by forming inactive complexes.
nerves. Therefore, antibodies protein destroy antigens.
(b) K+ (and Na + ions) are responsible for 43. (b) Sugar in DNA is 2-deoxyribose whereas
maintaining right electrical potential across sugar in RNA is ribose.
cell membrane.
(c) Mg2+ act as a cofactor for hydrolysis of 44. (c) The base pairs of the two strands of DNA
ATP. are linked together through H-bonds.
41. (d) 2, 4- Dinitroflurobenzene, also known as 45. (d) Enzymes are most reactive at optimum
Sanger's reagent, reacts with the H2N - group of temperature. The optimum temperature for
the peptide to from 2, 4- dinitrophenyl (DNP) enzyme activity is the human body temp.
derivative of the peptide. The DNP derivative of 46. (b) The DNA sequence that codes for a
the peptide is hydrolysed to give DNP derivative specific protein is called a Gene and thus every
of the single amino acid protein in a cell has a corrosponding gene.
H 2 NCHCONH CHCONH CHCOOH + 47. (a) In DNA the complimentary bases are
| | |
R1 R2 R3 Adenine and thymine;
Guanine and cytosine.
The genetic information for cell is contained in
O2N F ¾
¾®
the sequence of bases A, T, G and C in DNA
molecule.
NO2
2, 4, Dinitrofluoro benzene Adenine pair with thymine with two hydrogen
bonds and Guanine pairs with cytosine with three
hydrogen bonds.
O2N NHC HCONH C HCONH C HCOOH
| | |
R1 R2 R3 48. (c) Each nucleic acid consists of a pentose
NO2 sugar a heterocyclic base, and phosphoric acid.
The sugar present in DNA is -D (–) -2-deoxy
(DNP derivative of polypeptide) ribose and the sugar present in RNA is D (–)-
EBD_8336
314 CHEMISTRY
ribose. The chirality of DNA and RNA molecules 53. (b) Enzymes are made up of protein with
are due to the presence of sugar components. specific structure.
54. (d)
5
O
HOCH2 OH O Deoxyribose-Adenine ... Thymine -Deoxyribose O
4 1
OH P P OH
H H O Deoxyribose-Guanine ... Cytosine -Deoxyribose
O
H H OH P Deoxyribose-Guanine ... Cytosine -Deoxyribose
P OH
O O
3 2
OH OH OH P Deoxyribose-Adenine ... Thymine -Deoxyribose
P OH
D(–)–ribose
The hydrogen bonds are formed between the base
C1, C2, C3 and C4 are chiral carbons. (shown by dotted lines). Because of size and
geometrics of the bases, the only possible pairing
O in DNA are between G (Guanine) and C (Cytosine)
5
HOCH2 OH through three H-bonds and between A (Adenosine)
4 1 and T (Thymine) through two H-bonds.
H H 55. (b) Peptide bonds are present in enzyme.
H H
3 2 H
OH H
N C
D(–) -2-deoxy ribose
C1, C3 and C4 are chiral carbons. O
49. (b) Pepsin and Trypsin are two enzymes 56. (c) In digestion, large molecules are
involved in the process (hydrolysis of proteins) hydrolysed to give smaller molecules. For
Pepsin
Proteins ¾¾¾¾® Polypeptides example, protein gets hydrolysed to amino acids.
Proteases
Thus, chemically considering, digestion is
Trypsin basically hydrolysis.
® Amino acids
¾¾¾¾¾¾¾¾¾¾
Chemotrypsin 57. (b) Enzymes being biocatalyst can increase the
(Pancreatic juice Intestine)
rate of a reaction upto 10 million times. Even
50. (a) The sequence of bases in mRNA are read very small amount can accelerate a reaction.
in a serial order in groups of three at a time.
Each triplet of nucleotides (having a specific 58. (a) DNA consists of two polynucleotide
sequence of bases) is known as codon. Each chains, each chain forms a right handed helical
codon specifies one amino acid. spiral with ten bases in one turn of the spiral.
The two chains coil to double helix and run in
There are four bases A, G, C,T, therefore, 4 3 = 64 opposite direction held together by hydrogen
triplets or codons are possible. bonding.
59. (c) Adrenaline is a hormone produced by
51. (b) Triglycerides are lipids, hence these are
adrenal glands during high stress or exciting
hydrolysed by lipases to glycerol and fatty acids.
situations. This powerful hormone is part of the
A G human body’s acute stress response system,
52. (b) = =1
T C also called the fight or flight response.
Amount of A = T and that of G = C. 60. (b) Beri-Beri.
Biomolecules 315
61. (c) Thyroxine is the only hormone among the Vitamin H also known as Biotin is part of B
given choices that contains iodine. Its structure complex group of vitamin.
is as follows:
64. (d) Testosterone and Adrenaline are steroid
OH hormone, Thyroxin is a non-steroid hormone and
glucagon is a peptide hormone.
I I
65. (a) Vitamins are organic substances which
does not provide energy but are essential for
I healthy growth and proper functioning of body.
O Vitamins are not synthesized inside human body
but they are essential part of our diet.
66. (d) Insulin helps in converting glucose to
I
glycogen.
67. (c) Vit B12 also called Cyanocobalamin, is
H2N COOH
anti-pernicious anaemia vitamin.
68. (d) Progesterone (Gestogens) is a steroid
62. (a) Thyroxine is an amino hormone.
hormone, which controls the development and
63. (d) Vitamin B is water soluble whereas all other maintainance of pregnancy. Thryoxine and
are fat soluble. Adrenaline are Amine hormones.
EBD_8336
316 CHEMISTRY
29 Polymers
2020 2019 2018 2017 2016

natural polymers 1 E
Classification of
polymers biodegradable
1 E
polymers
properties of
1 A
Preparation and polymers
properties of polymers properties of
natural rubber
Topic 1: Classification of Polymers 5. Of the following which one is classified as

polyester polymer ? [2011]
1. Which of the following is a natural polymer?
(a) Terylene (b) Bakelite
(a) poly (Butadiene-styrene) [2020]
(c) Melamine (d) Nylone-66
(b) polybutadiene
(c) poly (Butadiene-acrylonitrile) 6. [NH(CH 2 ) 6 NHCO(CH 2 ) 4 CO]n is a
(d) cis-1, 4-polyisoprene [2006]
2. The biodegradable polymer is: [2019] (a) addition polymer
(a) nylon-6, 6 (b) thermosetting polymer
(b) nylon 2-nylon 6 (c) homopolymer
(c) nylon-6 (d) copolymer
(d) Buna-S 7. Which one of the following is a chain growth
3. Nylon is an example of : [NEET 2013] polymer? [2004]
(a) Polysaccharide (b) Polyamide (a) Starch (b) Nucleic acid
(c) Polythene (d) Polyester (c) Polystyrene (d) Protein
4. Which one of the following is not a 8. In elastomer, intermolecular forces are [1995]
condensation polymer ? [2012] (a) strong (b) weak
(a) Melamine (b) Glyptal (c) nil (d) none of these
(c) Dacron (d) Neoprene
Polymers 317
Topic 2: Preparation and Properties 14. Which of the following organic compounds
of Polymers polymerizes to form the polyester Dacron?
9. Regarding cross-linked or network polymers, [2014]
which of the following statements is incorrect? (a) Propylene and para HO—(C6H4)— OH
[2018] (b) Benzoic acid and ethanol
(a) They contain covalent bonds between (c) Terephthalic acid and ethylene glycol
various linear polymer chains.
(d) Benzoic acid and para HO–(C6H4)—OH
(b) They are formed from bi- and tri-functional
15. Which is the monomer of Neoprene in the
monomers.
following ? [NEET 2013]
(c) They contain strong covalents bonds in
their polymer chains. (a) CH 2 = C ¾ CH = CH 2
(d) Examples are bakelite and melamine. ½
CH 3
10. Natural rubber has [2016]
(a) all cis-configuration (b) CH 2 = C ¾ CH = CH 2
(b) all trans-configuration Cl
(c) alternate cis-and trans-configuration (c) CH2 = CH ¾ C º CH
(d) random cis-and trans-configuration (d) CH2 = CH ¾ CH = CH2
11. Biodegradable polymer which can be produced 16. Which of the following statements is false?
from glycine and aminocaproic acid is : [2015] [2012]
(a) PHBV (b) Buna - N (a) Artificial silk is derived from cellulose.
(c) Nylon 6, 6 (d) Nylon 2- nylon 6
(b) Nylon-6, 6 is an example of elastomer.
12. Caprolactum is used for the manufacture of :
(c) The repeat unit in natural rubber is
[2015 RS] isoprene.
(a) Nylon - 6 (b) Teflon (d) Both starch and cellulose are polymers of
(c) Terylene (d) Nylon - 6,6 glucose.
13. Which one of the following is an example of a 17. Which one of the following sets forms the
thermosetting polymer? [2014] biodegradable polymer? [2012 M]
(a) ( CH 2 - C = CH - CH 2 ) n (a) CH2 = CH – CN and CH2 = CH – CH = CH2
|
Cl (b) H2N – CH2 – COOH and
H2N–(CH2)5 – COOH
(b) ( CH 2 - CH ) n
| (c) HO – CH2 – CH2 – OH and
Cl
H H O O HOOC COOH
| | || ||
(c) ( N - (CH 2 )6 - N - C - (CH 2 )4 - C )n
OH OH (d) CH = CH2 and

CH2 CH2
(d) CH2 = CH – CH = CH2
n
EBD_8336
318 CHEMISTRY
18. Which of the following structures represents 22. The monomer of the polymer; [2005]
neoprene polymer? [2010] CH3
CH3
(a) –(CH 2 – C = CH – CH 2 –) n |
Å
| ÚÚÚÚÚCH 2 - C - CH 2- C
| is
Cl CH3 CH3
CN
| CH3
(b) –(CH 2 – CH –) n (a) H 2C = C
Cl CH3
|
(c) –( CH 2 – CH –)n (b) CH3CH=CHCH3
(d) –( CH – CH 2 –)n (c) CH3CH = CH2
|
C6 H5 (d) (CH3)2C = C(CH3)2
19. Structures of some common polymers are given. 23. Acrilan is a hard, horny and a high melting
Which one is not correctly presented? [2009] material. Which of the following represents its
(a) Neoprene; structure ? [2003]
æ ö
ç ÷ æ ö
ç -CH 2 - C = CH - CH 2 - CH 2 - ÷ (a) ç —CH 2 — CH — ÷
ç | ÷
ç | ÷
ç ÷ ç Cl ÷
è Cl øn è øn
(b) Terylene;
(b) æç —CH 2 — CH— ö÷
COOCH2 – CH2 – O–)n |
(– OC ç ÷
ç CN ÷
è øn
(c) Nylon 6, 6;
CH3
[ –NH(CH 2 )6 NH CO(CH2 )4 CO - ]n æ | ö
(c) ç —CH 2 — C — ÷
(d) Teflon; (-CF2 - CF2 -)n ç | ÷
ç COOCH3 ÷
20. Which one of the following statement is not true? ç ÷
è øn
[2008]
(a) In vulcanization the formation of sulphur æ ö
(d) ç—CH — CH ÷
bridges between different chains make 2
ç | ÷
rubber harder and stronger. ç COOC2H5 ÷
è øn
(b) Natural rubber has the trans -configuration
at every double bond 24. Which one of the following monomers gives the
(c) Buna-S is a copolymer of butadiene and polymer neoprene on polymerization ? [2003]
styrene (a) CF2 = CF2
(d) Natural rubber is a 1, 4 - polymer of isoprene (b) CH2 = CHCl
21. Which one of the following polymers is prepared (c) CCl2 = CCl2
by condensation polymerisation? [2007]
(a) Teflon (b) Natural rubber Cl
|
(c) Styrene (d) Nylon-6,6 (d) CH 2 = C — CH = CH 2
Polymers 319
28. Natural rubber is a polymer of [1999]

CH3
(a) butadiene (b) isoprene
25. Monomer of — C — CH2 — is [2002]
(c) 2-methylbutadiene (d) Hexa-1, 3-diene
CH3 n 29. Nylon 6, 6 is a polyamide obtained by the reaction
(a) 2-methylpropene (b) Styrene of [1996]
(c) Propylene (d) Ethene (a) COOH(CH2)4 COOH + NH2C6H4NH2–(p)
26. Which of the following is not correctly matched? (b) COOH(CH2)4 COOH + NH2 (CH2)6 NH2
[2001] (c) COOH (CH2)6 COOH + NH2 (CH2)4 NH2
O O (d) COOHC6H4 COOH–(p) + NH2 (CH2)6 NH2
(a) Terylene –OCH2–CH2–C– –C – 30. Bakelite is prepared by the reaction between
n (a) urea and formaldehyde [1995]
(b) ethylene glycol
(b) Neoprene (c) phenol and formaldehyde
(d) tetramethylene glycol
— CH 2 — C = CH — CH 2 —
31. An example of biopolymer is [1994]
Cl (a) Teflon (b) Neoprene
n
(c) Nylon-6, 6 (d) DNA
(c) Nylon-66
O O Topic 3: Uses of Polymers
–NH–(CH2)6–NH –C–(CH2)4–C–O– n 32. The polymer that is used as a substitute for wool
in making commercial fibres is
CH3 [NEET Odisha 2019]
(d) PMMA – CH2–C (a) Buna-N (b) melamine
COOCH3 n (c) nylon-6, 6 (d) polyacrylonitrile
33. Which one of the following is used to make "non-
27. CF2 = CF2 is a unit of [2000]
stick" cook-wares ? [1997]
(a) Teflon
(a) Polystyrene
(b) Buna – S
(b) Polyethylene terephthalate
(c) Bakelite
(c) Polytetrafluoroethylene
(d) Polyethene
(d) Polyvinyl chloride
A NSW E R K E Y
1 (d ) 5 (a) 9 (c) 13 (d ) 17 (b ) 21 (d ) 25 (a) 29 (b ) 33 (c)
2 (b ) 6 (d ) 10 (a) 14 (c) 18 (a) 22 (a ) 26 (a) 30 (c)
3 (b ) 7 (c) 11 (d ) 15 (b ) 19 (a) 23 (b ) 27 (a) 31 (d )
4 (d ) 8 (b ) 12 (a) 16 (b ) 20 (b ) 24 (d ) 28 (b ) 32 (d )
EBD_8336
320 CHEMISTRY
Hints & Solutions

1. (d) cis-1,4-Polyisoprene is a nautral polymer. 11. (d) H2 N—CH2—COOH
2. (b) nylon 2 – nylon 6 Glycine
+ H2 N — (CH2)5—COOH ®
3. (b) Nylon is a synthetic polyamide polymer. Aminocaproic acid
4. (d) Neoprene is an addition polymer of (HN—CH2—CO—NH— (CH2)5—CO) —
isoprene. Nylon-2-nylon-6
5. (a) Polyesters are condensation polymers of a 12. (a)
diabasic acid and a diol. e.g., Terylene.
O O
6. (d) The given compound is a copolymer of H
hexamethylene diamine and adipic acid. It is NH N
actually Nylon-6,6. n
Nylon–6
7. (c) Chain growth polymers involve a series (Caprolactum)
of reactions, each step of which consumes a
reactive particle and produce another similar 13. (d) Thermosetting polymers undergo chemical
particle. The reactive particles may be free changes when heated and set to hard mass when
radicals or ions to which monomers get added cooled e.g. Bakelite.
by a chain reaction.
Benzoyl Peroxide
nC6H5 – CH = CH2 ¾¾¾¾¾¾¾ ®
C 6H 5
(CH CH2)n
Polystyrene
8. (b) Elastomers are the polymers having very

weak intermolecular forces of attraction between
the polymer chain. The weak forces permit the
polymer to be streched.
Thermoset plastics contain polymers and cross
9. (c) Cross-linked or network polymers are linked together during the curing process to form
usually formed from bi-functional and tri- an irreversible chemical bond. Cross linking process
making thermosets plastic ideal for high heat
functional monomers and contain strong
applications.
covalent bonds between various linear polymer
chains like melamine, bakelite etc. 14. (c)
10. (a) Natural rubber is found to be a polymer of
cis-isoprene i.e. it is cis-polyisoprene
n HO.CH2CH2OH+n HOOC COOH
polymerisation
H2C C — CH CH2 ¾¾¾¾¾¾ ®
| Ethylene glycol Terephthalic acid
CH3 O O
Isoprene CH2 CH2 || ||
COOH D -( O CH2CH2–O– C C- )n
H3C H
Terylene
cis-polyisoprene
Polymers 321
It is resistant to mineral and organic acids. It is
used for blending with wool to provide better CH3
crease, in safety helmets and aircraft battery 22. (a) nH2C = C
boxes. CH3
Cl
| CH3
15. (b) CH 2 = C- CH = CH 2 (chloroprene) is the CH3
monomer of neoprene. C –H2C C CH2 C CH2–
CH3
16. (b) Nylon-6,6 is an example of first synthetic CH3
fibres produced from simple molecules. It is
23. (b) Acrilan is a polyacrylonitrile ( PAN).
prepared by condensation polymerisation of
adipic acid and hexamethylene diamine. Acrylic fibers are synthetic fibers made from
17. (b) Biodegradable polymer is Nylon-2- acrylonitridle monomer. Popular brand names are
Dralon, Orlon, Drytex, Courtelle, etc.
Nylon-6 which is copolymer of glycine
(H2N – CH2– COOH) and amino caproic acid Cl
(H2N–(CH2)5 – COOH). |
K S O
24. (d) nCH 2 = CH - C = CH 2 ¾¾2 ¾
2¾8®
nH2N – CH2 – COOH + Chloropren e
glycine nH2N – (CH2)5– COOH
amino caproic acid Cl
|
-( CH 2 - CH = C - CH 2 -
)n
O O
Neoprene
–( HN – CH2 – C – HN – (CH2)5 – C –) n
nylon – 2 – nylon – 6 é CH3 ù
ê | ú
25. (a) Monomer of ê — C — CH 2 — ú
18. (a) Neoprene is a polymer of chloroprene ê | ú
(2 – chloro – 1, 3 – butadiene). ëê CH3 ûú n
19. (a) Neoprene is a polymer of chloroprene. polymer is 2-methylpropene.
CH3 H CH2 26. (a) Terylene is prepared by condensing
20. (b) C=C terephthalic acid and ethylene glycol.
– CH2 CH2 CH3
CH2 CH3 H HOOC COOH + nHOCH2 – CH2OH

C=C C=C
H CH2 Terephthalic acid Ethylene glycol
CH2–
Natural rubber
(All cis configuration)
21. (d) Copolymer of adipic acid (6C) and —C — —C —OCH2 —OCH2—

300°C
hexamethylene diamine (6C). O O
Terylene n
n HOOC( CH 2 ) 4 COOH + nH 2 N ( CH 2 ) 6 NH 2 ®
Adipic acid Hexamethyl ene diamine Benzoyl Peroxide
27. (a) n CF2 = CF2 ¾¾¾¾¾¾¾¾¾¾® [—CF2 — CF2 —]
Ammonium peroxoSulphate
O O Tetrafluoroethene Teflon
(NH 4 )2S2 O8
|| ||
-( C- (CH 2 )4 - C- NH - (CH 2 ) 6 - NH -) n
Nylon-6,6 n CF2 = CF2 ¾¾¾¾¾¾¾¾¾¾® [—CF2 — CF2 —]
Ammonium peroxoSulphate n
Tetrafluoroethene Teflon
EBD_8336
322 CHEMISTRY
28. (b) Natural rubber is a polymer of isoprene,
OH OH
Polymerisation CH2OH
n CH2=CH–C=CH2
n Polymerisation
+ n
CH3
Isoprene
(2-methyl –CH2–CH=C–CH2– CH2OH
n
butadiene) CH3
Polyisoprene OH OH OH
(Natural rubber)
CH2 CH2 CH2
29. (b)
nHOOC (CH 2 ) 4 COOH + nH 2 N(CH 2 )6 NH 2
Adipic acid Hexamethylene CH2 CH2
diamine
O O CH2
¾¾¾¾
525K
® [– C – (CH2)4 – C –NH–(CH2) 6 – NH –]n CH2 CH2
Polymerisation Nylon 6, 6
OH OH OH
30. (c) Phenol and formaldehyde undergo
(cross linked Polymer Bakelite)
condensation polymerisation under two
different conditions to give a cross linked
polymer called bakelite. 31. (d) DNA is a biopolymer.
32. (d) Polyacrylonitrile is used as a substitute for
OH OH OH wool in making commercial fibre as orlon or
CH2OH acrilan.
–
OH 33. (c) Polytetrafluoroethylene commonly known
+ HCHO +
as teflon is a tough material. This is resistant to
heat and chemicals and have high melting point.
CH2OH
o & p-Hydroxy methyl phenol Therefore it is used for coating the cookware to
(intermediate) make them non-sticky.
Chemistry in Everyday Life 323
30 Chemistry in
Everyday Life
2020 2019 2018 2017 2016

Drugs and their Therapeutic action
1 E 1 E 1 E
classification of drugs
Cleansing agents detergents 1 A
1. Which of the following is a cationic detergent? (a) Dryer (b) Buffering agent
(a) Sodium stearate [2020] (c) Antiseptic (d) Softner
7. Artificial sweetner which is stable under cold
(b) Cetyltrimethyl ammonium bromide
conditions only is : [2014]
(c) Sodium dodecylbenzene sulphonate (a) Saccharine (b) Sucralose
(d) Sodium lauryl sulphate (c) Aspartame (d) Alitame
2. The artificial sweetener stable at cooking 8. Antiseptics and disinfectants either kill or
temperature and does not provide calories is prevent growth of microorganisms. Identify
which of the following statements is not true:
[NEET Odisha 2019] [NEET 2013]
(a) alitame (b) saccharin (a) Chlorine and iodine are used as strong
(c) aspartame (d) sucralose disinfectants.
3. Among the following, the narrow spectrum (b) Dilute solutions of Boric acid and
antibiotic is: [2019] Hydrogen Peroxide are strong antiseptics.
(a) penicillin G (b) ampicillin (c) Disinfectants harm the living tissues.
(c) amoxycillin (d) chloramphenicol (d) A 0.2% solution of phenol is an antiseptic
4. Mixture of chloroxylenol and terpineol acts as: while 1% solution acts as a disinfectant.
[2017] 9. Dettol is the mixture of [1996, NEET Kar. 2013]
(a) antiseptic (b) antipyretic (a) Terpineol and Bithionol
(c) antibiotic (d) analgesic (b) Chloroxylenol and Bithionol
5. Which of the following is an analgesic? [2016] (c) Chloroxylenol and Terpineol
(a) Novalgin (b) Penicillin (d) Phenol and Iodine
(c) Streptomycin (d) Chloromycetin 10. Chloroamphenicol is an : [2012 M]
(a) antifertility drug
6. Bithionol is generally added to the soaps as an (b) antihistaminic
additive to function as a/an : [2015] (c) antiseptic and disinfectant
(d) antibiotic-broad spectrum
EBD_8336
324 CHEMISTRY
11. Which one of the following is employed as tranquilizer? [2009]
Antihistamine ? [2011] (a) Naproxen (b) Tetracycline
(a) Chloramphenicol (c) Chlorpheninamine(d) Equanil
(b) Diphenyl hydramine 14. Which one of the following can possibly be used
(c) Norothindrone as analgesic without causing addiction and
(d) Omeprazole mood modification ? [1997]
12. Which one of the following is employed as a (a) Diazepam
tranquilizer drug? [2010] (b) Morphine
(a) Promethazine (b) Valium (c) N-acetyl-para-aminophenol
(c) Naproxen (d) Mifepristone (d) Tetrahydrocannabinol
13. Which one of the following is employed as a
ANSWER KEY
1 (b) 3 (a) 5 (a) 7 (c) 9 (c) 11 (b) 13 (d)
2 (d) 4 (a) 6 (c) 8 (b) 10 (d) 12 (b) 14 (c)
Hints & Solutions

8. (b) Dilute solutions of boric acid and
CH3 hydrogen peroxide are weak antiseptics.
–
1. (b) CH3 – (CH2)15 – N – CH3 Br Antiseptics are used for humans, pets, etc. but
disinfectants are used to kill bacteria etc. on floor,
CH3 wall surfaces.
Cetyltrimethyl ammonium bromide 9. (c) Dettol is a mixture of chloroxylenol and
terpineol.
2. (d) Sucralose is trichloro derivative of sucrose.
It is stable at cooking temperature. It does 10. (d) Chloroamphenicol is a broad spectrum
antibiotic.
not provide calories.
3. (a) Penicillin G 11. (b) Diphenyl hydramine also known as
4. (a) Dettol is a mixture of chloroxylenol and benadryl is an antihistamine.
terpineol which is a very commonly known 12. (b) Valium is used as a sedative.
antiseptic.
13. (d) Equanil is an important medicine used in
5. (a) Novalgin is most widely used as analgesic. depression and hypertension.
Analgesics are pain releiving
14. (c) We know that N-acetyl-para-aminophenol
6. (c) Bithionol is added to soaps to impart (or paracetamol) is an antipyretic which
antiseptic properties. can also be used as an analgesic to relieve
7. (c) Aspartame is stable under cold conditions. pains.
31
Nuclear Chemistry 325
Nuclear Chemistry
1. The half life of a substance in a certain enzyme- radioactive substance is 6 hours. Then injection
catalysed reaction is 138s. The time required for of maximum activity of radioactive substance
the concentration of the substance to fall from that can be injected will be [2001]
1.28 mg L–1 to 0.04 mg L–1, is : [2011] (a) 0.08 M (b) 0.04 M
(a) 414 s (b) 552 s (c) 0.32 M (d) 0.16 M
(c) 690 s (d) 276 s
7. If species ba X emits firstly a positron, then two
2. A nuclide of an alkaline earth metal undergoes
radioactive decay by emission of the a-particles a and two b and in last one a and finally converted
in succession. The group of the periodic table to species dc Y , so correct relation is [2001]
to which the resulting daughter element would (a) c = a – 5, d = b – 12
belong is [2005] (b) c = a – 6, d = b – 8
(a) Gr. 4 (b) Gr. 6 (c) c = a – 4, d = b – 12
(c) Gr. 14 (d) Gr. 16 (d) c = a – 5, d = b – 8
3. The radioactive isotope 60 which is used in 8. When a radioactive element emits successively
27 Co
the treatment of cancer can be made by (n, p) one a-particle and two b-particles, the mass
reaction. For this reaction the target nucleus is number of the daughter element [1999]
(a) is reduced by 4 units
(a) 59
28 Ni (b) 59
27 Co [2004]
(b) remains the same
(c) 60 (d) 60
28 Ni 27 Co (c) is reduced by 2 units
4. The radioactive isotope, tritium, (13 H ) has a half- (d) is increased by 2 units
9. Number of neutrons in a parent nucleus X, which
life of 12.3 years. If the initial amount of tritium is
gives 14
7 N
nucleus, after two successive b
32 mg, how many milligrams of it would remain
emissions, would be [1998]
after 49.2 years? [2003]
(a) 9 (b) 6
(a) 8 mg (b) 1 mg
(c) 7 (d) 8
(c) 2 mg (d) 4 mg 10. Carbon - 14 dating method is based on the fact
5. U 235 , nucleus absorbs a neutron and
92 that: [1997]
disintegrates into 54Xe139, 38Sr94 and x. So what (a) C-14 fraction is same in all objects
will be the product x ? [2002] (b) C-14 is highly insoluble
(a) 3-neutrons (b) 2-neutrons (c) Ratio of carbon-14 and carbon-12 is constant
(c) a-particle (d) b-particle (d) all the above
6. A human body required 0.01M activity of 11. 235 1 236
92 U + 0 n ® 92 U®
radioactive substance after 24 hours. Half life of
EBD_8336
326 CHEMISTRY
fission products + neutrons + 3.20 × 10–11 J 15. India has the world’s largest deposits of thorium
The energy released when 1 g of 92 235 in the form of [1994]
U finally
undergoes fission is [1997] (a) rutile (b) magnesite.
(a) 12.75 × 108 kJ (b) 16.40 × 107 kJ (c) lignite (d) monazite.
(c) 8.20 × 107 kJ (d) 6.50 × 106 kJ 16. If an isotope of hydrogen has two neutrons in its
12. One microgram of radioactive sodium 11 24
Na with atom, its atomic number and atomic mass number
a half-life of 15 hours was injected into a living will respectively be [1992]
system for a bio-assay. How long will it take for (a) 2 and 1 (b) 3 and 1
the radioactive subtance to fall up to 25% of the
initial value? [1996] (c) 1 and 1 (d) 1 and 3.
(a) 60 hours (b) 22.5 hours 17. The age of most ancient geological formations is
(c) 375 hours (d) 30 hours estimated by [1989]
13. Half-life for radioactive 14C is 5760 years. In how (a) Potassium–argon method
many years, 200 mg of 14C will be reduced to (b) Carbon-14 dating method
25 mg? [1995]
(c) Radium-silicon method
(a) 5760 years (b) 11520 years
(d) Uranium-lead method.
(c) 17280 years (d) 23040 years
14. In a radioactive decay, an emitted electron comes 18. Emission of an alpha particle leads to a [1989]
from [1994] (a) Decrease of 2 units in the charge of the atom
(a) The nucleus of atom (b) Increase of 2 units in the mass of the atom
(b) The orbit with principal quantum number 1 (c) Decrease of 2 units in the mass of the atom
(c) the inner orbital of the atom (d) Increase of 4 units in the mass of the atom.
(d) the outermost orbit of the atom.
ANSWER KEY
1 (c) 3 (c) 5 (a) 7 (a) 9 (a) 11 (c) 13 (c) 15 (d) 17 (d)
2 (c) 4 (c) 6 (d) 8 (a) 10 (c) 12 (d) 14 (a) 16 (d) 18 (a)
Nuclear Chemistry 327
Hints & Solutions

1. (c) For a first order reaction Total time 24
Used half life time (n) = = =4
Total time T = no. of half lives (n) × half life (t1/2) T1/2 6
n
N æ 1ö æ1ö
4
=ç ÷ So, 0.01 = Initial activity ´ ç ÷
N0 è 2 ø è2ø
where n = no. of half lives Initial activity = 0.01 × 16 = 0.16 M
Give N0 (original amount) = 1.28 mg/l
b b 0
N (amount of substance left after time T ) 7. (a) a X® a -1 X + 1e
= 0.04 mgL–1 –2a
b -8 4
a -5 X + 2 He
n n 5 n
0.04 æ 1 ö 1 æ1ö æ1ö æ1ö
\ =ç ÷ ; =ç ÷ ; ç ÷ =ç ÷
1.28 è 2 ø 32 è 2 ø è 2 ø è2ø –2b
b -8
n =5 a -3 X
T = 5 × 138 = 690 –a
b -12 4
2. (c) When IIA group element (Ra) emits one a -5 X + 2 He
a-particle its group no. decreases by two 8. (a) Mass number is affected by emmision of a
unit. i.e., go into zero group (Gr. 16) But as it particle while b-particle has negligible mass does
i s r a d i oa ct i ve t h us d ue t o successi ve
not effect mass number. e.g.
emission last product is Pb i.e., (Gr.14).
a b
ZX
A
® Z - 2 X A - 4 ¾¾
¾¾ ® Z - 2 +1 X A - 4
3. (c) [ X ] +10 n ®60 1
27 Co +1 H b
® Z X A- 4
¾¾
Balancing the mass and atomic numbers on both
60 9. (a) 5 X14 ¾-¾®b 14 -b
6 Y ¾¾® 7 N
14
sides +10 n ®60
28 X
1
27 Co +1 H
No. of neutrons = Mass number – No. of proton
Thus X should be 60 28 Ni =14 – 5 = 9
4. (c) Given t1/2 = 12.3 years 10. (c) By carbon dating method
Initial amount (N0) = 32 mg
Total time = 49.2 years 2.303 æN ö
Age of wood = ´ t½ log ç 0 ÷
0.693 è Nø
T 49.2
No. of half lives (n) = = =4 é ratio of C14 / C12 in living wood ù
t1/2 12.3 ê ú
14 12
n
æ1ö 32
4 êë ratio of C / C in dead wood úû
æ 1ö
Now Nt = N0 ç ÷ = 32ç ÷ = = 2 mg
è 2ø è2ø 16 Hence, it is based upon the ratio of C14 and C12.
Hence 32 mg becomes 2 mg in 49.2 years 11. (c) 1 atom of 235
92 U on fission gives energy
235 1 139 94
5. (a) 92 U + 0 n ® 54 Xe + 38 Sr +X = 3.2 × 10–11 J
92 + 0 = 54 + 38 + a Þ a = 0 6.023 × 1023 atom (1 mole) on fission gives energy
235 + 1 = 139 + 94 + b Þ b = 3 So, X = 3 0n1 = 3.2 × 10–11 × 6.023 × 1023 J
i.e 3 neutrons. 1 g of 235 on fission gives energy
6. (d) Remaining activity = 0.01M 92 U
after 24 hrs 6.023

n = ´ 3.2 ´ 1012 J = 8.2 × 107 kJ
æ 1ö 235
Remaining activity = Initial activity ´ ç ÷
è 2ø
EBD_8336
328 CHEMISTRY
n 14. (a) When a radioactive elements emits a or b

æ 1ö N
12. (d) N = N 0 ç ÷ ; here, N = 0 particle the new element formed may have
è 2ø 4 unstable nucleus. It may further disintegrate by
N0 æ 1ö
n
æ 1ö
n
æ 1ö
2 emitting a- or b particle forming a new element.
= N0 ç ÷ Þ ç ÷ = ç ÷ Þ n = 2 This process of integration may continue till end
4 è 2ø è 2ø è 2ø
product formed, is a stable compound.
Total time (T)= n × t1/2 = 2 × 15 = 30 hrs
15. (d) The ore of thorium is monazite.
13. (c) As we know that 16. (d) As number of neutron =
n
N æ 1ö Mass number – atomic number
=ç ÷
N0 è 2 ø Give number of neutron = 2
where N 0 original amount of radioactive \ Mass number will be 3 and atomic number
sustacnce will be one.
N = Amount of substance remain after n half lives 17. (d) Age of geological formations (i.e. predicting
the age of the earth and rocks) is estimated by
n n
25 æ 1 ö 1 æ 1ö U– Pb method, also known as helium dating.
\ = ç ÷ or = ç ÷
200 è 2 ø 8 è 2ø
C-14 dating method is used to predict the age of
3 n fossils or dead animals or a fallen tree.
æ 1ö æ 1ö
or çè ÷ø = çè ÷ø ; \ n = 3
2 2
now T = n × t½ 18. (a) Emission of a -particle ( 42 He ) leads to
where T = total time decrease of 2 units of charge. e.g.
T = 3 × 5760 years = 17280 years 238
92 U ®90 Th 234 + 2 He 4
¾¾

33 Years NEET Chapterwise & Topicwise Solved Papers CHEMISTRY 2020 PDF

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1 Some Basic Concepts

2020 2019 2018 2017 2016

LOD - Level of Difficulty E - Easy A - Average D - Difficult Qns - No. of Questions

Topic 1 : Significant Figures, Laws of Chemical (a) 4 : 1 (b) 16 : 1

8. 1.0 g of magnesium is burnt with 0.56 g O2 in a (c) 0.5 g of H2 gas

(a) N/2 (b) N 35. Percentage of Se in peroxidase anhydrase

Hints & Solutions

1 6. (b) If 6.022 × 1023 changes to 6.022 × 1020/mol

48 Thus, volume occupied by 1 molecule of water

For diatomic gas, F = 5 36. (c) Table for empirical formula :

Atomic wt. 2.9g

Trend Analysis with Important Topics & Sub-Topics

2020 2019 2018 2017 2016

8. In the photo-electron emission, the energy of (a) n = 6 to n = 1 (b) n = 5 to n = 4

Hints & Solutions

20. (a) The ionization energy of any hydrogen like h

13.6 6.626 ´ 10 -34

Trend Analysis with Important Topics & Sub-Topics

2020 2019 2018 2017 2016

Hints & Solutions

having half filled or fully filled orbitals are : .F. - F

4 Chemical Bonding and

2020 2019 2018 2017 2016

LOD - Level of Difficulty E - Easy A - Average D - Difficult Qns - No. of Questions

Topic 1: Electrovalent, Covalent and 5. Among the following electron deficient

Hints & Solutions

Formal charge = total no. of valence e– in the

covalent bonds. It has only 12 electrons instead of O O

O2 molecule which has purely double bond

39. (b) IBr2- , XeF2 1

42. (a) According to VSEPR theory order of 1

60. (c) Hybridization of Br in BrO3–

69. (a) For p-overlap the lobes of the atomic

E.S. p 2 px2 p 2 p 2y p* 2 px2 p* 2 p1y

dsp 2 Number of electrons in bonding -

N - Na 2 - 1 110. (c) MOT configurations of O2 and O2+ :

Nb - Na 6-4 2 O2 – (17) : KK (s2s)2 (s*2s)2 (s2pz)2 (p2px)2

114. (d) The shape of ozone molecule is

126. (d) In this configuration, there are four

order hence increases the bond strength.

O O 129. (a) Linear combination of two hybridized

Trend Analysis with Important Topics & Sub-Topics

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(a) 50.00 u (b) 12.25 u (b) Volume always remains constant.

Hints & Solutions

pN 2 = mole fraction of N 2 × PTotal x

Induced dipole forces result when an ion or a dipole r1 M2

200 36 200 400 600

15. (b) R = 0.082 litre atm K–1 mol–1 . 8RT

31. (c) In real gas equation, van der Wall constant

m Hydrogen bonding is in order H2O > C2H5OH >

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Topic 1: First Law and Basic Fundamentals

19. Consider the following processes : Enthalpy of formation of H2O (l) is

Topic 4: Spontaneity and Gibb's Free Energy Options:

2. A 20 litre container at 400 K contains CO2(g) at 7. 2NO(g),

1 1 9. (c) 2A(g) + B(g) 3C(g) + D(g)