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JEE Main
CHAPTERWISE
SOLUTIONS
2019-2002
Chemistry
All the 16 Question Papers
of JEE Main Online 2019 (Jan & Apr Attempt)
ARIHANT PRAKASHAN (Series), MEERUT

Arihant Prakashan (Series), Meerut
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PREFACE
JEE Main is a gateway examination for candidates expecting to seek

admission in Bachelor in Engineering (BE), Bachelor of Technology
(B.Tech) and Bachelor of Architecture (B.Arch) at Indian Institutes of
Information Technology (IIITs), National Institutes of Technology
(NITs), Delhi Technological University and other Centrally Funded
Technical Institutes (CFTIs).
JEE Main is also an examination which is like screening examination
for JEE Advanced (The gateway examination to India's most reputed
Technical Institutes, Indian Institutes of Technology— IITs).
To make the students well-versed with the pattern as well as the
level of the questions asked in the exam, this book contains
Chapterwise Solutions of Questions asked in Last 18 Years’
Examinations of JEE Main (formerly known as AIEEE). Solutions to
all the questions have been kept very detailed and accurate. Along
with the indication of level of the exam, this book will also teach you
to solve the questions objectively in the examination.
To give the students a complete practice, along with Chapterwise
Solutions, this book contains 5 Practice Sets, based exactly on JEE
Main Syllabus and Pattern. By practicing these sets, students can
attain efficiency in Time Management during the examination.
We hope this book would be highly beneficial for the students. We
would be grateful if any discrepancy or mistake in the questions or
answers is brought to our notice so that these could be rectified in
subsequent editions.
Publisher

CONTENTS
1. Some Basic Concepts of Chemistry 1-8

2. States of Matter 9-20
3. Atomic Structure 21-28
4. Chemical Bonding 29-40
5. Thermodynamics 41-56
6. Solutions 57-72
7. Equilibrium 73-90
8. Redox Reactions and Electrochemistry 91-107
9. Chemical Kinetics and Surface Chemistry 108-128
10. Periodicity of Elements 129-134
11. Principles and Processes of Metallurgy 135-140
12. Hydrogen, s-and p-Block Elements 141-165
13. d-and f-Block Elements and Coordination Chemistry 166-191
14. Environmental Chemistry 192-198
15. General Organic Chemistry 199-214
16. Hydrocarbons and their Halogen Derivatives 215-238
17. Organic Compounds Containing Oxygen (Alcohols, Ethers,
Aldehydes, Ketones, Carboxylic Acids and their Derivatives) 239-276
18. Organic Compounds Containing Nitrogen
(Amines and Diazonium Salts) 277-293
19. Polymers and Biomolecules 294-307
20. Analytical Chemistry and Chemistry in Everyday Life 308-314
PRACTICE SETS for JEE MAIN

Practice Set 1 315-320

SYLLABUS
SECTION- A (Physical Chemistry)

UNIT 1 Some Basic Concepts in hemistry Solid State Classification of solids: molecular,
Matter and its nature, Dalton's atomic theory; ionic, covalent and metallic solids, amorphous
Concept of atom, molecule, element and and crystalline solids (elementary idea); Bragg's
compound; Physical quantities and their Law and its applications, Unit cell and lattices,
measurements in Chemistry, precision and packing in solids (fcc, bcc and hcp lattices), voids,
accuracy, significant figures, S.I. Units, calculations involving unit cell parameters,
dimensional analysis; Laws of chemical imperfection in solids; electrical, magnetic and
combination; Atomic and molecular masses, dielectric properties.
mole concept, molar mass, percentage UNIT 3 Atomic Structure
composition, empirical and molecular
Discovery of sub-atomic particles (electron,
formulae; Chemical equations and
proton and neutron); Thomson and Rutherford
stoichiometry.
atomic models and their limitations; Nature of
UNIT 2 States of Matter electromagnetic radiation, photoelectric effect;
Classification of matter into solid, liquid and spectrum of hydrogen atom, Bohr model of
gaseous states. hydrogen atom - its postulates, derivation of the
relations for energy of the electron and radii of
Gaseous State Measurable properties of gases;
the different orbits, limitations of Bohr's model;
Gas laws - Boyle's law, Charle's law, Graham's
dual nature of matter, de-Broglie's relationship,
law of diffusion, Avogadro's law, Dalton's law of
Heisenberg uncertainty principle.
partial pressure; Concept of Absolute scale of
temperature; Ideal gas equation, Kinetic theory Elementary ideas of quantum mechanics,
of gases (only postulates); Concept of average, quantum mechanical model of atom, its
root mean square and most probable velocities; important features,ψ and ψ2, concept of atomic
Real gases, deviation from Ideal behaviour, orbitals as one electron wave functions; Variation
compressibility factor, van der Waals’ of ψ and ψ2 with r for 1s and 2s orbitals; various
quantum numbers (principal, angular
Equation, liquefaction of gases, critical momentum and magnetic quantum numbers)
constants. and their significance; shapes of s, p and d -
Liquid State Properties of liquids - vapour orbitals, electron spin and spin quantum number;
pressure, viscosity and surface tension and rules for filling electrons in orbitals – aufbau
effect of temperature on them (qualitative principle, Pauli's exclusion principle and Hund's
treatment only). rule, electronic configuration of elements, extra
stability of half-filled and completely filled
orbitals.

UNIT 4 Chemical Bonding and pressure - composition plots for ideal and non-ideal
Molecular Structure solutions.
Kossel Lewis approach to chemical bond Colligative properties of dilute solutions - relative
formation, concept of ionic and covalent bonds. lowering of vapour pressure, depression of freezing
point, elevation of boiling point and osmotic
Ionic Bonding Formation of ionic bonds, factors
pressure; Determination of molecular mass using
affecting the formation of ionic bonds;
colligative properties; Abnormal value of molar
calculation of lattice enthalpy.
mass, van’t Hoff factor and its significance.
Covalent Bonding Concept of electronegativity,
Fajan's rule, dipole moment; Valence Shell UNIT 7 Equilibrium
Electron Pair Repulsion (VSEPR) theory and Meaning of equilibrium, concept of dynamic
shapes of simple molecules. equilibrium.
Quantum mechanical approach to covalent Equilibria involving physical processes Solid -
bonding Valence bond theory - Its important liquid, liquid - gas and solid - gas equilibria, Henry’s
features, concept of hybridization involving s, p law, general characteristics of equilibrium involving
and d orbitals; Resonance. physical processes.
Molecular Orbital Theory Its important features, Equilibria involving chemical processes Law of
LCAOs, types of molecular orbitals (bonding, chemical equilibrium, equilibrium constants
antibonding), sigma and pi-bonds, molecular (K and K) and their significance, significance of ΔG
orbital electronic configurations of homonuclear and ΔG o in chemical equilibria, factors affecting
diatomic molecules, concept of bond order, equilibrium concentration, pressure, temperature,
bond length and bond energy. effect of catalyst; Le -Chatelier’s principle.
Elementary idea of metallic bonding. Hydrogen Ionic equilibrium Weak and strong electrolytes,
bonding and its applications. ionization of electrolytes, various concepts of acids
and bases (Arrhenius, Bronsted - Lowry and Lewis)
UNIT 5 Chemical Thermodynamics
and their ionization, acid-base equilibria (including
Fundamentals of thermodynamics System and multistage ionization) and ionization constants,
surroundings, extensive and intensive ionization of water, pH scale, common ion effect,
properties, state functions, types of processes. hydrolysis of salts and pH of their solutions, solubility
First law of thermodynamics Concept of work, of sparingly soluble salts and solubility products,
heat internal energy and enthalpy, heat capacity, buffer solutions.
molar heat capacity, Hess's law of constant heat
summation; Enthalpies of bond dissociation, UNIT 8 Redox Reactions and
combustion, formation, atomization, Electrochemistry
sublimation, phase transition, hydration, Electronic concepts of oxidation and reduction,
ionization and solution. redox reactions, oxidation number, rules for
Second law of thermodynamics Spontaneity of assigning oxidation number, balancing of redox
processes; ΔS of the universe and ΔG of the reactions.
system as criteria for spontaneity, ΔGo Eectrolytic and metallic conduction, conductance
(Standard Gibb's energy change) and in electrolytic solutions, specific and molar
equilibrium constant. conductivities and their variation with
concentration: Kohlrausch's law and its
UNIT 6 Solutions
applications.
Different methods for expressing
concentration of solution - molality, molarity, Electrochemical cells - Electrolytic and Galvanic cells,
mole fraction, percentage (by volume and mass different types of electrodes, electrode potentials
both), vapour pressure of solutions and Raoult's including standard electrode potential, half - cell and
Law - Ideal and non-ideal solutions, vapour cell reactions, emf of a Galvanic cell and its

measurement; Nernst equation and its UNIT 10 Surface Chemistry
applications; Relationship between cell potential Adsorption Physisorption and chemisorption and
and Gibbs’ energy change; Dry cell and lead their characteristics, factors affecting adsorption of
accumulator; Fuel cells; Corrosion and its
gases on solids- Freundlich and Langmuir

prevention. adsorption isotherms, adsorption from solutions.
UNIT 9 Chemical Kinetics Catalysis Homogeneous and heterogeneous,
activity and selectivity of solid catalysts, enzyme
Rate of a chemical reaction, factors affecting the rate
catalysis and its mechanism.
of reactions concentration, temperature, pressure
and catalyst; elementary and complex reactions, Colloidal state distinction among true solutions,
order and molecularity of reactions, rate law, rate colloids and suspensions, classification of
constant and its units, differential and integral forms colloids - lyophilic, lyophobic; multi molecular,
of zero and first order reactions, their characteristics macromole-cular and associated colloids
and half - lives, effect of temperature on rate of (micelles), preparation and properties of colloids
reactions - Arrhenius theory, activation energy and Tyndall effect, Brownian movement,
its calculation, collision theory of bimolecular electrophoresis, dialysis, coagulation and
gaseous reactions (no derivation). flocculation; Emulsions and their characteristics.
SECTION- B (Inorganic Chemistry)

UNIT 11 Classification of Elements and UNIT 14 s - Block Elements
Periodicity in Properties (Alkali and Alkaline Earth Metals)
Periodic Law and Present Form of the Periodic Group 1 and 2 Elements
Table, s, p, d and f Block Elements, Periodic General introduction, electronic configuration and
Trends in Properties of Elementsatomic and Ionic general trends in physical and chemical properties
Radii, Ionization Enthalpy, Electron Gain of elements, anomalous properties of the first
Enthalpy, Valence, Oxidation States and element of each group, diagonal relationships.
Chemical Reactivity.
Preparation and properties of some important
UNIT 12 General Principles and compounds - sodium carbonate, sodium chloride,
sodium hydroxide and sodium hydrogen carbonate;
Processes of Isolation of Metals
Industrial uses of lime, limestone, Plaster of Paris and
Modes of occurrence of elements in nature, cement; Biological significance of Na, K, Mg and Ca.
minerals, ores; steps involved in the extraction of
metals - concentration, reduction (chemical and UNIT 15 p - Block Elements
electrolytic methods) and refining with special
reference to the extraction of Al, Cu, Zn and Fe; Group 13 to Group 18 Elements
Thermodynamic and electrochemical principles General Introduction Electronic configuration and
involved in the extraction of metals. general trends in physical and chemical properties
of elements across the periods and down the
UNIT 13 Hydrogen groups; unique behaviour of the first element in
Position of hydrogen in periodic table, isotopes, each group.
preparation, properties and uses of hydrogen; Group wise study of the p – block elements
physical and chemical properties of water and
Group 13 Preparation, properties and uses of boron
heavy water; Structure, preparation, reactions
and aluminium; structure, properties and uses of
and uses of hydrogen peroxide; Classification of
borax, boric acid, diborane, boron trifluoride,
hydrides ionic, covalent and interstitial;
aluminium chloride and alums.
Hydrogen as a fuel.

Group 14 Tendency for catenation; Structure, UNIT 17 Coordination Compounds
properties and uses of allotropes and oxides of
Introduction to coordination compounds,

carbon, silicon tetrachloride, silicates, zeolites and Werner's theory; ligands, coordination number,
silicones. denticity, chelation; IUPAC nomenclature of
Group 15 Properties and uses of nitrogen and mononuclear coordination compounds,
phosphorus; Allotrophic forms of phosphorus; isomerism; Bonding Valence bond approach and
Preparation, properties, structure and uses of basic ideas of Crystal field theory, colour and
ammonia nitric acid, phosphine and phosphorus magnetic properties; importance of
halides,(PCl3, PCl5); Structures of oxides and oxoacids coordination compounds
of nitrogen and phosphorus. (in qualitative analysis, extraction of metals and in
Group 16 Preparation, properties, structures and biological systems).
uses of dioxygen and ozone; Allotropic forms of
sulphur; Preparation, properties, structures and uses Unit 18 Environmental Chemistry
of sulphur dioxide, sulphuric acid (including its Environmental pollution Atmospheric, water and
industrial preparation); Structures of oxoacids of soil.
sulphur. Atmospheric pollution Tropospheric and
Group 17 Preparation, properties and uses of stratospheric.
chlorine and hydrochloric acid; Trends in the acidic Tropospheric pollutants : Gaseous pollutants
nature of hydrogen halides; Structures of Oxides of carbon, nitrogen and sulphur,
Interhalogen compounds and oxides and oxoacids hydrocarbons; their sources, harmful effects and
of halogens. prevention; Green house effect and Global
Group 18 Occurrence and uses of noble gases; warming; Acid rain;
Structures of fluorides and oxides of xenon. Particulate pollutants Smoke, dust, smog, fumes,
mist; their sources, harmful effects and
UNIT 16 d – and f – Block Elements prevention.
Transition Elements General introduction, electronic Stratospheric pollution Formation and
configuration, occurrence and characteristics, breakdown of ozone, depletion of ozone layer - its
general trends in properties of the first row mechanism and effects.
transition elements - physical properties, ionization Water pollution Major pollutants such as,
enthalpy, oxidation states, pathogens, organic wastes and chemical
atomic radii, colour, catalytic behaviour, magnetic pollutants their harmful effects and prevention.
properties, complex formation, interstitial Soil pollution Major pollutants such as: Pesticides
compounds, alloy formation; Preparation, (insecticides, herbicides and fungicides), their
properties and uses of K2 Cr2 O7 and KMnO4. harmful effects and prevention.
Inner Transition Elements Lanthanoids Electronic Strategies to control environmental pollution.
configuration, oxidation states, chemical reactivity
and lanthanoid contraction. Actinoids Electronic
configuration and oxidation states.

SECTION- C (Organic Chemistry)

UNIT 19 Purification & Characterisation water, hydrogen halides (Markownikoff's and
of Organic Compounds peroxide effect); Ozonolysis, oxidation, and
polymerization.
Purification Crystallization, sublimation, distillation,
differential extraction and chromatography principles Alkynes acidic character; addition of hydrogen,
and their applications. halogens, water and hydrogen halides;
polymerization.
Qualitative analysis Detection of nitrogen, sulphur,
phosphorus and halogens. Aromatic hydrocarbons Nomenclature, benzene
structure and aromaticity; Mechanism of
Quantitative analysis (basic principles only) electrophilic substitution: halogenation, nitration,
Estimation of carbon, hydrogen, nitrogen, halogens, Friedel – Craft's alkylation and acylation, directive
sulphur, phosphorus. influence of functional group in mono-substituted
Calculations of empirical formulae and molecular benzene.
formulae; Numerical problems in organic quantitative
analysis. UNIT 22 Organic Compounds
Containing Halogens
UNIT 20 Some Basic Principles General methods of preparation, properties and
of Organic Chemistry reactions; Nature of C—X bond; Mechanisms of
Tetravalency of carbon; Shapes of simple molecules substitution reactions. Uses/environmental effects of
hybridization (s and p); Classification of organic chloroform, iodoform
compounds based on functional groups:
UNIT 23 Organic Compounds
—C=C—,—C=C— and those containing halogens,
oxygen, nitrogen and sulphur, Homologous series; Containing Oxygen
Isomerism - structural and stereoisomerism. General methods of preparation, properties,
Nomenclature (Trivial and IUPAC) reactions and uses.
Covalent bond fission Homolytic and heterolytic free Alcohols, Phenols and Ethers
radicals, carbocations and carbanions; stability of Alcohols Identification of primary, secondary and
carbocations and free radicals, electrophiles and tertiary alcohols; mechanism of dehydration.
nucleophiles. Phenols Acidic nature, electrophilic substitution
Electronic displacement in a covalent bond Inductive reactions: halogenation, nitration and
effect, electromeric effect, resonance and sulphonation, Reimer - Tiemann reaction.
hyperconjugation. Ethers Structure.
Common types of organic reactions Substitution, Aldehyde and Ketones Nature of carbonyl group;
addition, elimination and rearrangement. Nucleophilic addition to >C=O group, relative
reactivities of aldehydes and ketones; Important
UNIT 21 Hydrocarbons
reactions such as - Nucleophilic addition reactions
Classification, isomerism, IUPAC nomenclature, general (addition of HCN, NH3 and its derivatives), Grignard
methods of preparation, properties and reactions. reagent; oxidation; reduction (Wolff Kishner and
Alkanes Conformations: Sawhorse and Newman Clemmensen) acidity of α-hydrogen, aldol
projections (of ethane); Mechanism of halogenation of condensation, Cannizzaro reaction, Haloform
alkanes. reaction; Chemical tests to distinguish between
Alkenes Geometrical isomerism; Mechanism of aldehydes and Ketones. Carboxylic Acids Acidic
electrophilic addition: addition of hydrogen, halogens, strength and factors affecting it.

UNIT 24 Organic Compounds drugs, antibiotics, antacids, antihistamins - their

Containing Nitrogen meaning and common examples.
General methods of preparation, properties, reactions Chemicals in food Preservatives, artificial
and uses. sweetening agents - common examples.
Amines Nomenclature, classification, structure basic Cleansing agents Soaps and detergents, cleansing
character and identification of primary, secondary and action.
tertiary amines and their basic character.
UNIT 28 Principles Related to
Diazonium Salts Importance in synthetic organic
Practical Chemistry
chemistry.
— Detection of extra elements (N, S, halogens) in
UNIT 25 Polymers organic compounds; Detection of the following
General introduction and classification of polymers, functional groups: hydroxyl (alcoholic and
general methods of polymerization-addition and phenolic), carbonyl (aldehyde and ketone),
condensation, copolymerization; Natural and synthetic carboxyl and amino groups in organic
rubber and vulcanization; some important polymers compounds.
with emphasis on their monomers and uses - — Chemistry involved in the preparation of the
polythene, nylon, polyester and bakelite. following
— Inorganic compounds Mohr's salt, potash alum.
UNIT 26 Biomolecules — Organic compounds Acetanilide,
General introduction and importance of biomolecules. p-nitroacetan ilide, aniline yellow, iodoform.
Carbohydrates Classification: aldoses and ketoses; — Chemistry involved in the titrimetric excercises -
monosaccharides (glucose and fructose), constituent Acids bases and the use of indicators, oxali acid vs
monosaccharides of oligosacchorides (sucrose, lactose, KMnO4, Mohr's salt vs KMnO4.
maltose) and polysaccharides (starch, cellulose, — Chemical principles involved in the qualitative salt
glycogen). analysis
2+ 2+ 3+ 3+ 2+ 2+ 2+ 2+
Proteins Elementary Idea of α-amino acids, peptide — Cations — Pb , Cu , Al , Fe , Zn , Ni , Ca , Ba ,
2+ 4+ 2- 2- 2-
bond, . polypeptides; proteins: primary, secondary, Mg NH . Anions – CO3 , S , SO4 , NO2, NO3,
tertiary and quaternary structure (qualitative idea Cl-, Br-, I- (Insoluble salts excluded).
only), denaturation of proteins, enzymes. — Chemical principles involved in the following
Vitamins Classification and functions. experiments
Nucleic Acids Chemical constitution of DNA and RNA. 1. Enthalpy of solution of CuSO4
Biological functions of Nucleic acids. 2. Enthalpy of neutralization of strong acid and
strong base.
UNIT 27 Chemistry in Everyday Life 3. Preparation of lyophilic and lyophobic sols.
Chemicals in medicines Analgesics, tranquilizers, 4. Kinetic study of reaction of iodide ion with
antiseptics, disinfectants, antimicrobials, antifertility hydrogen peroxide at room temperature.

1
Some Basic Concepts

of Chemistry
1. In order to oxidise a mixture of one mole of
Exp. (d)
each of FeC 2O4 , Fe 2 (C 2O4 )3 , FeSO4 and Given, WCa(HCO 3 )2 = 0.81 g
Fe 2 (SO4 )3 in acidic medium, the number of WMg(HCO ) = 0.73 g
3 2
moles of KMnO4 required is MCa(HCO 3 )2 = 162 g mol −1,

[JEE Main 2019, 8 April Shift-I] MMg(HCO 3 )2 = 146 mol −1
(a) 2 (b) 1 (c) 3 (d) 1.5 MH 2O = 100 mL
Exp. (a) Now, neq (CaCO 3)= neq [Ca(HCO 3 )2 ] + neq [Mg(HCO 3 )2 ]
W 0.81 073
.
The oxidation of a mixture of one mole of each of ×2 = ×2 + ×2
100 162 146
FeC 2O 4 , Fe 2 (C 2O 4 )3 FeSO 4 and
W
Fe 2 (SO 4 )3 in acidic medium with KMnO 4 is as follows : ∴ = 0.005 + 0.005
100
FeC 2O 4 + KMnO 4 → Fe 3+ + CO 2 + Mn2 + …(i) W = 0.01 × 100 = 1
Fe 2(C 2O 4 )3 + KMnO 4 → Fe 3+ + CO 2 + Mn2 + …(ii) Thus, hardness of water sample =
1
× 10 6
FeSO 4 + KMnO 4 → Fe 3+ + SO 24− + Mn2 + …(iii) 100
= 10,000 ppm
Change in oxidation number of Mn is 5. Change in
oxidation number of Fe in (i), (ii) and (iii) are
+3, + 6, + 1, respectively. 3. 0.27 g of a long chain fatty acid was dissolved in
neqKMnO 4 = neq [FeC 2O 4 + Fe 2 (C 2O 4 )3 + FeSO 4 ] 100 cm3 of hexane. 10 mL of this solution was
n × 5 = 1× 3 + 1× 6 + 1× 1 added dropwise to the surface of water in a
∴ n=2 round watch glass. Hexane evaporates and a
monolayer is formed. The distance from edge
2. 100 mL of a water sample contains 0.81 g of to centre of the watch glass is 10 cm. What is
calcium bicarbonate and 0.73 g of magnesium the height of the monolayer?
bicarbonate. The hardness of this water [Density of fatty acid = 0.9 g cm −3 ; π = 3]
sample expressed in terms of equivalents of [JEE Main 2019, 8 April Shift-II]
CaCO3 is (molar mass of calcium bicarbonate (a) 10−6
m (b) 10 −4
m (c) 10−8 m (d) 10−2 m
is 162 g mol −1 and magnesium bicarbonate is
146 g mol −1 ) [JEE Main 2019, 8 April Shift-I] Exp. (a)
(a) 5,000 ppm 100 mL (cm3) of hexane contains 0.27 g of fatty acid.
(b) 1,000 ppm In 10 mL solution, mass of the fatty acid,
(c) 100 ppm 0.27
(d) 10,000 ppm m= × 10 = 0.027 g
100

2 JEE Main Chapterwise Chemistry
Density of fatty acid, d = 0.9 g cm−3 Here, H 2 gas does not act as limiting reagent since
∴Volume of the fatty acid over the watch glass, 7.5 g of H 2 gas is required for 35 g of N 2 and 8 g of H 2
m 0.027 is present in reaction mixture. Mass of H 2 left unreacted
V = = = 0.03 cm3
d 0.9 = 8 − 7.5 g of H 2. = 0.5 g of H 2.
Let, height of the cylindrical monolayer = h cm Similarly, in option (c) and (d), H 2 does not act as
limiting reagent.
Q Volume of the cylinder = Volume of fatty acid
For 14 g of N 2 + 4 g of H 2.
As we know 28 g of N 2 reacts with 6 g of H 2.
6
14 g of N2 reacts with × 14 g of H 2 ⇒ 3 g of H 2.
28
h cm
For 28 g of N 2 + 6 g of H 2, i.e. 28 g of N 2 reacts with 6 g
of H 2 (by equation I).
10 cm 5. At 300 K and 1 atmospheric pressure,

10 mL of a hydrocarbon required 55 mL of O2
⇒ V = πr × h 2
for complete combustion and 40 mL of CO2 is
V 0.03 cm3 formed. The formula of the hydrocarbon is
⇒ h= =
πr 2
3 × (10)2 cm2 [JEE Main 2019, 10 April Shift-I]
−4
= 1 × 10 cm = 1 × 10 −6 m (a) C4 H7Cl (b) C4 H6
(c) C4 H10 (d) C4 H8
4. For a reaction,
N2 ( g ) + 3 H2 ( g ) → 2 NH3 ( g ), identify Exp. (b)
dihydrogen ( H2 ) as a limiting reagent in the In eudiometry,
C xH y +  x +  O 2 → x CO 2 + H 2O
300 K
following reaction mixtures. y y
[JEE Main 2019, 9 April Shift-I]  4 1 atm 2
(a) 56 g of N2 + 10 g of H2  y
1 mol x+  mol x mol
 4
(b) 35 g of N2 + 8 g of H2
 y
(c) 14 g of N2 + 4 g of H2 1 mL  x +  mL

x mL
4
(d) 28 g of N2 + 6 g of H2  y
10 mL  x +  × 10 mL 10x mL
 4
Exp. (a)
Given, (i) VCO2 = 10 x = 40 mL ⇒ x = 4
Key Idea The reactant which is present in the lesser
(ii) VO2 = 10  x +  mL = 55 mL
y
amount, i.e. which limits the amount of product formed
 4
is called limiting reagent.
10  4 +  = 55
y
⇒ [Q x = 4]
When 56 g of N 2 + 10 g of H 2 is taken as a  4
combination then dihydrogen (H 2 ) act as a limiting y × 10
reagent in the reaction. ⇒ 40 + = 55
4
N 2( g ) + 3H 2( g ) → 2NH 3( g ) …(I)
10 4
2 × 14g 3 × 2g 2( 14 + 3) ⇒ y× = 15 ⇒ y = 15 × =6
28g 6g 34g 4 10
28 g N 2 requires 6 g H 2 gas. So, the hydrocarbon (C xH y ) is C 4H 6.
6g
56 g of N 2 requires × 56 g = 12 g of H 2 6. The minimum amount of O2 ( g ) consumed per
28 g
12 g of H 2 gas is required for 56 g of N 2 gas but gram of reactant is for the reaction (Given
only 10 g of H 2 gas is present in option (a). atomic mass : Fe = 56, O =16, Mg = 24, P = 31,
Hence, H 2 gas is the limiting reagent. C =12, H =1) [JEE Main 2019, 10 April Shift-II]
In option (b), i.e. 35 g of N 2 + 8 g of H 2. (a) C 3H 8 ( g ) + 5O 2( g ) → 3CO 2( g ) + 4H 2O(l )
As 28 g N 2 requires 6 g of H 2. (b) P4 ( s ) + 5O 2( g ) → P4O 10 ( s )
6g (c) 4Fe( s ) + 3O 2( g ) → 2Fe 2O 3( s )
35 g N 2 requires × 35 g H 2 ⇒ 7.5 g of H 2.
28 g
(d) 2Mg( s ) + O 2 ( g ) → 2MgO( s )

Some Basic Concepts of Chemistry 3
Exp. (b) From equation (i) and (ii)

1 (M A + 2 M B )
= 
125 
(a) C 3H8 (g ) + 5O 2 (g ) → 3CO 2 (g ) + 4H2O(l ) 
44g 160g 2 (2 M A + 2 M B )  300 
160 On solving the equation, we obtain
⇒ 1g of reactant = g of O 2 consumed
M A = 5 × 10 −3 and M B = 10 × 10 −3
44
= 3.64 g So, the molar mass of A( M A ) is
(b) P4 (s ) + 5O 2 (g ) → P4O10 (s ) 5 × 10 −3 kgmol −1 and B( M B )is10 × 10 −3 kgmol −1.
124g 160g
160
⇒ 1g of reactant g of O 2 consumed = 129
. g 8. 25 g of an unknown hydrocarbon upon
124
burning produces 88 g of CO2 and 9 g of H 2O.
(c) 4Fe(s ) + 3O 2 (g ) → 2Fe 2O 3 (s )
244g 96g This unknown hydrocarbon contains
[JEE Main 2019, 12 April Shift-II]
96
⇒ 1 g of reactant g of O 2 consumed (a) 20 g of carbon and 5 g of hydrogen
224
= 0.43 g (b) 22 g of carbon and 3 g of hydrogen
(d) 2Mg(s ) +O 2 (g ) → 2MgO(s ) (c) 24 g of carbon and 1 g of hydrogen
48 g 32 g (d) 18 g of carbon and 7 g of hydrogen
32
⇒ 1 g of reactant g of O 2 consumed
48 Exp. (c)
= 0.67 g
So, minimum amount of O 2 is consumed per gram of Hydrocarbon containing C and H upon burning
reactant (Fe) in reaction (c). produces CO 2 and water vapour respectively. The
equation is represented as
7. 5 moles of AB 2 weight125 × 10 −3 kg and 10 moles C xH y + ( x + y / 4)O 2 → xCO 2 + ( y / 2 ) H 2O
12
of A 2 B 2 weight 300 × 10 −3 kg. The molar mass of Mass of carbon = × mass of CO 2
44
A ( M A )and molar mass of B ( M B )in kg mol −1 are 12
= × 88 g = 24 g
[JEE Main 2019, 12 April Shift-I] 44
(a) M A = 10 × 10 −3 and M B = 5 × 10 −3 2
Mass of hydrogen = × mass of H 2O
(b) M A = 50 × 10 −3 and M B = 25 × 10 −3 18
(c) M A = 25 × 10 −3 and M B = 50 × 10 −3 2
= × 9 = 1g
(d) M A = 5 × 10−3 and M B = 10 × 10−3 18
So, the unknown hydrocarbon contains 24 g of carbon
Exp. (d) and 1g of hydrogen.
Key Idea To find the mass of A and B in the given 9. For the following reaction, the mass of water
question, mole concept is used. produced from 445 g of C57H110O6 is :
given mass ( w )
Number of moles ( n) =
molecular mass ( M ) 2C57H110O6(s ) + 163O2( g ) → 114CO2( g )
Compound Mass of A (g) Mass of B (g) + 110 H2O (l )

(a) 490 g (b) 495 g (c) 445 g (d) 890 g
AB2 MA 2MB
A 2B2 2MA 2MB Exp. (b)
We know that, 2 C 57H110O 6( s )+ 163 O 2( g ) →
given mass ( w ) 110 H 2O( l ) + 114 CO 2( g )
Number of moles ( n) =
molecular mass ( M ) Molecular mass of C 57H110O 6
= 2 × (12 × 57 + 1 × 110 + 16 × 6) g = 1780 g
n × M = w …(A)
Molecular mass of 110 H 2O = 110 (2 + 16) = 1980 g
Using equation (A), it can be concluded that
1780 g of C 57H110O 6 produced = 1980 g of H 2O.
5( M A + 2 M B ) = 125 × 10 −3 kg …(i) 1980
445g of C 57H110O 6 produced = × 445 g of H 2O
−3
10(2 M A + 2 M B ) = 300 × 10 kg …(ii) 1780
= 495 of H 2O

10. In the reaction of oxalate with permanganate 12. The hardness of a water sample (in terms of
in acidic medium, the number of electrons equivalents of CaCO3 ) containing
involved in producing one molecule of CO2 is 10 −3 M CaSO4 is
(a) 2 (b) 5 (Molar mass of CaSO4 = 136 g mol−1 )
(c) 1 (d) 10 (a) 100 ppm (b) 10 ppm

[JEE Main 2019, 10 Jan Shift-II] (c) 50 ppm (d) 90 ppm
Exp. (c) [ JEE Main 2019, 12 Jan Shift-I]
Reaction of oxalate with permanganate in acidic Exp. (a)

medium.
Hardness of water sample can be calculated in terms
5C 2O 42− + 2MnO −4 → 10CO 2 + 2Mn2 + + 8H 2O of ppm concentration of CaCO 3.
n-factor : ( 4 − 3) × 2 = 2 (7 − 2 ) = 5 Given, molarity = 10 −3M
No. of mole 5 2 10 i.e. 1000 mL of solution contains10 −3 mole ofCaCO 3.
∴Hardness of water = ppm of CaCO 3
⇒ 5C 2O 42– ions transfer 10 e − to produce
10 −3 × 1000
10 molecules of CO 2. = × 10 6
So, number of electrons involved in producing 1000
10 molecules of CO 2 is 10. Thus, number of electrons = 100 ppm
involved in producing 1 molecule of CO 2 is 1.
13. Decomposition of X exhibits a rate constant of
11. A 10 mg effervescent tablet containing sodium 0.05 µg/year. How many years are required for
bicarbonate and oxalic acid releases 0.25 mL of the decomposition of 5 µg of X into 2.5 µg?
CO2 at T = 298.15 K and p =1 bar. If molar (a) 20 (b) 25
volume of CO2 is 25.0 L under such condition, (c) 40 (d) 50
what is the percentage of sodium bicarbonate [ JEE Main 2019, 12 Jan (Shift-I)]
in each tablet?
[Molar mass of NaHCO 3 = 84 g mol −1 ]
Exp. (d)
Given, rate constant (k) = 0.05 µg/year
(a) 8.4 (b) 0.84
Thus, from the unit of k, it is clear that the reaction is
(c) 16.8 (d) 33.6 zero order. Now, we know that
[ JEE Main 2019, 11 Jan Shift-I] a
half-life (t 1/ 2 ) for zero order reaction = o
2k
Exp. (a)
where, ao = initial concentration,
2NaHCO 3 + H 2C 2O 4 → 2CO 2 + Na 2C 4O 4 + H 2O
k = rate constant
2 mol 1 mol 2 mol
5 µg
⇒ In the reaction, number of mole of CO 2 t 1/ 2 =
2 × 0.05 µg / year
produced.
pV 1 bar × 0.25 × 10 −3 L = 50 years
n= = Thus, 50 years are required for the decomposition of
RT 0.082 L atm K −1mol −1 × 298.15 K
5 µg of X into 2.5 µg.
= 1.02 × 10 −5 mol
Number of mole of NaHCO 3
14. The ratio of mass per cent of C and H of an
Weight of NaHCO 3 organic compound (C x H yOz ) is 6 : 1. If one
= molecule of the above compound (C x H yOz )
Molecular mass of NaHCO 3
contains half as much oxygen as required to burn
∴ wNaHCO 3 = 1.02 × 10 −5 × 84 × 10 3 mg
one molecule of compound C x H y completely
= 0.856 mg to CO2 and H 2O. The empirical formula of
0.856
⇒ NaHCO 3 % = × 100 compound C x H yOz is [ JEE Main 2018]
10
(a) C 3H 6O 3 (b) C 2H 4O
= 8.56%
(c) C 3H 4O 2 (d) C 2H 4O 3

Exp. (d) Exp. (c)

We can calculate the simplest whole number ratio of C Given, abundance of elements by mass
and H from the data given, as oxygen = 614. %, carbon = 22.9%, hydrogen = 10% and
nitrogen = 2.6%
Element Relative Molar Relative Simplest
Total weight of person = 75 kg
mass mass mole whole no.

ratio 75 × 10
Mass due to 1H = = 7.5 kg
6 0.5 100
C 6 12 = 0.5 =1
12 0.5 1
H atoms are replaced by 2H atoms,
H 1 1 1 1 Mass due to 2H = (7.5 × 2) kg

=1 =2
1 0.5 ∴Mass gain by person = 7.5 kg
Alternatively this ratio can also be calculated directly 16. 1 g of a carbonate (M 2CO3 ) on treatment with
in the terms of x and y as excess HCl produces 0.01186 mole of CO2 . The
12 x 6
= (given and molar mass of C = 12, H = 1) molar mass of M 2CO3 in g mol − 1 is
y 1 [ JEE Main 2017 (Offline)]
Now, after calculating this ratio look for condition 2 (a) 1186 (b) 84.3
given in the question i.e. quantity of oxygen is half (c) 118.6 (d) 11.86
of the quantity required to burn one molecule of
compound C xHy completely to CO 2 and H2O. We Exp. (b)
can calculate number of oxygen atoms from this as M2CO 3 + 2HCl → 2M Cl + H 2O + CO 2
consider the equation. 1g 0.01186 mole
Number of moles of M2CO 3 reacted = Number of moles
C xH y +  x +  O 2 → xCO 2 + H 2O
y y
 4  2 of CO 2 evolved
1
Number of oxygen atoms required = 0.01186 [M = molar mass of M2CO 3]
M
= 2 ×  x +  = 2 x + 
y y 1
 M = = 84.3 g mol − 1
4   2  0.01186
Now given, z = 2 x +  =  x + 
1 y y
2  2   4 
17. At 300 K and 1 atm, 15 mL of a gaseous
hydrocarbon requires 375 mL air containing
Here we consider x and y as simplest ratios for C
20% O 2 by volume for complete combustion.
and H so now putting the values of x and y in the
above equation. After combustion, the gases occupy 330 mL.
Assuming that the water formed is in liquid
z =  x +  = 1 +  = 1.5
y 2
 
4   4  form and the volumes were measured at the
same temperature and pressure, the formula
Thus, the simplest ratio figures for x, y and z are
x = 1, y = 2 and z = 15
. of the hydrocarbon is [ JEE Main 2016 (Offline)]
Now, put these values in the formula given i.e. (a) C3 H8 (b) C4 H8
C xH yO z = C 1H 2O1.5 (c) C4 H10 (d) C3 H6
So, empirical formula will be
Exp. (None)
[C 1H 2O1.5 ] × 2 = C 2H 4O 3
C xH y ( g ) +  x +  O 2( g ) → xCO 2 ( g ) + H 2O ( l )
y y
15. The most abundant elements by mass in the  4 75 mL 2 30 mL
body of a healthy human adult are Oxygen O 2 used = 20% of 375 = 75 mL

(61.4%); Carbon (22.9%), Hydrogen (10.0 %); Inert part of air = 80% of 375 = 300 mL
Total volume of gases = CO 2 + Inert part of air
and Nitrogen (2.6%). The weight which a 75 kg
= 30 + 300 = 330 mL
person would gain if all 1 H atoms are replaced y
by 2 H atoms is x+
[ JEE Main 2017 (Offline)] x 30 4 75 y
= ⇒ x=2 ⇒ = ⇒ x+ =5
(a) 15 kg (b) 37.5 kg 1 15 1 15 4
(c) 7.5 kg (d) 10 kg ⇒ x = 2, y = 12 ⇒ C 2 H12

18. The molecular formula of a commercial resin

20. The ratio of masses of oxygen and nitrogen in a
used for exchanging ions in water softening is
particular gaseous mixture is 1 : 4. The ratio of
C 8H 7 SO3 Na (mol. wt. = 206). What would be
number of their molecule is [ JEE Main 2014]
the maximum uptake of Ca 2+ ions by the resin
(a) 1 : 4 (b) 7 : 32
when expressed in mole per gram resin?
(c) 1 : 8 (d) 3 :16

[ JEE Main 2015] Exp. (b)
1 1 2 1
(a) (b) (c) (d) The number of moles is given by
103 206 309 412 weight ( w )
n=
Exp. (d) molecular weight ( M )
We know the molecular weight of C 8H 7SO 3Na Thus, ratio of moles of O 2 and N 2 is given by
= 12 × 8 + 1 × 7 + 32 + 16 × 3 + 23 = 206 nO 2  WO 2 / MO 2   WO 2   MN 2 
=  =   
We have to find, mole per gram of resin. W / M  W  M 
n N2  N2 N2   N2   O2 
∴ 1 g of C 8H 7SO 3Na has number of mole
=   ×   =
1 28 7
Weight of given resin 1
= = mol  4   32  32
Molecular weight of resin 206
Hence, ratio of nO 2 and n N 2 is 7 : 32 .
Now, reaction looks like
2C 8H 7SO 3Na + Ca 2 + → (C 8H 7SO 3 )2Ca + 2Na +
21. The molarity of a solution obtained by mixing
2+ 750 mL of 0.5 M HCl with 250 mL of 2M HCl
Q 2 moles of C 8H 7SO 3Na combines with 1 mol Ca
1 will be [JEE Main 2013]
∴ 1 mole of C 8H 7SO 3Na will combine with mol Ca 2 +
2 (a) 0.875 M (b) 1.00 M
(c) 1.75 M (d) 0.0975 M
1
∴ mole of C 8H 7SO 3Na will combine with
206 Exp. (a)
1 1 1
× mol Ca 2 + = mol Ca 2 + The molarity of a resulting solution is given by
2 206 412 M V + M 2V2 750 × 0.5 + 250 × 2 875
M = 11 = =
V1 + V2 750 + 250 1000
19. 3 g of activated charcoal was added to 50 mL of
= 0.875 M
acetic acid solution (0.06 N) in a flask. After an
hour it was filtered and the strength of the 22. A gaseous hydrocarbon gives upon combustion,
filtrate was found to be 0.042 N. The amount of 0.72 g of water and 3.08 g of CO2 . The empirical
acetic acid adsorbed (per gram of charcoal) is formula of the hydrocarbon is [ JEE Main 2013]
[JEE Main 2015] (a) C2 H4 (b) C3 H4 (c) C6 H5 (d) C7 H8
(a) 18 mg (b) 36 mg (c) 42 mg (d) 54 mg
Exp. (d)
Exp. (a) 18 g H 2O contain 2g H.
Given, initial strength of acetic acid = 0.06N ∴ 0.72 g H 2O contain 0.08 g H
Final strength = 0.042 N
44 g CO 2 contain 12 g C.
Volume given = 50 mL
∴ Initial m moles of CH 3COOH = 0.06 × 50 = 3 ∴ 3.08 g CO 2 contain 0.84 g C.
0.84 0.08
Final m moles of CH 3COOH = 0.042 × 50 = 2.1 ∴ C :H = :
∴ m moles of CH 3COOH adsorbed 12 1
= 3 − 2.1 = 0.9 m mol = 0.07 : 0.08 = 7 : 8
∴ Empirical formula = C 7 H 8
Hence, mass of CH 3COOH absorbed per gram of
charcoal 23. The density of a solution prepared by
0.9 × 60 dissolving 120 g of urea (mol. mass = 60 u) in
=
3 1000 g of water is 1.15 g/mL. The molarity of
(Q molar mass of CH 3COOH = 60 gmol −1) this solution is [AIEEE 2012]
54 (a) 0.50 M (b) 1.78 M
= = 18 mg.
3 (c) 1.02 M (d) 2.05 M

Exp. (d) 1g
= 300 mL × [Q1 dm3 = 1000 mL]
mL
Total mass of solution = 1000 g water + 120 g urea
= 1120 g = 300 g
Density of solution = 1.15 g / mL Mass of solvent = 300 g − 0.0100 g
Thus, volume of solution =

mass
=
1120 g = 299.9 g = 0.2999 kg
density 1.15 g / mL 0.0100

Molality = = 5.55 × 10 −4 mol kg −1
= 973.91 mL = 0.974 L 60 × 0.2999
120 26. Amount of oxalic acid present in a solution can
Moles of solute = = 2 mol
60 be determined by its titration with KMnO4
moles of solute 2 mol
Molarity = = solution in the presence of H 2 SO4 . The titration
volume (L) of solution 0.974 L
gives unsatisfactory result when carried out in
= 2.05 mol L−1 the presence of HCl because HCl [AIEEE 2008]
(a) gets oxidised by oxalic acid to chlorine
24. The mass of potassium dichromate crystals
(b) furnishes H + ions in addition to those from
required to oxidise 750 cm3 of 0.6 M Mohr’s salt oxalic acid
solution is (molar mass = 392) [AIEEE 2011] (c) reduces permanganate to Mn 2 +
(a) 0.49 g (b) 0.45 g (d) oxidises oxalic acid to carbon dioxide and water
(c) 22.05 g (d) 2.2 g
Exp. (c)
Exp. (c) Titration of oxalic acid by KMnO 4 in the presence of HCl
gives unsatisfactory result because HCl is a better
Mohr’s salt is FeSO4 ⋅ (NH 4 )2SO 4 ⋅ 6H 2O.
reducing agent than oxalic acid and HCl reduces
Only oxidisable part Fe 2+ is preferably MnO –4 to Mn2+ .
[Fe 2+ → Fe 3+ + e − ] × 6
27. In the reaction,
Cr2O 27 − +14H+ + 6e − → 2Cr 3+ +7H2O 2Al (s ) + 6HCl (aq ) → 2Al 3+ (aq )
6Fe 2+ +Cr2O 27 − +14H+ → + 6Cl − (aq ) + 3H 2( g ) [AIEEE 2007]
6Fe 3+ +2Cr 3 + +7H2O (a) 6L HCl (aq ) is consumed for every 3L H2 ( g )
Millimoles of Fe 2+ = 750 × 0.6 = 450 produced
(b) 33.6 L H2 ( g ) is produced regardless of
450
Moles of Fe 2+ = = 0.450 mol temperature and pressure for every mole Al
1000 that reacts
6 mol Fe 2 + ≡ 1 mol Cr2O 27 − (c) 67.2 L H2 ( g ) at STP is produced for every mole
0.450 Al that reacts
∴ 0.450 mol Fe 2+ ≡ = 0.075 mol Cr2O 2−
7
6 (d)11.2 L H2 ( g ) at STP is produced for every mole
= 0.075 × 294 g = 22.05 g HCl (aq ) consumed
25. The molality of a urea solution in which Exp. (d)

0.0100 g of urea, [( NH 2 )2 CO] is added to 2Al( s ) + 6HCl( aq ) → 2Al 3+ ( aq ) + 6Cl − ( aq ) + 3H 2( g )
0.3000 dm 3 of water at STP is [AIEEE 2011] From the equation, it is clear that,
(a) 5.55 × 10 − 4 M (b) 33.3M 6 mol of HCl produces 3 mol of H 2
(c) 3.33 × 10 −2 M (d) 0.555 M 3 × 22.4
or 1 mole of HCl = L of H 2 = 11.2 L of H 2
6
Exp. (a)
moles of the solute
28. How many moles of magnesium phosphate,
Molality = Mg 3 (PO4 )2 will contain 0.25 mole of oxygen
mass of the solvent in kg
atoms? [AIEEE 2006]
0.0100 g
Moles of urea ( nurea ) = (a) 0.02 (b) 3.125 × 10 −2
60 g mol −1
(c) 1.25 × 10 −2 (d) 2.5 × 10 −2
Mass of 1000 mL of solution = volume × density
Exp. (b)
8 moles of O-atom are contained by 1 mole Mg 3(PO 4 )2.

Hence, 0.25 moles of O-atom are contained by (c) Both (a) and (b) (d) None of these
1
= × 0.25 mol Mg 3 ( PO 4 )2 = 3.125 × 10 −2
8 Exp. (c)
560 g of Fe
29. If we consider that 1/6, in place of 1/12, mass of 560 g
Number of moles = = 10 mol
carbon atom is taken to be the relative atomic 56 g mol −1

mass unit, the mass of one mole of a substance
For 70 g of N
will [AIEEE 2005] 14 g N = 1 mol of N -atom
(a) be a function of the molecular mass of the
70 g N = 5 mol of N -atom
substance
For 20 g of H
(b) remain unchanged
(c) increase two fold 1 g H = 1 mol of H -atom
(d) decrease twice 20 g H ≡ 20 mol of H -atom
Exp. (b) 32. In an organic compound of molar mass
The mass of one mole of a substance will remain 108 g mol –1 C, H and N atoms are present in
unchanged.
9 : 1 : 3.5 by weight. Molecular formula can be
30. What volume of hydrogen gas, at 273 K and [AIEEE 2002]
1 atm pressure will be consumed in obtaining (a) C 6 H 8 N 2 (b) C 7 H 10 N
21.6 g of elemental boron (atomic mass = 10.8) (c) C 5H 6 N 3 (d) C 4 H 18 N 3
from the reduction of boron trichloride by Exp. (a)
hydrogen? [AIEEE 2003]
Molar mass 108 g mol −1
(a) 89.6 L (b) 67.2 L
Total part by weight = 9 + 1 + 3.5 = 13.5
(c) 44.8 L (d) 22.4 L
9
Weight of carbon = × 108 = 72 g
Exp. (b) 13.5
2BCl 3 + 3H 2 → 2B + 6HCl Number of carbon atoms =
72
=6
2 mol 3 mol 2 mol 12
21.6 g 1
Weight of hydrogen = × 108 = 8 g
21.6 g B = 2 mol B ≡ 3 mol H 2 13.5
pV = nRT 8
Number of hydrogen atoms = = 8
nRT 1
∴ V = p 3.5
Weight of nitrogen = × 108 = 28 g
3 × 0.0821 × 273 13.5
= = 67.2 L
1 28
Number of nitrogen atom = =2
31. Number of atoms in 560 g of Fe 14
(atomic mass = 56 g mol −1 ) is [AIEEE 2002] Hence, molecular formula = C 6H 8N 2.
(a) twice that of 70 g N (b) half that of 20 g H

2
States of Matter
1. Element ‘B ’ forms ccp structure and ‘A ’
Exp. (b)
occupies half of the octahedral voids, while Key Idea Packing efficiency
oxygen atoms occupy all the tetrahedral voids. Volume occupied by sphere
The structure of bimetallic oxide is = × 100
Volume of cube
[JEE Main 2019, 8 April Shift-I]
Given, rB = 2 rA
(a) A 2 BO 4 (b) AB2O 4
50
(c) A 2B2O (d) A 4 B2O a2 = a1 + a1 = 15
. a1
100
Exp. (b) For bcc lattice
The number of element ‘B ’ in the crystal 4rA = 3 a1
structure = 4 N 3 a1
rA =
Number of tetrahedral voids = 2N 4
Number of octahedral voids = N 4r
a1 = A
N 4 3
∴Number of ‘A’ in the crystal = = = 2
4r 3 4r
2 2 ∴ .  A  =  A 
a2 = 15
Number of oxygen (O) atoms = 2 N = 2 × 4 = 8  3 2  3
∴The structure of bimetallic oxide = A2 B4 O 8 a2 = 2 3 rA
= AB2 O 4 4 3 4
πrA × zA + πrB3 × zB
Packing efficiency = 3 3
2. Consider the bcc unit cells of the solids 1 and 2 a23
with the position of atoms as shown below.
[As the atoms A are present at the edges only
The radius of atom B is twice that of atom A. 1
The unit cell edge length is 50% more is solid 2 zA = × 8 = 1, atom B is present only at the body
8
than in 1. What is the approximate packing centre zB = 1]
efficiency in solid 2?
 4 πr 3 × 1 +  4 πr 3 × 1
A A    
 A
 3 B 
PE 2 = 3
A A
∴ 3
A a2
A A A
4 3 4
B πrA + π (2 rA )3
A
A = 3 3
A A A (2 3 rA )3
A A 4 3
A A πrA × 9
Solid 1 Solid 2 π
= 3 =
(a) 65% (b) 90% (c) 75% (d) 45% 8 × 3 3 rA3 2 3
[JEE Main 2019, 8 April Shift-II] = 90.72% ≈ 90%

pV − pb = RT
3. Consider the van der Waals’ constants,
⇒ pV = RT + pb
a and b, for the following gases.
pV pb
= 1+
Gas Ar Ne Kr Xe RT RT
pV
6
a/(atm dm mol ) −2
1.3 0.2 5.1 4.1 As, Z=
RT
b/(10 −2 dm 3 mol −1) 3.2 1.7 1.0 5.0 so, Z = 1+
pb
⇒ y = c + mx
RT
Which gas is expected to have the highest The plot of z vs p is found to be
critical temperature ?
b
(a) Kr (b) Xe (c) Ar (d) Ne slope =
RT
Z
Exp. (a)
Critical temperature is the temperature of a
gas above which it cannot be liquefied what
ever high the pressure may be. The kinetic
p
energy of gas molecules above this
temperature is sufficient enough to overcome The gas with high value of b will be steepest as
the attractive forces. It is represented as Tc . slope is directly proportional to b. b is the van der
8a Waals’ constant and is equal to four times the actual
Tc =
27 Rb volume of the gas molecules. Xe gas possess the
8 × 1.3 largest atomic volume among the given noble gases
For Ar, Tc = = 0.0144
27 × 8.314 × 3.2 (Ne, Kr, Ar). Hence, it gives the steepest increase in
8 × 0.2 the plot of Z (compression factor) vsp.
For Ne, Tc = = 0.0041
27 × 8.314 × 1.7
8 × 51 . 5. 10 mL of 1 mM surfactant solution forms a
For Kr, Tc = = 0.18
27 × 8.314 × 1.0 monolayer covering 0.24 cm 2 on a polar substrate.
8 × 4.1 If the polar head is approximated as a cube, what
For Xe, Tc = = 0.02 is its edge length? [JEE Main 2019, 9 April Shift-II]
27 × 8.314 × 5.0
The value of Tc is highest for Kr (Krypton). (a) 2.0 pm (b) 0.1 nm (c) 1.0 pm (d) 2.0 nm
Exp. (a)
4. At a given temperature T , gases Ne, Ar, Xe
and Kr are found to deviate from ideal gas Given, volume = 10 mL, Molarity = 1mM = 10−3 M
behaviour. Their equation of state is given ∴Number of millimoles = 10 mL × 10−3 M = 10−2
RT Number of moles = 10−5
as, p = atT .
V −b Now, number of molecules
Here, b is the van der Waals’ constant. = Number of moles × Avogadro’s number
Which gas will exhibit steepest increase in = 10−5 × 6 × 1023 = 6 × 1018
the plot of Z (compression factor)vs p?
Surface area occupied by 6 × 1018 molecules
= 0.24 cm2
(a) Xe (b) Ar (c) Kr (d) Ne
∴Surface area occupied by 1 molecule
Exp. (a) 0.24
= = 0.04 × 10−18 cm2
Noble gases such as Ne, Ar, Xe and Kr found 6 × 1018
to deviate from ideal gas behaviour. As it is given that polar head is approximated as cube.
Xe gas will exhibit steepest increase in plot of Thus, surface area of cube = a2 ,
Z vs p. Equation of state is given as: where, a = edge length
RT
p= ∴ a2 = 4 × 10−20 cm2
(V − b)
a = 2 × 10−10 cm = 2 pm
⇒ p(V − b ) = RT

States of Matter 11
6. Consider the following table. 7. Points I, II and III in the following plot
respectively correspond to (v mp : most
Gas a/(k Pa dm6 mol−1) b/(dm3 mol−1 )
probable velocity)
A 642.32 0.05196 [JEE Main 2019, 10 April Shift-II]
B 155.21 0.04136
Distribution function f( v)
C 431.91 0.05196
D 155.21 0.4382
a and b are van der Waals’ constants. The

correct statement about the gases is
(a) gas C will occupy lesser volume than gas A; gas
B will be lesser compressible than gas D I II III
(b) gas C will occupy more volume than gas A; gas Speed, v
B will be more compressible than gas D
(c) gas C will occupy more volume than gas A; gas (a) v mp of H2 (300 K); v mp of N 2 (300 K); v mp
B will be lesser compressible than gas D of O 2 (400 K)
(d) gas C will occupy more volume than gas A; gas (b)v mp of O 2 (400 K); v mp of N 2 (300 K); v mp
B will be lesser compressible than gas D of H2 (300 K)
Exp. (b) (c) v mp of N 2 (300 K); v mp of O 2 ( 400 K ); v mp
For 1 mole of a real gas, the van der Waals’ of H2 (300 K)
equation is (d)v mp of N 2 (300 K); v mp of H2 (300 K); v mp
 p + a  (V − b ) = RT of O 2 (400 K)
 
 V2 
Exp. (c)
The constant ‘a’ measures the intermolecular
force of attraction of gas molecules and the Key Idea From kinetic gas equation,
constant ‘b’ measures the volume correction by
2 RT
gas molecules after a perfectly inelastic binary Most probable velocity (v mp ) =
collision of gas molecules. M
For gas A and gas C given value of ‘b’ is where, R = gas constant, T = temperature,
0.05196 dm3 mol −1. Here, M = molecular mass
a ∝ intermolecular force of attraction 2 RT
∝ compressibility ∝ real nature vmp =
M
1
∝ T
volume occupied i.e. vmp ∝
6 −1
M
Value of a/(kPa dm mol ) for gas A (642.32) >
gas C (431.91) So, gas C will occupy more Gas M T(K) T /M
volume than gas A. Similarly, for a given value of
a say 155.21 kPa dm 6 mol −1 for gas B and gas D H2 2 300 300 / 2 = 150 …III (Highest)
1
∝ intermolecular force of attraction N2 28 300 300 / 28 = 1071
. …I (Lowest)
b
∝ compressibility ∝ real nature O2 32 400 400 / 32 = 12.5 … II
1
∝
volume accupied So,
3 −1
b/(dm mol ) for gas B (0.04136) < Gas D I corresponds to vmp of N2 (300 K)
(0.4382) II corresponds to vmp of O 2 (400 K)
So, gas B will be more compressible than gas D. III corresponds to vmp of H2 (300 K)

8. An element has a face-centred cubic (fcc) 10. At 100°C, copper (Cu) has FCC unit cell
structure with a cell edge of a. The distance structure with cell edge length of x Å. What is
between the centres of two nearest tetrahedral the approximate density of Cu (in g cm −3 ) at
voids in the lattice is this temperature?
[Atomic mass of Cu = 63.55 u]

(a) 2a (b) a 211 205
(a) (b)
a 3 x3 x3
(c) (d) a
2 2 105 422
(c) (d)
x3 x3
Exp. (c) [JEE Main 2019, 9 Jan Shift-II]
In fcc unit cell, two tetrahedral voids are formed on
each of the four non-parallel body diagonals of the Exp. (d)
cube at a distance of 3a / 4 from every corner For fcc, rank of the unit cell (Z ) = 4
along the body diagonal.
Mass of one Cu-atom, M = 63.55 u
One of the body diagonal Avogadro’s number, NA = 6.023 × 1023 atom
of cubic unit cell
A Edge length, a = x Å = x × 10−8 cm
1 Z×M
— AB density (d ) =
4
Position of 2 TVs
NA × a3
√3 a
— A′ 1 on one of the 4 × 63.55
4 —(AB)
2 body diagonal
=
of the unit cell
6.023 × 1023 × ( x × 10−8 )3
422.048
= g cm−3
B′ 1 x3
—(AB)
4
B 11. Which primitive unit cell has unequal edge
√3 a
—
4 lengths (a ≠ b ≠ c ) and all axial angles different
from 90°?
The angle between body diagonal and an edge (a) Hexagonal (b) Monoclinic
is cos −1 (1/ 3 ). So, the projection of the line on (c) Tetragonal (d) Triclinic
an edge is a/ 4. [JEE Main 2019, 10 Jan Shift-I]
Similarly, other tetrahedral void also will be a/4 Exp. (d)
away.
Triclinic primitive unit cell has dimensions as,
So, the distance between these two is
a ≠ b ≠ c and α ≠ β ≠ γ ≠ 90° .
a − a  − a = a .
 Among the seven basic or primitive crystalline
4  4 2 systems, the triclinic system is most
unsymmetrical. In other cases, edge length and
9. The ratio of number of atoms present in a axial angles are given as follows :
simple cubic, body centered cubic and face Hexagonal : a = b ≠ c and α = β = 90°, γ = 120°
centered cubic structure are, respectively.
Monoclinic : a ≠ b ≠ c and α = γ = 90°, β ≠ 90°
Tetragonal : a ≠ b ≠ c and α = β = γ = 90°
(a) 8 : 1 : 6
(b) 1 : 2 : 4 12. A compound of formula A 2B3 has the hcp
(c) 4 : 2 : 1 lattice. Which atom forms the hcp lattice and
(d) 4 : 2 : 3 what fraction of tetrahedral voids is occupied
Exp. (b) by the other atoms ?
2
The ratio of number of atoms present in simple (a) hcp lattice- A, tetrahedral voids-B
3
cubic, body centred cubic and face centered 1
cubic structure are 1 : 2 : 4 respectively. (b) hcp lattice-A, tetrahedral voids-B
3

States of Matter 13
1
(c) hcp lattice-B, tetrahedral voids-A 14. The radius of the largest sphere which fits
3
2 properly at the centre of the edge of a body
(d) hcp lattice-B, tetrahedral voids-A centred cubic unit cell is
3
(Edge length is represented by ‘a’)
[JEE Main 2019, 10 Jan Shift-II]
(a) 0.134 a (b) 0.027 a

Exp. (c) (c) 0.047 a (d) 0.067 a
Total effective number of atoms in hcp unit lattice = [JEE Main 2019, 11 Jan Shift-II]
Number of octahedral voids in hcp = 6
Exp. (d)
∴ Number of tetrahedral voids (TV) in hcp
For body centred cubic bcc structure,
= 2 × Number of atoms in hcp lattice
3
= 2 × 6 = 12 radius (R ) = a ...(i)
4
As, formula of the lattice is A2 B3 .
Where, a = edge length
Suppose, A B
According to question, the structure of cubic unit
 1 × TV  (hcp)
  cell can be shown as follows:
3 
1 R 2r R
⇒ × 12 6
3
2
⇒ 1
3
⇒ 2 3
1
So, A = tetrahedral voids, B = hcp lattice
3
13. A solid having density of 9 × 10 3 kgm−3 forms

face centred cubic crystals of edge length a
200 2 pm. What is the molar mass of the solid? ∴ a = 2(R + r ) ...(ii)
[Avogadro constant = 6 × 10 23 mol−1 , π = 3] On substituting the value of R from Eq. (i) to Eq. (ii),
(a) 0.03050 kg mol −1 (b) 0.4320 kg mol −1 we get
a 3
(c) 0.0432 kg mol −1 (d) 0.0216 kg mol −1 = a+ r
2 4
[JEE Main 2019, 11 Jan Shift-I] a 3 2 a − 3a
r= − a=
Exp. (a) 2 4 4
a(2 − 3 )
Density of a crystal r=
4
M×Z d × NA × a3
d= ⇒ M= ⇒ r = 0.067 a
NA × a3 Z
Given, d = 9 × 103 kg m −3 15. The volume of gas A is twice than that of gas B.
M = Molar mass of the solid
The compressibility factor of gas A is thrice
than that of gas B at same temperature. The
Z = 4 (for fcc crystal)
pressures of the gases for equal number of
NA = Avogadro’s constant = 6 × 1023 mol −1
moles are
a = Edge length of the unit cell (a) p A = 2p B (b) 2p A = 3p B
= 200 2 pm (c) p A = 3p B (d) 3p A = 2p B
= 200 2 × 10−12 m [JEE Main 2019, 12 Jan Shift-I]
On substituting all the given values, we get Exp. (b)
3 −3 23 −1 −12 3 3
(9 × 10 ) kg m × (6 × 10 ) mol × (200 2 × 10 ) m Given, Z A = 3Z B
=
4 pV
Compressibility factor (Z) = [for real gases]
= 0.0305 kg mol −1 nRT

On substituting in equation (i), we get Exp. (c)

pA VA 3 pB VB It is the ‘‘Frenkel defect’’ in which cations leave
= …(ii)
nA RTA nB RTB their original site and occupy interstitial site as
shown below.
Also, it is given that
VA = 2 VB , nA = nB and TA = TB + – + – + – + – Original
– + – + – + – + vacant site
∴ Eq. (ii) becomes – – + – + – of cation
+ +
pA × 2 VB 3 pB VB – + – – + – +
= Cation in
nB RTB nB RTB + – + – + – + – interstitial site
+
– + – + – + – +
⇒ 2 pA = 3 pB
+ – + – + – + –
– + – + – + – +
16. An open vessel at 27ºC is heated until two fifth
of the air (assumed as an ideal gas) in it has
escaped from the vessel. Assuming that the
18. A metal crystallises in a face centred cubic
structure. If the edge length of its unit cell is ‘a’,
volume of the vessel remains constant, the
the closest approach between two atoms in
temperature at which the vessel has been
metallic crystal will be [ JEE Main 2017 (Offline)]
heated is a
(a) 750 K (b) 500 K (a) 2 a (b) 2 2 a (c) 2 a (d)
2
(c) 750ºC (d) 500ºC
[JEE Main 2019, 12 Jan Shift-II] Exp. (d)
Exp. (b) For fcc arrangement, 4r = 2 a
where, r = radius and a = edge length
Given, temperature(T1 ) = 27 ° C = 273 + 27 = 300K
2 a a
Volume of vessel = constant ∴ Closest distance = 2 r = =
2 2
Pressure in vessel = constant
2
19. Two closed bulbs of equal volume (V )
Volume of air reduced by so the remaining containing an ideal gas initially at pressure pi
5
3 and temperature T1 are connected through a
volume of air is . narrow tube of negligible volume as shown in
5
the figure below. The temperature of one of the
Let at T1 the volume of air inside the vessel is n so at
bulbs is then raised to T2 . The final pressure p f
3
T2 the volume of air will be n. is [ JEE Main 2016 (Offline)]
5
Now, as p and V are constant, so T1 T2 T1 T2
3 pi, V pi, V pf, V pf, V
n ⋅T1 = n T2 ...(i)
5
Putting the value of T1 in equation (i) we get,  T1   T2 
(a) 2pi   (b) 2pi  
3  T1 + T2   T1 + T2 
n × 300 = n × T2
5
 TT   TT 
5 (c) 2pi  1 2  (d) pi  1 2 
or T2 = 300 × = 500 K  T1 + T2   T1 + T2 
3
Exp. (b)
17. Which type of ‘defect’ has the presence of
cations in the interstitial sites? [ JEE Main 2018] Initially,
pV
(a) Schottky defect Number of moles of gases in each container = i
RT1
(b) Vacancy defect
(c) Frenkel defect Total number of moles of gases in both containers
pV
(d) Metal deficiency defect =2 i
RT1

States of Matter 15
After mixing, number of moles in left chamber 21. The intermolecular interaction that is
pV
= f dependent on the inverse cube of distance
RT1 between the molecules is [ JEE Main 2015]
pV
Number of moles in right chamber = f (a) ion-ion interaction (b) ion-dipole interaction
RT2
(c) London force (d) hydrogen bond

Total number of moles
pV pV pV  1 1 Exp. (b)
= f + f = f  + 
RT1 RT2 R  T1 T2  Ion-ion interaction is dependent on the square of
1
As total number of moles remains constant. distance, i.e. ion-ion interaction ∝ 2
r
2 pV
i = pf V + pf V 1
Hence, Similarly, ion-dipole interaction ∝ 3
RT1 RT1 RT2 r
 T2  1
⇒ pf = 2 pi   London forces ∝ 6
 T1 + T2  r
1
and dipole-dipole interactions ∝ 3
20. Sodium metal crystallises in a body centred r
cubic lattice with a unit cell edge of 4.29 Å. The Superficially it seems as both ion dipole interaction
radius of sodium atom is approximately and hydrogen bonding vary with the inverse cube
of distance between the molecules but when we
[ JEE Main 2015]
look at the exact expressions of field (force) created
(a) 1.86 Å (b) 3.22 Å in two situations it comes as
(c) 5.72 Å (d) 0.93 Å 2| P|
|E | or |F| =
Exp. (a) 4 π ε0 r 3
(In case of ion-dipole interaction)
2q 2 r − 4q 2 a
D and F=
4 πε0 r 3
r
a (In case of dipole-dipole interaction)
2r From the above it is very clear, the ion-dipole
C interaction is the better answer as compared to
r dipole-dipole interaction i.e. hydrogen bonding.
a
A B 22. If Z is a compressibility factor, van der Waals’
a equation at low pressure can be written as
From this figure , [ JEE Main 2014]
RT a
2
( AC ) =( AB ) +( BC) 2 2 (a) Z = 1 + (b) Z = 1 −
pb VRT
( AC )2 = a2 + a2 = 2 a2 pb pb
(c) Z = 1 − (d) Z = 1 +
Also, ( AD)2 =( AC)2 +( DC )2 RT RT
(4r )2 = 2 a2 + a2 Exp. (b)
van der Waals’ equation is given by
16 r2 =3 a2
 p + a  ( V − b ) = RT
3  
⇒ r= a  V2 
4 a
At low pressure, V decreases. Thus, increases.
Now, when Na metal crystallises in bcc unit cell V2
with unit cell edge, a = 4.29Å However, V is still large enough in comparison to
‘b’, hence, ‘b’ can be neglected. Thus, van der
We have the formula for radius,
Waals’ equation becomes
3  p + a  V = RT ⇒ pV + a = RT
i.e. r= × 4.29 Å = 1.86 Å  
4  V2  V

a
⇒ pV = RT − 26. For gaseous state, if most probable speed is
V
pV a denoted by C *, average speed by C and mean
⇒ = 1−
RT RTV square speed by C, then for a large number of
a Q pV = Z  molecules, the ratios of these speeds are
Z = 1−
 RT  C* : C :C =1. 225 : 1.128 : 1
RTV (a) [JEE Main 2013]

(b) C* : C : C = 1.128 : 1.225 :1
23. CsCl crystallises in body centered cubic lattice. (c) C * : C : C = 1:1.128 : 1.225
If ‘a’ its edge length, then which of the following (d) C * : C : C = 1 : 1.225 : 1.128
expressions is correct? [JEE Main 2014]
3a Exp. (c)
(a) rCs + + rCl − = 3a (b) rCs + + rCl − =
2 C* = most probable speed = 2RT / M
3
(c) rCs + + rCl − = a (d) rCs + + rCl − = 3a C = average speed = 8 RT / πM
2
Exp. (c) C = Mean square speed corrected as
In CsCl, Cl − lie at the corners of simple cube and rms =
3RT
Cs + at the body centre. Therefore, along the body M
diagonal, Cs + and Cl − touch each other. *
∴ C < C < C
3
Hence, a = rCs + + rCl − * 4 3
2 Hence, C : C : C = 1 : :
π 2
24. Which of the following exists as covalent = 1: 1.128 : 1.225
crystals in the solid state? [JEE Main 2013] Note As no option correspond to mean square speed,
(a) Iodine (b) Silicon it is understood as misprint. It should be root
(c) Sulphur (d) Phosphorus mean square speed.
Exp. (b) 27. The compressibility factor for a real gas at high
Silicon exists as covalent crystal in solid state. pressure is [AIEEE 2012]
(Network like structure, like diamond). RT
(a) 1 + (b) 1
pb
25. Experimentally, it was found that a metal oxide
pb pb
has formula M 0.98O. Metal M, present as M 2 + (c) 1 + (d) 1 −
RT RT
and M 3 + in its oxide. Fraction of the metal
which exists as M 3 + would be [JEE Main 2013] Exp. (c)
(a) 7.01% (b) 4.08% (c) 6.05% (d) 5.08% van der Waals’ equation for one mole of real gas is
 p + a  ( V − b ) = RT
Exp. (b)  
 V2 
M 0.98O a
When pressure is high p >> 2
Consider one mole of the oxide. V
Moles of M = 0.98 mole of O 2 −= 1 Such that p+ a  ≈ p
 
 V2 
Let moles of M 3+ = x
Thus, p(V − b ) = RT
⇒ Moles of M 2+ = 0.98 − x
pV − pb = RT
⇒ On balancing charge, pV = RT + pb
(0.98 − x) × 2 + 3 x − 2 = 0 ∴ Compressibility factor,
⇒ 1.96 − 2 x + 3 x − 2 = 0 ⇒ x = 0.04
pV  pb 
0.04 Z= = 1 + 
⇒ Percentage of M 3 + = × 100 = 4.08% RT  RT 
0.98

States of Matter 17
28. Lithium forms body-centred cubic structure.

31. The molecular velocity of any gas is
The length of the side of its unit cell is 351 pm. (a) inversely proportional to the square root of
temperature
Atomic radius of the lithium will be [AIEEE 2012]
(b) inversely proportional to absolute
(a) 75 pm (b) 300 pm (c) 240 pm (d) 152 pm temperature
Exp. (d) (c) directly proportional to square of temperature

(d) directly proportional to square root of
In body-centred cubic structure, temperature [AIEEE 2011]
Edge length = a = 351 pm, Radius = r = ?
3a 3 × 351 Exp. (d)
Then, r= = Molecular velocity can be
4 4
8RT
= 152 pm average velocity =
πM
3RT
29. a and b are van der Waals’ constants for gases. root mean square velocity =
Chlorine is more easily liquefied than ethane M
because [AIEEE 2011] 2RT
most probable velocity =
(a) a and b for Cl 2 > a and b for C2 H6 M
In all cases, molecular velocity ∝ T
(b) a and b for Cl 2 < a and b for C2 H6
(c) a for Cl 2 > a forC2 H6 but b forCl 2 > b forC2 H6 32. Copper crystallises in fcc lattice with a unit cell
(d) a for Cl 2 > a forC2 H6 but b forCl 2 < b forC2 H6 edge of 361 pm. The radius of copper atom is
Exp. (d) [AIEEE 2011]
(a) 181 pm (b) 108 pm (c) 128 pm (d) 157 pm
van der Waals’ constant a is due to force of
attraction and b due to finite size of molecules. Exp. (c)
Thus, greater the value a and smaller the value of Copper crystallises in fcc lattice.
b, larger the liquefaction. If, r = radius, a = edge length
Thus, a(Cl 2 ) > a (C 2H6 ) a 361
then r = = pm = 127.633 pm ≈ 128 pm
2 2 2 2
and b (Cl 2 ) < b (C 2H6 )
33. When r, p and M represent rate of diffusion,
30. In a face-centred cubic lattice, atom A occupies pressure and molecular mass, respectively,
the corner positions and atom B occupies the then the ratio of the rates of diffusion (rA / rB ) of
face centred positions. If one atom of B is two gases A and B, is given as [AIEEE 2011]
missing from one of the face centred points, (a) (p A / p B )1/ 2 ( M A / M B )
the formula of the compound is [AIEEE 2011]
(b) (p A / p B )( M B / M A )1/ 2
(a) A 2 B (b) AB2
(c) A 2 B2 (d) A 2 B2 (c) (p A / p B )1/ 2 ( M B / M A )
(d) (p A / p B )( M A /M B )1/ 2
Exp. (d)
1 Exp. (b)
Number of atoms ( A) per unit cell = 8 × =1
8 Rate of diffusion, r ∝ p
Number of atoms (B) per unit cell 1 p
1 5 r= ∴r∝
= (6 − 1) × = (one atom B is missing) M M
2 2 p
For gas A, rA ∝ A …(i)
MA
pB
For gas B, rB ∝ …(ii)
MB
Dividing Eq. (i) by Eq. (ii), we get
1/ 2
rA p MB pA  M B 
= A⋅ or =  
Thus, formula is A1B5 / 2 = A 2 B5 rB pB MA pB  M A 

34. If10 −4 dm 3 of water is introduced into a1.0 dm 3 Exp. (b)

flask at 300 K, then how many moles of water In fcc unit cell 2 a = 4r
are in the vapour phase when equilibrium is 2a 2 × 361
established? r= = = 127 pm
4 4
(Given, vapour pressure of H 2O at 300 K is 3170
Pa; R = 8.314 JK −1 mol −1 ) [AIEEE 2010] 38. In a compound, atoms of element Y form ccp
(a) −3
5.56 × 10 mol lattice and those of element X occupy 2/3rd of
(b) 1.53 × 10−2 mol tetrahedral voids. The formula of the
(c) 4.46 × 10−2 mol compound will be [AIEEE 2008]
(d) 1.27 × 10−3 mol (a) X 4Y 3 (b) X 2Y 3
(c) X 2Y (d) X 3Y 4
Exp. (d)
pV 3170 × 10−3
Exp. (a)
Number of moles, n = = Suppose atoms of element Y in ccp = 100
RT 8.134 × 300
= 1.27 × 10−3 mol Number of tetrahedral voids = 2 × 100
Number of atoms of element
35. The edge length of a face centered cubic cell of 2 400 X 400
X = × 200 = ⇒ =
an ionic substance is 508 pm. If the radius of 3 3 Y 300
the cation is 110 pm, the radius of the anion is Formula = X 4 Y3
[AIEEE 2010]
(a) 288 pm (b) 398 pm 39. Total volume of atoms present in a
(c) 618 pm (d) 144 pm
face-centred cubic unit cell of a metal is (r is
atomic radius) [AIEEE 2006]
Exp. (d) 20 3 24 3
(a) πr (b) πr
For fcc arrangement 3 3
12 16 3
2(r + + r − ) = edge length (c) πr 3 (d) πr
2 (110 + r − ) = 508 3 3
So, r − = 144 pm Exp. (d)
Total number of atoms in face centred cubic unit
36. Percentage of free space in cubic close packed cell = 4
structure and in body centred packed structure 1
At corner = 8 × = 1
are respectively [AIEEE 2010] 8
(a) 30% and 26% (b) 26% and 32% 1
On faces = 6 × = 3
(c) 32% and 48% (d) 48% and 26% 2
Total = 4
Exp. (b)
π 4 πr 3 16 3
Packing fraction of ccp = = 0.74 ⇒ 74% Total volume = 4 × = πr
3 2 3 3
% free space in ccp = 26% 40. Which one of the following statements is not
π 3 true about the effect of an increase in
Packing fraction of bcc = = 0.68 = 68%
8 temperature on the distribution of molecular
% free space in bcc = 32% speeds in a gas? [AIEEE 2005]
(a) The area under the distribution curve remains
37. Copper crystallises in fcc with a unit cell length the same as under the lower temperature
of 361 pm. What is the radius of copper atom? (b) The distribution becomes broader
[AIEEE 2009] (c) The fraction of the molecules with the most
(a) 108 pm (b) 127 pm probable speed increases
(c) 157 pm (d) 181 pm (d) The most probable speed increases

States of Matter 19
Exp. (c) Exp. (c)

Distribution of molecules (N) with velocity (u ) at two van der Waals’ equation for one mole of a gas is
temperatures T1 and T2 (T2 > T1 ) is shown below  p + a  [ V − b ] = RT
At both temperatures, distribution of molecules  V 2 
with increase in velocity first increases, reaches to
a maximum value and then decreases. where, b is volume correction. It arises due to finite
size of molecules.
N
T1
44. What type of crystal defect is indicated in the
T2 diagram shown below? [AIEEE 2004]
Na+ Cl– Na+ Cl–

u
Cl– Cl– Cl– Na+
41. An ionic compound has a unit cell consisting
of A ions at the corners of a cube and B ions on Na+ Cl– Cl–
the centres of the faces of the cube. The
empirical formula for this compound would be Cl– Na+ Cl– Na+
[AIEEE 2005]
(a) Frenkel defect
(a) A 3 B (b) AB 3 (c) A 2 B (d) AB (b) Schottky defect
Exp. (b) (c) Interstitial defect
Unit cell consists of A ions at the corners. (d) Frenkel and Schottky defects
8 Exp. (b)
Thus, number of ions of the type A = = 1
8
When equal number of cations and anions (such
Unit cell consists of B ions at the centre of the six
that charges are equal) are missing
faces.
6 (1Na +, 1Cl − / 1 Fe 2+, 2Cl − ) then, it is a case of
Thus, number of ions of the type B= = 3 Schottky defect.
2
[Each corner is shared by 8 cubes and each face
is shared by 2 faces] 45. According to the kinetic theory of gases, in an
Thus, formula is AB3 . ideal gas, between two successive collisions a
gas molecule travels
42. As the temperature is raised from 20°C to 40°C, (a) in a circular path [AIEEE 2003]
the average kinetic energy of neon atoms (b) in a wavy path
changes by a factor of which of the following?
(c) in a straight line path
[AIEEE 2004]
(d) with an accelerated velocity
(a) 1/2 (b) 313 / 293
(c) 313/293 (d) 2
Exp. (c)
In between two successive collisions, no force is
Exp. (c) acting on the gas molecules. Resultantly they
3 travel with uniform velocity during this interval and
Average KE = RT / N0 ⇒ (KE) ∝ T
2 hence, moves along a straight line.
313
∴ (KE)313 / (KE)293 = 46. How many unit cells are present in a cube
293
shaped ideal crystal of NaCl of mass 1.00 g?
43. In van der Waals’ equation of state of the gas [Atomic mass : Na = 23, Cl = 35.5 ]
law, the constant ‘b’ is a measure of (a) 2.57 × 10 21
(a) intermolecular repulsions [AIEEE 2004] (b) 5.14 × 10 21
(b) intermolecular attraction
(c) 1.28 × 10 21
(c) volume occupied by the molecules
(d) intermolecular collisions per unit volume (d) 1.71 × 10 21 [AIEEE 2003]

Exp. (a)
48. For an ideal gas, number of moles per litre in
Mass of one unit cell (m) = volume × density
terms of its pressure p , temperatureT and gas
= a3 × d constant R is [AIEEE 2002]
Mz Mz
= a3 × = (a)
pT
(b) pRT (c)
p
(d)
RT
N0 a3 N0
R RT p
58.5 × 4
m = g Exp. (c)
6.02 × 10 23
1 6.02 × 1023 According to ideal gas equation, pV = nRT
∴ Number of unit cells in 1g = = pV p × 1 p
m 58.5 × 4 Number of moles, n = = =
RT RT RT
= 2.57 × 10 21
47. Based on kinetic theory of gases following laws

49. Number of atoms in the unit cell of Na (bcc
type crystal) and Mg (fcc type crystal) are,
can be proved [AIEEE 2002]
respectively [AIEEE 2002]
(a) Boyle’s law (b) Charles’ law
(a) 4, 4 (b) 4, 2 (c) 2, 4 (d) 1, 1
(c) Avogadro’s law (d) All of these
Exp. (c)
Exp. (d)
In Na unit cell (body centred cubic)
On the basis of kinetic theory of gases 1
1 8 (corner atoms) × = 1
pV = Nmv 2 8
3 Atoms placed inside the unit cell = 1
1 2 3 Total atoms = 2
and mv = kT
2 2 In Mg unit cell (face centred cubic)
1 N 1
p =   mv 2 8 (corner atoms) × = 1
3 V 8
1
2  N  1 mv 2 = 2  N   3  kT 6 (face atoms) × = 3
or p=       2
3 V 2 3 V 2
Total atoms = 4
or pV = NkT

3
Atomic Structure
1. The quantum number of four electrons are photoelectron, the wavelength of the light
given below: should be
1 (Assume kinetic energy of ejected
I. n = 4,l = 2 , ml = − 2 , m s = − photoelectron to be very high in comparison
2
1 to work function) [JEE Main 2019, 8 April Shift-II]
II. n = 3,l = 2 , ml = 1, m s = + 4 3 2 1
2 (a) λ (b) λ (c) λ (d) λ
1 9 4 3 2
III. n = 4,l = 1, ml = 0, m s = +
2 Exp. (a)
1
IV. n = 3,l = 1, ml = 1, m s = − The expression of kinetic energy of photo
2 electrons,
The correct order of their increasing 1
KE = mv 2 = E − E0
energies will be [JEE Main 2019, 8 April Shift-I] 2
(a) IV < III < II < I (b) I < II < 1III < IV When, KE > > E0 , the equation becomes,
(c) IV < II < III < I (d) I < III < II < IV 1
KE = mv 2 = E
2
Exp. (c) 1 hc p2 hc
⇒ mv 2 = ⇒ =
Smaller the value of (n + l ), smaller the energy. If 2 λ 2 m2 λ
two or more sub-orbits have same values of 2 1 1
(n + l ), sub-orbits with lower values of n has lower ⇒ λ = hc × 2 m × 2 ⇒ λ ∝ 2
p p
energy. The (n + l ) values of the given options are hc
as follows : E= = energy of incident light.
λ
I. n = 4, l = 2 ;n+ l = 6
E0 = threshold energy or work functions,
II. n = 3, l = 2; n + l = 5
1 1 (mv )2 1 p2
III. n = 4, l = 1, n + l = 5 mv 2 = × = × 2
IV. n = 3, l = 1, n + l = 4
2 2 m2 2 m
Q p = momentum = mv
Among II and III, n = 3 has lower value of energy.
Thus, the correct order of their increasing As per the given condition,
2
energies will be λ 2  p1 
= 
IV < II < III < I λ1  p2 
2 2
2. If p is the momentum of the fastest electron λ2  p  2 4
⇒ =  =  =
λ . × p
 15  3 9
ejected from a metal surface after the
irradiation of light having wavelength λ, 4 Q λ1 = λ 
⇒ λ2 = λ  p = p
then for 1.5 p momentum of the 9  1 

3. For any given series of spectral lines of 4. Which one of the following about an
atomic hydrogen, let ∆ν = νmax − νmin be electron occupying the 1s-orbital in a
the difference in maximum and minimum hydrogen atom is incorrect? (The Bohr
frequencies in cm −1. The ratio radius is represented by a 0)
∆ νLyman / ∆ νBalmer is

[JEE Main 2019, 9 April Shift-I] (a) The electron can be found at a distance 2a 0
(a) 27 : 5 (b) 5 : 4 (c) 9 : 4 (d) 4 :1 from the nucleus.
(b) The magnitude of the potential energy is
Exp. (c) double that of its kinetic energy on an
For any given series of spectral lines of atomic average.
hydrogen. (c) The probability density of finding the
Let ∆ν = νmax − νmin be the difference in electron is maximum at the nucleus.
maximum and minimum frequencies in cm−1. (d) The total energy of the electron is maximum
when it is at a distance a 0 from the nucleus.
For Lyman series,
∆ν = νmax − νmin Exp. (d)
General formula: Statement (d) is incorrect. For 1s-orbital radial
1 1 probability density (R 2 ) against r is given as:
ν = 109677  2 − 2 
 ni nf 
For Lyman n1 = 1, n2 = 2, 3, K
1 1 1
νmax = 109,677  −  = 109,677  − 0
1 ∞ 1  R2
1s
= 109,677
1 1 
νmin = 109,677  − 2 
 1 (2 )  r
∆νLyman = νmax − νmin For 1s-orbital, probability density decreases

sharply as we move away from the nucleus.
109,677 × 3  109,677
= 109,677 −  = The radial distribution curves obtained by plotting
 4  4 radial probability functions vs r for 1s-orbital is
For Balmer series,
 1 1 109677
νmax = 109,677  2 −  ⇒
 (2 ) ∞ 4
4πrR2
 1 1  109677 × 5
νmin = 109,677  2 − 2  ⇒
 (2 ) (3)  36
∆ν = νmax − νmin
109,677  109,677
∆νBalmer = − × 5 r
4  36 
The graph initially increases and then decreases. It
 1 reaches a maximum at a distance very close to the
= 109,677  
 9 nucleus and then decreases. The maximum in the
∆ νLyman 109,677 / 4 curve corresponds to the distance at which the
=
∆ νBalmer 109,677 / 9 probability of finding the electron in maximum.
∆ νLyman 9
= 5. The graph between | ψ |2 and r (radial
∆ νBalmer 4
distance) is shown below. This represents
∆ νLyman [JEE Main 2019, 10 April Shift-I]
∴ The ratio of is 9 : 4.
∆ νBalmer

Atomic Structure 23
Exp. (a)
According to Rydberg’s equation,
2
|Ψ| 1 RH  1 1 1  1 1
=  −  or ∝ − 
λ hc  n12 n22  λ  n12 n22 
For shortest wavelength, i.e. highest energy

spectral line, n2 will be (∞ ).
r For the given spectral series, ratio of the shortest
(a) 1s-orbital (b) 2p-orbital wavelength of two spectral series can be
(c) 3s-orbital (d) 2s-orbital calculated as follows :
1 1 1
− 2 −0
Exp. (d) λL 2
∞ = 9 1
(a) = 3 =
λP 1 1 1 − 0 9
The graphs between|ψ|2 and r are radial density −
12 ∞ 2
plots having (n − l − 1) number of radial nodes. For 1 1
1s, 2s, 3s and 2 p-orbitals these are respectively. − 2
λBk 5 2
∞ 1 16 16
(b) = = × =
λPf 1 1 25 1 25
2
− 2
4 ∞
|Ψ|2 For 1s-orbital 1 1
− 2
number of radial node = 1–0–1=0 λ 2
∞ = 1 × 9= 9
(c) P = 5
λPf 1 1 25 1 25
−
r 32 ∞ 2
1 1
− 2
λB 4 2
∞ 1 4 1
(d) = = × =
λBk 1 1 16 1 4
−
|Ψ|2 For 2s-orbital
22 ∞2
number of radial node = 2–0–1=1
Note Lyman = L (n1 = 1), Balmer = B (n1 = 2 )
Paschen = P (n1 = 3), Brackett = Bk (n1 = 4)
r Pfund = Pf (n1 = 5)
7. The electrons are more likely to be found

|Ψ|2 For 3s-orbital [JEE Main 2019, 12 April Shift-I]
a Ψ (x)
r
b x
–x
|Ψ|2 For 2p-orbital
c
r
Thus, the given graph between |ψ|2 and r (a) in the region a and c
represents 2s-orbital. (b) in the region a and b
(c) only in the region a
6. The ratio of the shortest wavelength of two (d) only in the region c
spectral series of hydrogen spectrum is
found to be about 9. The spectral series are Exp. (a)
[JEE Main 2019, 10 April Shift-II] The electrons are more likely to be found in the
(a) Lyman and Paschen (b) Brackett and Pfund region a and c. At b, wave function becomes zero
(c) Paschen and Pfund (d) Balmer and Brackett and is called radial nodal surface or simply node.

a III. According to wave mechanics, the

Y (x) ground state angular momentum is
b +x → h
equal to .
← –x 2π
IV. The plot of ψ vs r for various azimuthal
c quantum numbers, shows peak

shifting towards higher r value.
The graph between wavefunction (ψ) and distance
(r) from the nucleus helps in determining the shape (a) I, III (b) II, III (c) I, II (d) I, IV
of orbital. [ JEE Main 2019, 9 Jan Shift-II]
Exp. (d)
8. For emission line of atomic hydrogen from nh
ni =8 to n f = n, the plot of wave number ( ν ) (I) Angular momentum, mvr =
2π
 1 ⇒ mvr ∝ n ∝ distance from the nucleus
against  2  will be (The Rydberg constant,
n  (II) This statement is incorrect as size of an orbit
R H is in wave number unit) ∝ Azimuthal quantum number( l ) (Qn = constant)
(a) non linear (III) This statement is incorrect as at ground state,
(b) linear with slope −RH n = 1, l = 0
(c) linear with slope RH ⇒ Orbital angular momentum (wave mechanics)
(d) linear with intercept −RH = l (l + 1)
h
=0 [Q l = 0]
[ JEE Main 2019, 9 Jan Shift-I] 2π
(IV) The given plot is
Exp. (c)
According to Rydberg’s formula, l=0 (n=1)
1 1 l=1 (n=2)
wave number (ν) = RH Z 2  2 − 2 
n
 i n f  l=2 (n=3)
Given, ni = n, nf = 8 ψ
[Q it is the case of emission] l=3 (n=4)
1 1
ν = RH × (1)2  2 − 2 
 n 8 
1 1
ν = RH  2 −  = H2 − H
R R r
 n 64  n 64
10. Which of the graphs shown below does not
On comparing with equation of straight line,
represent the relationship between incident
y = mx + c, we get
−RH light and the electron ejected from metal
Slope = RH , intercept = .
64 surface? [ JEE Main 2019, 10 Jan Shift-I]
1
Thus, plot of wave number (ν) against 2 will be
n K.E. of K.E. of
linear with slope (+ RH ).
e ss ess
9. Which of the following combination of (a) (b)
statements is true regarding the
interpretation of the atomic orbitals? 0
Energy of
0
Intensity of
I. An electron in an orbital of high light light
angular momentum stays away from Number K.E. of
the nucleus than an electron in the of ess ess
orbital of lower angular momentum.
(c) (d)
II. For a given value of the principal
quantum number, the size of the orbit 0 0
Frequency of Frequency of
is inversely proportional to the light light
azimuthal quantum number.

Atomic Structure 25
Exp. (d) 11. The 71st electron of an element X with an

For photoelectric effect, atomic number of 71 enters into the orbital
(i) KE = E − E 0 (a) 4f (b) 6p (c) 5d (d) 6s
where, [ JEE Main 2019, 10 Jan Shift-II]
KE = Kinetic energy of ejected electrons.
E = Energy of incident light = hν Exp. (c)

E 0 = Threshold energy = hν 0 In the lanthanoid series, atomic number of
ν = Frequency of incident light fourteen 4f-block elements ranges from 58 (Ce) to
ν 0 = Threshold frequency 71 (Lu).
Ytterbium, Yb(Z = 70) has electronic configuration
: [Xe]4f14 6s 2 . So, the 71nth electron of lutetium,
KE Lu(Z = 71) should enter into 5d orbital and its
0 (here, Lu is ‘X’) electronic configuration will be :
E0 E
[Xe]4f14 5d 1 6s 2 . It happens so, because f-block
elements have general electronic configuration,
(n − 2 )f1 − 14 (n − 1)d 1−10 ns 2 . Therefore, option (c) is
Slope = ± 1, intercept = − E 0 correct.
So, option (a) is correct.
(ii) KE of ejected electrons does not depend on the 12. The ground state energy of hydrogen atom is
intensity of incident light. −13.6 eV. The energy of second excited state
of He+ ion in eV is
KE (a) −54.4 (b) −3.4 (c) −6.04 (d) −27.2
[ JEE Main 2019, 10 Jan Shift-II]
Exp. (c)
0 The ground state energy of H-atom is + 13.6 eV.
Intensity of light
For second excited state, n = 2 + 1 = 3
So, option (b) is correct. Z2
(iii) When, number of ejected electrons is plotted with ∴ E3 (He + ) = − 13.6 × 2 eV [Q for He + , Z = 2]
n
frequency of light, we get
22
= − 13.6 × 2 eV = − 6.04 eV
3
Number
of e–’s 13. Heat treatment of muscular pain involves
radiation of wavelength of about 900 nm.
Which spectral line of H-atom is suitable for
0 this purpose? [R H = 1 × 105 cm –1,
Frequency of light (n)
h = 6.6 × 10 Js, c = 3 × 10 ms−1]
−34 8
So, option (c) is also correct. (a) Paschen, 5 →3 (b) Paschen, ∞ → 3

(iv) KE = hν − hν 0 (c) Lyman, ∞ → 1 (d) Balmer, ∞ → 2
[ JEE Main 2019, 11 Jan Shift-I]
KE Exp. (b)
0 1   1 1 
n0 n = hc ×  RH  2 − 2  × Z 2 
∆E = hc ×
λ   n1 n2  
1 1 hc
⇒ 2 − 2 = [for H, atom Z = 1]
n1 n2 RH × λ × Z 2 × hc
Slope = + h, intercept = − hν 0 1 1 1
= = ×
So, option (d) is not correct. RH × λ (1 × 10 m ) (900 × 10−9 m)
7 −1

1 1 1 Given : λ = 4000 Å = 4000 × 10−10 m

⇒ − =
n12 n22 9 v = 6 × 105 ms −1,
1 1 1 ∴ n = 3, 
1 me = 9 × 10−31 kg, c = 3 × 108 ms −1
So, in option (b) 2 − 2 = − 0 =  1
3 ∞ 9 9  n2 = ∞ 
h = 6.626 × 10−34 Js
14. The de-Broglie wavelength ( λ ) associated Thus, on substituting all the given values in Eq. (i),
we get
with a photoelectron varies with the 1
frequency ( ν ) of the incident radiation as, × 9 × 10−31 kg × (6 × 105 ms −1 )2
2
[ν 0 is threshold frequency]
6.626 × 10−34 J s × 3 × 108 ms −1
1 1 = −φ
(a) λ ∝ 1
(b) λ ∝ 3 4000 × 10−10 m
( ν − ν0 )4 ( ν − ν0 ) 2 . × 10−21 kgm 2 s −2 − 4.96 × 10−19 J
∴φ = 162
(c) λ ∝
1
(d) λ ∝
1 = 3.36 × 10−19 J [1 kg m2s −2 = 1J]
1
( ν − ν0 ) = 2.1 eV
( ν − ν0 )2
[ JEE Main 2019, 11 Jan Shift-II] 16. If the de-Broglie wavelength of the electron
Exp. (d) in n th Bohr orbit in a hydrogenic atom is
equal to 1.5 πa 0 (a 0 is Bohr radius), then the
de-Broglie wavelength (λ) for electron is given by value of n / Z is
h
λ= ...(i) (a) 1.0 (b) 0.75 (c) 0.40 (d) 1.50
2 m K.E
Also, according to photoelectric effect
KE = hν − hν0 Exp. (b)
On substituting the value of KE in Eq (i), we get Circumference
Number of waves =
h Wavelength
λ=
2 m × (hν − hν0 ) 2 πr
n=
1 λ
∴ λ∝ ∴ 2 πr = nλ ...(i)
(ν − ν0 )1/ 2
Also, we know that radius (r ) of an atom is given by
15. What is the work function of the metal, if the a n2
r= 0
light of wavelength 4000 Å generates Z
photoelectron of velocity6 × 105 ms −1 from it? Thus, Eq. (i) becomes
(Mass of electron = 9 × 10−31 kg 2 πa0
n2
= nλ ...(ii)
Velocity of light = 3 × 108 ms −1 Z
Planck’s constant = 6.626 × 10−34 Js n2
∴ 2 πa0 = n (1.5 πa0 )[Given, λ = 1 .5 πa0 ]
Z
Charge of electron = 1.6 × 10−19 JeV −1)
n 1.5πa0 1.5
= = = 0.75
(a) 4.0 eV (b) 2.1 eV (c) 0.9 eV (d) 3.1 eV Z 2 πa0 2
[JEE Main 2019, 12 Jan Shift-I]
Exp. (b) 17. The radius of the second Bohr orbit for
hydrogen atom is (Planck’s constant
Work function of metal (φ) = hν0
(h ) = 6.6262 × 10− 34 Js; mass of electron
where, ν0 = threshold frequency
1 = 9.1091 × 10− 31 kg ; charge of electron
Also, me v 2 = hν − hν0
2 (e ) = 1.60210 × 10− 19 C; permitivity of vacuum
1
or me v 2 = hν − φ …(i) ( ∈0 ) = 8.854185 ×10 −12 kg − 1 m − 3 A 2 )
2
[JEE Main 2017 (Offline)]
1 hc
me v 2 = −φ …(ii) (a) 1.65 Å (b) 4.76 Å (c) 0.529 Å (d) 2.12 Å
2 λ

Atomic Structure 27
Exp. (d) Exp. (c)

2 2
Bohr radius (rn ) = ∈0 n h
n2 h2 1 n=4
rn = 2 2
⇒k= n=3
4π me kZ 4 π ∈0
n=2
n2 h2 ∈0 a0
∴ rn = = n2 n=1
πme 2 Z Z
where, m = mass of electron, e = charge of electron Maximum population
of e– of H-atom
h = Planck’s constant,
k = Coulomb constant Since, at n = 1, the population of electrons is
n2 × 0.53 maximum i.e. at ground state. So, maximum
rn = Å excitation will take place from n = 1to n = 2.
Z
Hence, n = 2 is the possible excited state.
Radius of nth Bohr orbit for H-atom
Now, we have the formula for energy of H-atom
= 0.53 n2 Å [Z = 1for H-atom]
Z2
∴Radius of 2nd Bohr orbit for H-atom ( En )H = −13.6 eV
n2
= 0.53 × (2 )2 = 2.12 Å
where, Z = atomic number
18. A stream of electrons from a heated filament Z for H-atom = 1
was passed between two charged plates kept 1 13.6
at a potential differenceV esu. If e and m are ∴ ( En )H = −13.6 × 2 eV = − eV = − 3.4 eV
2 4
charge and mass of an electron, respectively,
then the value ofh/λ (where, λ is wavelength 20. The correct set of four quantum numbers for
associated with electron wave) is given by the valence electrons of rubidium atom
[JEE Main 2016 (Offline)] [ Z = 37] is [JEE Main 2014]
(a) 2 meV (b) meV (c) 2 meV (d) meV 1 1
(a) 5, 0, 0, + (b) 5,1, 0, +
2 2
Exp. (c) 1 1
(c) 5,1,1, + (d) 5, 0,1, +
/ As you can see in options, energy term is 2 2
mentioned hence, we have to find out
h Exp. (a)
relation between and energy. For this, we
λ The electronic configuration of rubidium atom
shall use de-Broglie wavelength and kinetic (Z = 37 ) is given by
energy term in eV. Rb = [Kr ] 5 s1
h
de-Broglie wavelength for an electron (λ ) =
p Hence, the quantum numbers for 5 s1 electron is
h
⇒ p= …(i) given by
λ 1 1
Kinetic energy of an electron = eV n = 5, l = 0, m = 0, s = + or −
2 2
p2
As we know that, KE =
2m 21. Energy of an electron is given by
p2  Z 2
∴ eV = or p = 2meV …(ii)
2m E = − 2.178 × 10−18 J  2  . Wavelength of
h n 
From equations (i) and (ii), we get = 2meV
λ light required to excite an electron in an
hydrogen atom from level n = 1 to n = 2 will
19. Which of the following is the energy of a be [JEE Main 2013]
possible excited state of hydrogen? ( h = 6.62 × 10 −34
J s and c = 3.0 × 108 ms −1)
[JEE Main 2015]
(a) 1.214 × 10−7 m (b) 2.816 × 10−7 m
(a) + 13.6 eV (b) − 6.8 eV
(c) 6.500 × 10−7 m (d) 8.500 × 10−7 m
(c) − 3.4 eV (d) + 6.8 eV

Exp. (a) 1 1 1
∴ = +
Energy change λ λ1 λ 2
1 1 1 1 1
∆E = 2.178 × 10−18  2 − 2  =
hc
= +
1 2  λ 355 680 λ 2
1 1
=2.178 × 10−18  2 − 2  λ 2 = 742 .77 nm ≈ 743 nm

1 2 
24. The frequency of light emitted for the
6.62 × 10−34 × 3.0 × 108 transition n = 4 to n = 2 of He + is equal to the
=
λ transition in H atom corresponding to
∴ λ ≈ 1.214 × 10−7 m which of the following? [AIEEE 2011]
(a) n = 3 to n =1 (b) n = 2 to n =1
22. The electrons identified by quantum (c) n = 3 to n = 2 (d) n = 4 to n = 3
numbers n and l
(1) n = 4, l = 1 (2) n = 4,l = 0 Exp. (b)
(3) n = 3,l = 2 (4) n = 3,l = 1 2 π 2 mZ 2e 4 k 2  1 1
∆E = hu = 2  2 − 2
can be placed in the order of increasing h  n1 n2 
energy as [AIEEE 2012] if electron falls from n2 -level to n1- level.
(a) ( 3) < ( 4) < ( 2 ) < (1 ) (b) ( 4) < ( 2 ) < ( 3) < (1 ) ∴ In He+, for n2 = 4 to n1 = 2 transition
(c) ( 2 ) < ( 4) < (1 ) < ( 3) (d) (1 ) < ( 3) < ( 2 ) < ( 4) 1 1
v + = constant (4)  2 − 2  [Q ZHe + = 2]
He  2 4 
Exp. (b)
3 3
nl (suborbit) n+ l = constant × 4   = × constant
n l  16  4
(a) 4 1 4p 5
1 1
(b) 4 0 4s 4 v ( H) = constant (1)2  2 − 2 
(c) 3 2 3d 5  n1 n2 
(d) 3 1 3p 4 1 1
= constant ×  2 − 2 
Higher the value of (n + l ), higher is the energy. If n
 1 n2
(n + l ) are same, then suborbit with lower value of
(a) For n2 = 3 and n1 = 1,
n has lower energy. Thus,
1 1
3 p < 4s < 3 d < 4 p v ( H) = constant  − 
(4) <(2) < (3) < (1)  1 9 
8 3
= × constant ≠ × constant
23. A gas absorbs photon of 355 nm and emits at 9 4
two wavelengths. If one of the emission is at (b) For n2 = 2 and n1 = 1,
680 nm, the other is at [AIEEE 2011]
1 1
(a) 1035 nm (b) 325 nm (c) 743 nm (d) 518 nm v ( H) = constant ×  − 
 1 4 
Exp. (c) 3
= × constant = v( He + )
Energy values are always additive. 4
Etotal = E1 + E2 (c) For n = 3 and n1 = 2
1 1
hc hc hc v ( H) = constant ×  2 − 2 
= +  2 3 
λ λ1 λ2
5
= × constant ≠ v ( He+ )
36
E1
(d) For n2 = 4 and n1 = 3
E
1 1
v ( H) = constant ×  2 − 2 
E2  3 4 

4
Chemical Bonding
1. The ion that has sp 3d 2 hybridisation 2. Among the following molecules/ions,
for the central atom, is C2− 2− 2−
2 , N 2 , O2 , O2
[JEE Main 2019, 8 April Shift-II] Which one is diamagnetic and has the shortest
(a) [ICl 2 ]− (b) [BrF2 ]− bond length? [JEE Main 2019, 8 April Shift-II]
(c) [ICl 4 ]− (d) [IF6 ]− (a) C22 − (b) O2 (c) O22 − (d) N22 −
Exp. (c) Exp. (a)
Key Idea The hybridisation for a central Species MO energy Bond order n, no. of Magnetic
atom in a species can be calculated order (BO) unpaired e− character
using formula
1 C 2− −
2 (14e ) [8e ]π 6−0 0 Diamagnetic
H = (V + M − C + A) 2p x2 =3
2 2
= π σ
2p y2 2p z2
where,
H = No. of hybridised orbitals used O 2(16e − ) [8e ]σ π 6−2 2 Paramagnetic
2p z2 2p x2 =2
by central atoms. 2
*
= π π 2p1
V = No. of valence electrons of the 2p y2 x
central atom. *
= π 2p1
M = No. of mono-valent atoms y
(bonded). O 2− −
2 (18e ) [8e ]σ 2p 2 π 6−4 0 Diamagnetic
2p x2 =1
C = No. of cationic (positive) charge.
z
* 2
= π π 2p 2
A = No. of anionic (negative) charge. 2p y2 x
*
= π 2p 2
y
The hybridisation of given species are as
N 2− −
2 (16e )
[8e ]π 2p 2 6−2 2 Paramagnetic
follows : x =2
*
− − = π 2p 2 σ π 2p1 2
● For [ICl 2 ] and [BrF2 ] y 2p z2 x
1 *
H = (7 + 2 − 0 + 1) = 5 (sp3d ) = π 2p1y
2
For [ICl 4 ]− , 1
●
Bond length ∝
1 BO (Bond order)
H = (7 + 4 − 0 + 1) = 6 (sp3d 2 )
2 So order of bond length C 22 < O 2 = N22 − < O 22 −
(BO = 3) (BO = 2) (BO = 1)
● For [IF6 ]− , The diamagnetic species with shortest bond length is
1 C 2−
H= (7 + 6 − 0 + 1) = 7 (sp3d 3 ) 2 (option-a).
2

Among the given options, CO is a diamagnetic

3. Among the following, the molecule molecule. It can be proved by molecular orbital
expected to be stabilised by anion formation
(MO) theory. The electronic configuration of given
is C 2 , O2 , NO, F2. [JEE Main 2019, 9 April Shift-I] diatomic molecules are given below.
(a) C2 (b) F2 (c) NO (d) O 2
● CO (Number of electrons = 14)
Exp. (a) Electronic configuration

C 2 will be stabilised after forming anion. The = σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , σ2 pz2 , π2 p2x ≈ π2 py2
electronic configuration of carbon is 1s 2 2 s 2 2 p2 . Since, there is no unpaired electron in the CO
There are twelve electrons in C 2 . After forming molecule, so it is diamagnetic.
anion (i.e. C –2 ), the electronic configuration is ● NO (Number of electrons = 15)
● C −2 : Electronic configuration = σ1s 2 , σ* 1s 2 , σ2 s 2 ,
σ* 2 s 2 , σ2 pz2 , π2 p2x ≈ π2 py2 , π* 2 p1x ≈ π* 2 py0
( σ1s )2 ( σ *1s )2 ( σ2 s )2 ( σ * 2 s )2 ( π2 p2x = π2 py2 )
Since, NO has one unpaired electron in π* 2 p1x
( σ2 p1z ) or KK( σ2 s )2 ( σ * 2 s )2 ( π2 p2x = π2 py2 ). σ2 p1z
orbital, so it is paramagnetic.
1 1
Bond order = (Nb − Na ) = (9 − 4) = 2 .5 ● B 2 (Number of electrons = 10)
2 2
Electronic configuration
For other options such as F2− , O −2 , NO − , the
= σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , π2 p1x ≈ πp1y
electronic configurations are as follows :
Since, two unpaired electrons are present in
● F2− : ( σ 1s )2 ( σ *1s )2( σ 2 s )2( σ *2 s )2( σ 2 pz )2 π2 p1x and π2 p1y orbital. So, it is paramagnetic.
( π2 px2 = π2 py2 ) ( π* 2 p2x = π* 2 py2 )(σ* 2 p1z ) ● O 2 (Number of electrons = 16)
Bond order = 1 / 2(Nb − Na ) = 1 / 2(10 − 9) = 0.5 Electronic configuration = σ1s 2 , σ* 1s 2 , σ2 s 2 ,
● O −2 : ( σ 1s )2. ( σ *1s )2 ( σ 2 s )2 ( σ *2 s )2 ( σ 2 pz )2 σ* 2 s 2 , σ 2 pz2 , π2 p2x ≈ π2 py2 , π* 2 p1x ≈ π* 2 p1y
( π2 px2 = π2 py2 ) ( π *2 px2 = π *2 p1y ) Since, two unpaired electrons are present in
π* 2 p1x and π* 2 p1y orbital. So, it is also
1 1
Bond order = (Nb − Na ) = (10 − 7 ) = 15
. paramagnetic.
2 2
● NO − : ( σ 1s )2 ( σ *1s )2 ( σ 2 s )2 ( σ * 2 s )2( σ 2 pz )2 5. The correct statements among I to III are :
( π2 p2x = π2 py2 ) ( π* 2 p1x = π* 2 p1y ) I. Valence bond theory cannot explain
1 1 the color exhibited by transition metal
Bond order = (Nb − Na ) = (10 − 6) = 2
2 2 complexes.
The value of bond order of C−2 is highest among II. Valence bond theory can predict
the given options. Bond order between two
atoms in a molecule may be taken as an quantitatively the magnetic properties
approximate measure of the bond length. of transition metal complexes.
The bond length decreases as bond order III. Valence bond theory cannot
increases. As a result, stability of a molecule distinguish ligands as weak and
increases.
strong field ones.
4. Among the following species, the [JEE Main 2019, 9 April Shift-II]
diamagnetic molecule is (a) II and III only (b) I, II and III
[JEE Main 2019, 9 April Shift-II] (c) I and II only (d) I and III only
(a) CO (b) B2 (c) NO (d) O 2 Exp. (d)
Exp. (a) Among the given statements, correct statements
are I and III only. Valence bond theory (VBT)
Key Idea Magnetic nature can be detected by cannot explain the colour exhibited by transition
molecular orbital theory. Presence of unpaired metal complexes. This theory cannot distinguish
electrons means paramagnetic and absence of ligands as weak and strong field ones.
unpaired electrons means diamagnetic in nature.

Chemical Bonding 31
So, in the formation of O −2 from O 2 , the 17th

6. The isoelectronic set of ions is
electron goes to the *π 2 px or π* 2 py molecular
orbital (anti-bonding) which is half-filled in O 2 .
(a) F − , Li + , Na + and Mg 2 +
(b) N 3 − , Li + , Mg 2 + and O 2 − 8. According to molecular orbital theory,
(c) Li + , Na + , O 2 − and F − which of the following is true with respect to

(d) N 3− 2− −
, O , F and Na + Li+2 and Li−2 ?
(a) Both are unstable
Exp. (d) (b) Li +2 is unstable and Li −2 is stable
(c) Both are stable
Key Idea Isoelectronic species contains same
number of electrons. (d) Li +2 is stable and Li −2 is unstable
The species with its atomic number and number
of electrons are as follows : Exp. (d)
Species (ions) At. no. (Z ) No. of electrons Considering molecular orbital theory (MOT) :
3− The electronic configuration of
N 7 7 + 3 = 10
2−
Li +2 (Z = 5) = σ1s 2 , σ* 1s 2 , σ2 s1
O 8 8 + 2 = 10
Nb − Na
F− 9 9 + 1 = 10 Bond order (BO) =
2
Na +
11 11 − 1 = 10 3−2 1
= =
Li +
3 3−1= 2 2 2
2+ The electronic configuration of
Mg 12 12 − 2 = 10
Li −2 (Z = 7 ) = σ1s 2 , σ* 1s 2 , σ2 s 2 , σ ∗2 s1
Thus, option (d) contains isoelectronic set of
Nb − Na
ions. Bond order (BO) =
2
7. During the change of O2 to O−2 , the incoming 4−3 1
= =
2 2
electron goes to the orbital.
For the species having the same value of BO,
the specie having lesser number of antibonding
(a) π2p x (b) π * 2p x (c) π2p y (d) σ * 2p z
electrons[ Na ] will be more stable.
Here, N a of Li+2 (2 ) < Na of Li −2 (3) .
Exp. (b)
So, their order of stability will be Li +2 > Li −2 .
The change of O2 to O−2 can be as follows:
+e – –
O2 (16 e –) O2 (17 e–) 9. In which of the following processes, the
[Dioxygen] [Super-oxide] bond order has increased and paramagnetic
Energy Energy
character has changed to diamagnetic?
[8e– ] σ2p2z π2px2 [8e– ] σ2p2z π2p2x = π2p2y π* 2px2 (a) O2 → O+2
= π2py2 π* 2px1 = π* 2p1y = π* 2p1y (b) N2 → N+2
Half-filled
(c) O2 → O22 −
anti-bonding (d) NO → NO+ [ JEE Main 2019, 9 Jan Shift-II]
π*-MOs

Exp. (d)
 N − Na 
Species Valence MOs Bond Order  b  Paramagnetic/Diamagnetic Nature
 2 
NO(15e − ) [8e − ] π2 px2 = π2 py2σ 2 pz2 6−1

= 2.5
Paramagnetic
2
–e− π * 2 p1x = π * 2 py0σ * 2 pz 0
[8e ] −
π2 px2 = π2 py2σ 2 pz2 6−0 Diamagnetic
=3
NO + (14e − ) 2
π * 2 px0 = π * 2 py0σ * 2 pz0
N 2(14e − ) [8e − ]π2 px2 = π2 py2σ2 pz2 6− 0 Diamagnetic

=3
–e− 2
N 2+ (13e − ) π * 2 px0 = π * 2 py0, σ 2 pz0 5−0 Paramagnetic
= 2.5
− 2
[8e ]π2 px2 = π2 py2σ 2 pz 1
π* 2 px0 = π* 2 py0σ * 2 pz0
− −
O2(16e ) [8e ] σ 2 pz2 π2 px2 = π2 py2 6−2 Paramagnetic
=2
2
π* 2 p1x = π* 2 p1y σ * 2 pz0
–e−
−
O2+ (15e − ) [8e ] σ 2 pz2 π2 px2 = π2 py2
6−1
π * 2 p1x = π * 2 py0σ * 2 pz0 = 2.5 Paramagnetic
+2e− 2
−
[8e ] σ 2 pz2 π2 px2 = π2 py2
O22− (18e − )
6−4
π * 2 px2 = π * 2 py2σ * 2 pz0 =1
2 Diamagnetic
So, only in the conversion of NO → NO+ , the bond order has increased (2.5 → 3) and paramagnetic character has
changed to diamagnetic.
10. Two pi and half sigma bonds are present in 11. According to molecular orbital theory,
(a) O+2 (b) N2 which of the following will not be a viable
(c) N+2 (d) O2 molecule? [JEE Main 2018]
(a) He22 + (b) He+2 (c) H−2 (d) H22 −
Exp. (c)
The energy order of MOs of the given species
Exp. (d)
are as follows:
Key Idea According to M.O.T, the viability of
O2 (16e − ’ s) = σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , σ2 pz2 , any molecule can be judged through the
π2 p2x = π2 p2y , π* 2 p1x = π* 2 p1y , calculation of bond order.
O+2 (15e − ’ s) = σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , σ2 p2z , Electronic Configuration Bond order

π2 p2x = π2 *
py2 , π 2 p1x ≈ π 2 *
p0y He 2+ σ 1 s 2 σ 1*s1 2 −1
= 0.5
2
N2 (14e − ’ s) = σ 1s 2 σ* 1s 2 , σ 2 s 2 , σ* 2 s 2
H −2 σ 1 s 2 σ 1*s1 2 −1
π2 p2x = π2 py2 , σ2 p2z = 0.5
2
N2+ (13e − ’ s) = σ1s 2 σ* 1s 2 σ2 s 2 σ* 2 s 2 2 −2
H 2−
2 σ 1 s 2 σ 1*s 2 =0
π2 p2x = π2 p2z σ2 p1z 2
Thus, in case of N+2 , two π-bonds and half σ-bond He 22 + σ 1 s2 2 −0
=1
are present in the bonding MOs. 2

Chemical Bonding 33
The molecule having zero bond order will not be (b) CO (6 + 8 = 14) − σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 ,
viable hence, H2−
2 (option d) is the correct π2 p2x = π2 py2 , σ2 pz2
answer.
No unpaired electron is present.
Hence, it is diamagnetic.
12. Which of the following compounds (c) O 2(8 + 8 = 16) − σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 ,
contain(s) no covalent bond(s)?

σ2 pz2 , π2 p2x = π2 p2x , π* 2 p1x = π* 2 p1y
KCl, PH 3, O2, B 2H 6 , H 2SO4 [JEE Main 2018]
Two unpaired electrons are present.
(a) KCl, B2 H6 , PH3 (b) KCl, H2 SO 4
Hence, it is paramagnetic.
(c) KCl (d) KCl, B2 H6 (d) B 2(5 + 5) − σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , π2 p1x
Exp. (c) = π2 p1y
KCl is the only ionic compound. The structure of Two unpaired electrons are present.
PH3 , O 2 , B 2H6 and H2SO 4 are given below Hence, it is paramagnetic.
Covalent 14. The group having isoelectronic species is

P bond [JEE Main 2017 (Offline)]
O O
H H (O2) (a) O 2 − , F − , Na + , Mg 2 +
H
(PH3) Covalent (b) O − , F − , Na, Mg +
H H 1. 33 Å Bonds (c) O 2 − , F − , Na, Mg 2 +
Å H
1.19
120° B 97° B (d) O − , F − , Na + , Mg 2 +
H H H
Exp. (a)
H H H Isoelectronic species are those which contains
H H H same number of electrons.
B B B B
H H H Species Atomic number
Number of
electrons
H H (B2H6) H Banana bond
O O2 − 8 10
−
F 9 10
S
+
Na 11 10
HO OH O
Sulphuric acid Mg 2 + 12 10
(H2SO4) O− 8 9
All bond between S and O atom are covalent Na 11 11
bonds.
Mg + 12 11
13. Which of the following species is not
paramagnetic? [JEE Main 2017 (Offline)] ∴ Option (a) is correct which contains
(a) NO (b) CO (c) O 2 (d) B2 isoelectronic species O 2 − , F − , Na + , Mg 2 + .
Exp. (b) 15. The correct statement for the molecule CsI 3
To identify the magnetic nature we need to check is [JEE Main 2014]
the molecular orbital configuration. If all orbitals (a) It is a covalent molecule
are fully occupied, species is diamagnetic while (b) It contains Cs+ and I−3
when one or more molecular orbitals is/are singly
(c) It contains Cs3 + and I− ions
occupied, species is paramagnetic.
(a) NO (7 + 8 = 15) − σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , (d) It contains Cs+ , I− and lattice I2 molecule
π2 p2x = π2 py2 , π2 pz2 , π* 2 p1x = π* 2 py0 Exp. (b)

One unpaired electron is present. CsI3 contains Cs + and I−3 ions.
Hence, it is paramagnetic.

It is also a diamagnetic specie because of the

16. For which of the following molecule absence of unpaired electrons.
significant µ ≠ 0 ? [JEE Main 2014]
O 2 (8 + 8 = 16)
Cl Cl ∗
or S2 = σ1s 2 , σ* 1s 2 , σ2 s 2 , σ 2 s 2 ,
* *
σ2 pz2 , π2 p2x ≈ π2 py2 , π 2 p1x ≈ π 2 p1y
(i) (ii)
Since, O 2 or S2 contain 2 unpaired electrons,
therefore they are paramagnetic.
Cl CN 18. In which of the following pairs of

OH OH molecules/ions both the species are not
likely to exist? [JEE Main 2013]
(a) H +2 , He22 – (b) H–2 , He22 –
(iii) (iv) (c) H22 + , He2 (d) H–2 , He22 +
Exp. (c)
OH SH
Species having zero or negative bond order do
(a) Only (i) (b) (i) and (ii) not exist.
(c) Only (iii) (d) (iii) and (iv) H 22 + (1 + 1 − 2 = 0) = σ1s 0
OH SH Bond order = 0
Exp. (d) * 1s 2
He 2 (2 + 2 = 4) = σ1s 2 , σ
In quinol and thioquinol, OH and Nb − Na 2 − 2
Bond order = = =0
2 2
OH SH So, both H 2+
SH groups do not cancel their dipole moments 2 and He 2 do not exist.
and hence exists as different conformations.

H H 19. Stability of the species Li2 , Li2− and Li+2
Cl Cl O O
increases in the order of [JEE Main 2013]
(a) Li 2 < Li 2+ < Li –2 (b) Li –2 < Li +2 < Li 2
(c) Li 2 < Li 2– < Li +2 (d) Li –2 < Li 2 < Li +2
Cl CN O O
Exp. (b)
µ=0 µ=0 H H Li 2 (3 + 3 = 6) = σ1s 2 , σ* 1s 2 , σ2 s 2
2 different conformers [∴ µ ≠ 0] N − Na 4 − 2
Bond order = b = =1
[same as thioquinol] 2 2
Li + (3 + 3 − 1 = 5) = σ1s 2 , σ* 1s 2 , σ2 s1
2
17. Which one of the following molecules is 3−2 1
expected to exhibit diamagnetic Bond order = = = 0.5
2 2
behaviour? [JEE Main 2013]
* 1s 2 , σ2 s 2 , σ
Li 2 (3 + 3 + 1 = 7 ) = σ1s 2 , σ
– * 2 s1
(a) C2 (b) N 2 (c) O 2 (d) S 2
4−3 1
Bond order = = = 0.5
Exp. (a, b) 2 2
* 1s 2 , σ2 s 2 , σ
C 2(6 + 6 = 12 ) = σ1s 2 , σ * 2 s2, Stability order is Li 2 >Li+2 >Li –2 (because Li –2 have
π2 p2x ≈π2 py2 more number of electrons in antibonding orbitals
which destabilises the species).
Since, all the electrons are paired, it is a
diamagnetic specie. 20. The molecule having smallest bond angle is
* 1s 2, σ2 s 2 ,
N2 (7 + 7 = 14) = σ1s 2 , σ [AIEEE 2012]
* 2 s 2 , π2 p2 ≈ π2 p2 , σ2 p2
σ (a) NCl 3 (b) AsCl 3
x y z
(c) SbCl 3 (d) PCl 3

Chemical Bonding 35
Exp. (c) N  Exp. (b)

Group = 15
P  Count σ-bond, lone pairs and unpaired electrons
 or count number of atoms directly attached, lone
As Valence 
=5 pairs and unpaired electrons.
Sb  electrons This is = 2, then sp = 5 , then sp3d
MCl 3 has sp3 hybridized M-element with one = 3, then sp2 = 6, then sp3d 2
lone-pair. = 4, then sp3
Lone-pair and bond-pair repulsion decreases O
bond angle. However, the bond-pairs of electrons NO −3 (I) O N
–
are much farther away from the central atom than O
they are in NCl 3 . Thus, lone-pair causes even +
O==N==O
greater distortion in PCl 3 , AsCl 3 and SbCl 3 . Thus, NO +2 (II)
bond angle decreases from NCl 3 (maximum) to H
SbCl 3 (minimum). ⊕
N
21. In which of the following pairs, the two NH+4 (III) H H
species are not isostructural? [AIEEE 2012] H
(a) CO 23 − and NO −3 (b) PCl +4 and SiCl 4 Unpaired
σ-bond Lone pair Total
(c) PF5 and BrF 5 (d) AlF 36 − and SF 6 electron
I. 3 × × 3 ( sp2 )
Exp. (c)
(a) CO 2− −
Triangular planar II. 2 × × 2 ( sp)
3 , NO 3
+
(b) PCl 4 , SiCl 4 Tetrahedral III. 4 × × 4 ( sp3 )
(c) PF5 Trigonal bipyramidal
BrF5 Square pyramidal 24. The structure of IF7 is [AIEEE 2011]
(a) square pyramid (b) trigonal bipyramid
(d) AlF63− , SF6 Octahedral
(c) octahedral (d) pentagonal bipyramid
22. Among the following, the maximum Exp. (d)
covalent character is shown by the IF7 Outer orbital diagram of I
compound [AIEEE 2011] I( 53 ) 5 5p 5d 0
(a) FeCl 2 (b) SnCl 2 (c) AlCl 3 (d) MgCl 2 5s2
I(53)
Exp. (c) in ground state
Covalent character is favoured by Fajan’s rule. 5s1 5p3 5d 3
(i) Larger the charge on the ions,
(ii) Smaller the size of cations,
(iii) Larger the size of anions, sp 3d 3 hybridisation in excited state
(iv) Cation with 18-electron structure (e. g ., Cu+ ), A B C D E F G
then larger the polarising power and the covalent
character is favoured.
In all the given compounds, anion is same (Cl − ),
Inclined at 72° at 90° with
hence polarising power is decided by size and
with one each other ABCDE plane
charge of cation. 3
Seven sp3 d hybrid orbitals
Al 3+ with maximum charge and smallest size has forming s-bonds with F-atoms,
maximum polarising power hence, AlCl 3 is F
maximum covalent. F
F
23. The hybridization of orbitals of N atom in 90°
F I 72°
NO−3 , NO+2 and NH +4 are respectively
[AIEEE 2011] F
(a) sp , sp 2 , sp 3 (b) sp 2 , sp , sp 3 F
F
(c) sp , sp 3 , sp 2 (d) sp 2 , sp 3 , sp Pentagonal-bipyramidal structure

25. Which of the following has maximum 29. Which one of the following pairs of species
number of lone pairs associated with Xe? have the same bond order? [AIEEE 2008]
(a) XeO 3 (b) XeF4 [AIEEE 2011] (a) CN – and NO + (b) CN – and CN +
(c) XeF6 (d) XeF2 (c) O –2 and CN – (d) NO + and CN +
Exp. (d) Exp. (a)

CN− and NO + both have same number of
Hybridisation Lone pair Bonding electrons and same bond order (3).
Species
of Xe on Xe pairs
(a) XeO3 sp3 1 3 30. Which of the following species exhibits
(b) XeF4 3 2
sp d 2 4 diamagnetic behaviour? [AIEEE 2007]
(c) XeF6 sp3d 3 1 6

(a) O 22 − (b) O +2
(c) O 2 (d) NO
(d) XeF2 sp3d 3 (max) 2
Exp. (a)
26. The number of types of bonds between two The correct option is O 2− 2 . This species has
carbon atoms in calcium carbide is 18 electrons, which are filled in such a way that all
(a) one sigma, two pi (b) one sigma, one pi molecular orbitals are fully filled, so diamagnetic.
(c) two sigma, one pi (d) two sigma, two pi σ1s 2 , σ
*
1s 2 , σ2 s 2 , σ
*
2 s 2 , σ2 pz2 , π2 p2x ≈ π2 py2 ,
[AIEEE 2011] *
π 2 p2x ≈ π
*
2 py2
Exp. (a)
2+
CaC 2 º Ca + C 2−
2 31. In which of the following ionisation
Carbide ion
processes, the bond order has increased and
In carbide ion, two carbon atoms are joined by the magnetic behaviour has changed?
triple bond (It is isoelectronic with N2).
[AIEEE 2007]
—C ≡≡ C —
with two π and one σ-bonds. (a) C2 → C+2 (b) NO → NO +
(c) O 2 → O 2+ (d) N 2 → N +2
27. Using MO theory, predict which of the
following species has the shortest bond
Exp. (b)
length? [AIEEE 2009] NO → NO + + e −
(a) O 22 + (b) O +2 (c) O −2 (d) O 22 − (NO+ ) Total electrons = 14
σ1s 2 , σ* 1s 2 , σ 2 s 2 , σ* 2 s 2 , π2 pz2 ≈ π2 p2x , σ2 py2
Exp. (a)
Diamagnetic,
Higher the bond order, shorter is the bond length 10 − 4
Bond order = =3
O 2+
2 has the shortest bond length ( BO = 3) 2
Bond order of remaining species are (NO) Total electrons = 15
O +2 (2.5), O −2 (1.5) and O 2−
2 (1) σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , σ2 pz2 , π 2 p1x + 1 ≈ π2 p1y + 1,
28. Which one of the following constitutes a π 2 p1x ≈ *π 2 py

*
group of the isoelectronic species? 10 − 5

Paramagnetic, Border = = 2.5
[AIEEE 2008] 2
(a) C 22 – , O –2 , CO, NO (b) NO + , C 22 – , CN – , N 2 Electron is taken away from non-bonding
molecular orbital, that’s why bond order
(c) CN – , N 2 , O 22 – , CO 22 – (d) N 2 ,O 2– , NO + , CO increases.
Exp. (b) 32. Which of the following hydrogen bond is the

Isoelectronic species have same number of strongest? [AIEEE 2007]
electrons, NO+, C 2–
2 , CN
–
and N 2 all have (a) O  H L N (b) F  H L F
14 electrons. (c) O  H LO (d) O  H L F

Chemical Bonding 37
Exp. (b) As the electronegativity of central atom increases,

bonded electron polarise towards central atom
Since, H −bond is the electrostatic force of
more, so repulsion increases and bond angle
attraction between H −atom and electronegative
increases.
element. Thus, fluorine being the most
electronegative element forms stronger H −bonds. 35. Which of the following molecules/ions does
On the other hand, H − F possesses larger not contain unpaired electrons? [AIEEE 2006]
electronegative difference than O − H.
(a) O 22 − (b) B2 (c) N +2 (d) O 2
Therefore, H − F molecule is more polarised than
O − H, due to which H −atom of H − F bears larger Exp. (a)
amount of partial charge than that of O − H. This
suggests H −atom of H − F attracts more strongly Molecular orbital configuration of given molecules
F −atom than that of O − H. are
Hence, H − F forms more stronger H −bonds with O 2−
2 (Total number of electrons = 18)
fluorine than that of O − H.
σ1s 2 , σ
*
1s 2 , σ2 s 2 , σ
*
2 s 2 , σ2 pz2 , π2 p2x ≈ π2 py2 ,
33. In which of the following molecules/ions, all π 2 p2x ≈ π
* *
2 py2
the bonds are not equal? [AIEEE 2006]
B 2 ( Total number of electrons = 10)
(a) SF4 (b) SiF4 (c) XeF4 (d) BF4−
σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , π2 p1x ≈ π2 p1y
Exp. (a)
N+2 ( Total number of electrons = 13)
SF4 has trigonal bipyramidal geometry, lone pair of
electrons repels the axial bond pair and σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , π2 p2x ≈ π2 py2 , σ2 p1z
decreases the bond angle to 173°. O 2 ( Total number of electrons = 16)
F
σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , σ2 pz2 ,
SiF4 Si π2 p2x ≈ π2 p1y , π* 2 p1x

F F Regular
tetrahedral Thus, O 2−
2 does not contain any unpaired electron.
F 36. Lattice energy of an ionic compound

F F depends upon [AIEEE 2005]
XeF4 Xe Square (a) charge on the ion and size of the ion
planar (b) packing of ions only
F F (c) size of the ion only
F (d) charge on the ion only
Exp. (a)
BF4
– B
F F Tetrahedral Greater the charge and smaller the radius, larger
the polarising power and thus, greater the covalent
F nature. This leads to increase in lattice energy.
37. The molecular shapes of SF4 ,CF4 and XeF4

34. The decreasing values of bond angles from are
NH 3 (107° ) to SbH 3 (91°) down group-15 of (a) different with 1, 0 and 2 lone pair of electrons
the periodic table is due to [AIEEE 2006] on the central atom, respectively
(a) increasing bp -bp repulsion (b) different with 0, 1 and 2 lone pair of electrons
(b) increasing p -orbital character in sp 3 on the central atom, respectively
(c) the same with 1, 1 and 1 lone pair of electrons
(c) decreasing lp -bp repulsion
on the central atom, respectively
(d) decreasing electronegativity
(d) the same with 2, 0 and 1 lone pair of electrons
on the central atom, respectively [AIEEE 2005]
Exp. (d)
NH3 > PH3 > AsH3 > SbH3 Exp. (a)

Hybridisation
Molecule Structure of central Lone pair
40. Which one of the following has the regular
atom tetrahedral structure ? [AIEEE 2004]
(Atomic number : B = 5, S = 16, Ni = 28,
Xe = 54)
F (a) XeF4 (b) SF4

sp3d one
SF4 F S (c) BF4− (d) [Ni(CN)4 ]2 −
F Exp. (c)
F
F Tetrahedral structure is associated with sp3
hybridised central atom without any lone pair. The
CF4 C sp3 zero structure of all the compounds given are as follows
F 2−
F
F CN CN
2–
[Ni(CN)4] Ni
Square
F F planar
Xe CN CN
XeF4 sp3d 2 two
F F F F
Distorted
XeF4 Xe octahedral
38. Which one of the following species is F
diamagnetic in nature? [AIEEE 2005] F
(a) H −2 (b) H +2 (c) H2 (d) He +2
Exp. (c) F Distorted
SF4
A species is said to be diamagnetic, if it has all F S trigonal
paired electrons. F bipyramidal
MO electronic Magnetic F
Species Electrons
configuration behaviour
F
H −2 3 *
σ 1s 2, σ 1s1 Paramagnetic
BF4– B Tetrahedral
H 2+ 1 σ1s1 Paramagnetic
F F
H2 2 σ1s 2 Diamagnetic
F
He 2+ 3 2 *
σ 1s , σ 1s1 Paramagnetic
41. The correct order of bond angles (smallest
first) in H 2S, NH 3 , BF3 and SiH 4 is
39. The maximum number of 90° angles (a) H2 S < SiH4 < NH3 < BF3 [AIEEE 2004]
between bond pair-bond pair of electrons is
observed in [AIEEE 2004] (b) NH3 < H2 S < SiH4 < BF3
(a) dsp 3 hybridisation (b) sp 3d hybridisation (c) H2 S < NH3 < SiH4 < BF3
(c) dsp 2 hybridisation (d) sp 3d 2 hybridisation (d) H2 S < NH3 < BF3 < SiH4
Exp. (c)
Exp. (d)
Bond
sp3d 2 hybridisation has octahedral structure Species Structure lp bp VSEPR
angle
such that four hybrid orbitals are at 90° wrt each ••
other and others two at 90° with first four. 2 2 lp-lp 90°
H 2S S
H •• H lp-bp
bp-bp
••
1 3 lp-bp 107°
N
NH 3 H H bp →3bp

H

Chemical Bonding 39
Bond Exp. (b)

Species Structure lp bp VSEPR
angle
XeF2 contains sp3d hybridised Xe atom with three
F 0 3 bp-bp 120°
lone pairs of electrons. Fluorine atoms occupy
BF3 F B
axial positions while three lone pairs of elelctrons
F occupy equitorial positions in trigonal bipyramid.
H 0 4 bp-bp 109° 28′ Since, lone pair of electrons do not considered for
 the shape of the molecule, thus, shape of XeF2
SiH 4 Si H
H H comes out to be linear. While C −atom of CO 2 is sp
hybridised and thus, possesses a linear shape.
Thus, the order of bond angles is
F
H 2S < NH3 < SiH4 < BF3 .
42. The states of hybridisation of boron and

oxygen atoms in boric acid (H3 BO3 ) are Xe O C O
sp hybridised
(a) sp 2 and sp 2 (b) sp 2 and sp 3 C-atom
F
(c) sp 3 and sp 2 (d) sp 3 and sp 3 sp3d hybridised
Xe-atom
Exp. (b)
H3BO 3 has structure 45. Which one of the following compounds has
3 2 the smallest bond angle? [AIEEE 2003]
sp sp
(a) SO 2 (b) OH2
H— O—B—O—H (c) SH2 (d) NH3
|
O —H Exp. (c)
2
Boron has three bonds, thus sp hybridised. Each
Molecule Hybridisation Repulsion Bond angle
oxygen has two bonds and two lone pairs, hence
SO 2 2 lp − bp, bp − bp 119.5°
sp3 hybridised. sp
lp − lp, bp − lp
43. The bond order in NO is 2.5 while that in OH 2 sp3 bp − bp 104.5°
NO + is 3. Which of the following statements
3
is true for these two species? [AIEEE 2004] SH 2 sp —do— 90°
+
(a) Bond length in NO is greater than in NO NH 3 sp3 lp − bp, bp − bp 107°
(b) Bond length in NO is greater than in NO +
(c) Bond length in NO + is equal to that in NO
(d) Bond length is unpredictable 46. Which one of the following pairs of
molecules will have permanent dipole
Exp. (b) moments for both members? [AIEEE 2003]
Bond length is inversely proportional to (a) SiF4 and NO 2 (b) NO 2 and CO 2
bond order. Bond order in NO+ = 3 (c) NO 2 and O 3 (d) SiF4 and CO 2
and NO = 2.5
Thus, bond length in NO > NO+ .
Exp. (c)
Both NO 2 and O 3 have angular geometry,
44. The pair of species having identical shapes thus possess permanent dipole moment. While
for molecules of both species, is [AIEEE 2003] SiF4 possesses regular tetrahedral structure and
(a) CF4 , SF4 CO 2 possesses a linear structure. In SiF4 and CO 2 ,
(b) XeF2 , CO 2 the individual dipoles on the Si F and O bonds
(c) BF3 , PCl 3 cancel and the molecules have no diple moment.
(d) PF5 , IF5

µ1 µ2 µ1 µ2
N O Thus, number of lone pairs of electrons in
O µ O O µ O XeF2 , XeF4 and XeF6 are 3, 2, 1 respectively.
total (µ1 + µ2) total (µ1 + µ2)
Thus, µ total ≠ 0 Thus, µ ≠0 49. Bond angle of 109°28′ is found in [AIEEE 2002]
total ⊕ ⊕
F (a) NH3 (b) H2O (c) C H 5 (d) N H4
µ1 µ2
µ4
O— C — µ3 µ1
— —O Exp. (d)
Si
µ total = 0 (µ1 = – µ2) F µ2 F 109° 28 ′, it means pure regular tetrahedral
F µ resultant geometry.
( µ 1 + µ2 + µ3 = – µ 4 ) (a) NH3 , sp3 , pyramidal (b) H2O, sp3 , bent
∴µ =0
total (c) CH +5 , does not exist (d) NH +4 , sp3 , tetrahedral
47. Select the correct statement. [AIEEE 2002] 50. Hybridisation of the underline atom
(a) When a covalent bond is formed, transfer of changes in [AIEEE 2002]
electrons takes place
(b) Pure H2O does not contain any ion (a) AlH3 changes to AlH−4
(c) A bond is formed when attractive forces (b) H2 O changes to H3O +
overcome repulsive forces (c) N H3 changes to NH+4
(d) HF is less polar than HBr (d) In all cases
Exp. (c) Exp. (a)

(a) AlH 3 H Change in
A bond is formed when attractive forces
 hybridisation as
[NA − e A and NB − e B or NA − e B and NB − e A ] sp2 −
H  Al  H
balances the force of repulsion [e A − e B or well as in shape
sp 3
NA − NB ]. Here, NA and NB are the nucleus of two H
atoms, e A and e B are the electrons of two atoms. (b) H 2O H 3O+ Change in
48. The number of lone pairs on Xe in XeF2, shape only, bent
sp3 sp3
to pyramidal
XeF4 and XeF6 respectively, are [AIEEE 2002]
(2 bp +2 lp) (3bp + 1 lp)
(a) 3, 2, 1 (b) 2, 4, 6 (c) 1, 2, 3 (d) 6, 4, 2
(c) NH 3 NH+4 Change in
Exp. (a) 3 shape only,
sp sp3
pyramidal to
Number of lone pairs (3 bp + 1 lp) (4 bp) tetrahedral
= ( Total number of electron pairs)
−( Number of shared pairs)
51. Increasing order of bond strength of
Number of electron pairs O2 , O−2 , O22− and O+2 is [AIEEE 2002]
1 Number of valence electrons of central atom
=  (a) O +2 < O 2 < O 2− < O 2− (b) O 2 < O 2+ < O −2 < O 22 −
2 + Number of atoms linked to central atom 
(c) O 2− < O 22 − < O +2 < O 2 (d) O 22 − < O 2− < O 2 < O 2+
For XeF2
1
Number of e − pairs = [8 + 2 ] = 5 Exp. (d)
2 Higher the bond order, greater is the bond strength.
Number of lone pairs = 5 − 2 = 3
1 Species Bond order
For XeF4 , Number of e − pairs = [8 + 4] = 6
2 O 2− 1
2
O −2 1.5
For XeF6 ,
1 O2 2.0
Number of e − pairs = [8 + 6] = 7
2 O+2 2.5

5
Thermodynamics
1. For silver,C p ( J K −1mol −1 ) = 23 + 0.01 T. If the Exp. (b)
temperature (T ) of 3 moles of silver is raised From the 1st law of thermodynamics,
from 300 K to 1000 K at 1 atm pressure, the ∆U = q + W
value of ∆H will be close to where, ∆U = change in internal energy
[JEE Main 2019, 8 April Shift-I] q = heat, W = work done
(a) 62 kJ (b) 16 kJ (c) 21 kJ (d) 13 kJ The above equation can be represented for the
given processes involving ideal gas as follows:
Exp. (a) (a) Cyclic process For cyclic process, ∆U = 0
According to Kirchoff’s relation, ∴ q = −W
T2 Thus, option (a) is correct.
∆H = n ∫ C p dT …(i) (b) Adiabatic process For adiabatic process,
T1 q=0
where, ∆H = Change in enthalpy. ∴ ∆U = W
C p = Heat capacity at constant pressure. Thus, option (b) is incorrect.
Given, n = 3 moles, T1 = 300 K, T2 = 1000 K, (c) Isochoric process For isochoric process,
C p = 23 + 0.01 T ∆V = 0. Thus, W = 0 (QW = p∆V).
On substituting the given values in Eq. (i), we get ∴ ∆V = q
1000 1000
∆H = 3 ∫ (23 + 0.01 T )dT = 3 ∫ 23dT + 0.01T dT Thus, option (c) is correct.
300 300 (d) Isothermal process For isothermal process,
1000 ∆U = 0
 0.01 T  2
= 3 23T +  ∴ q = −W
 2  300
Thus, option (d) is correct.
= 3 23 (1000 − 300) + (10002 − 3002 )
0.01
 2 
3. 5 moles of an ideal gas at 100 K are allowed
= 3 [16100 + 4550] = 61950 J ≈ 62 kJ to undergo reversible compression till its
2. Which one of the following equations does temperature becomes 200 K. IfC V = 28 JK −1
not correctly represent the first law of mol −1, calculate ∆U and ∆pV for this
thermodynamics for the given processes
process. (R = 8.0 JK −1mol−1 )
involving an ideal gas? (Assume non- expansion
work is zero) [JEE Main 2019, 8 April Shift-I] [JEE Main 2019, 8 April Shift-II]
(a) Cyclic process : q = − W (a) ∆U = 2.8 kJ; ∆(pV ) = 0.8 kJ
(b) Adiabatic process : ∆U = − W (b) ∆U = 14 J; ∆(pV ) = 0.8 J
(c) Isochoric process : ∆U = q (c) ∆U = 14 kJ; ∆(pV ) = 4 kJ
(d) Isothermal process : q = − W (d) ∆U = 14 kJ; ∆(pV ) = 18 kJ

Exp. (c) ∆H ∆S Comment on ∆G Comment on the

temperature (T) process
Given,
<0 >0 at any temp. <0 spontaneous
n = 5 mol, T2 = 200 K, T1 = 100 K
>0 <0 at any temp. >0 non-spontaneous
C V = 28 JK −1mol −1
<0 <0 at lower temp. <0 spontaneous

∆U = nC V ∆T = nC V (T2 − T1 )
= 5 mol × 28 JK −1mol −1 × (200 − 100) K >0 >0 at higher temp. <0 spontaneous
= 14,000 J = 14 kJ
∆pV = nR∆T = nR(T2 − T1 )
6. The difference between ∆H and ∆U
( ∆H − ∆U ), when the combustion of one
= 5 mol × 8 JK −1mol −1 × (200 − 100) K
mole of heptane (l) is carried out at a
= 4000 J = 4 kJ temperature T, is equal to
4. Among the following the set of parameters (a) − 4 RT (b) 3 RT
that represents path functions, is (c) 4 RT (d) − 3 RT
(A) q +W (B) q Exp. (a)
(C) W (D) H − TS
(a) (A) and (D) (b) (A), (B) and (C) Key Idea The relation between ∆H and ∆U is
(c) (B), (C) and (D) (d) (B) and (C) ∆H = ∆U + ∆ng RT
where, ∆ng = Σnp − ΣnR
Exp. (d) = number of moles of gaseous products −
q (heat) and W (work) represents path functions. number of moles of gaseous reactants.
These variables are path dependent and their The general combustion reaction of a
values depends upon the path followed by the hydrocarbon is as follows :
system in attaining that state. They are inexact
C xHy +  x +  O 2 → xCO 2 + H2O
y y
differentials whose integration gives a total
 4 2
quantity depending upon the path.
Option (a), i.e. q + W and option (d), i.e. H–TS For heptane, x = 7, y = 16
are state functions. The value of state functions ⇒ C 7H16 (l ) + 11O 2 (g )→ 7CO 2 (g ) + 8H2O(l )
is independent to the way in which the state is ∴ ∆ng = 7 − 11 = − 4
attained. All the state functions are exact Now, from the principle of thermochemistry,
differentials and cyclic integration involving a ∆H = ∆U + ∆ng RT
state functions is zero.
⇒ ∆H − ∆U = ∆ng RT = − 4RT
5. A process will be spontaneous at all 7. An ideal gas is allowed to expand from 1 L to
temperature if [JEE Main 2019, 10 April Shift-I]
10 L against a constant external pressure of 1
(a) ∆H > 0 and ∆S < 0 bar. The work done in kJ is
(b) ∆H < 0 and ∆S > 0 [JEE Main 2019, 12 April Shift-I]
(c) ∆H < 0 and ∆S < 0
(a) − 90
. (b) + 100
.
(d) ∆H > 0 and ∆S > 0 (c) − 0.9 (d) − 2.0
Exp. (b) Exp. (c)
A process will be spontaneous when its free
energy (Gibb’s energy) change will be negative, Key Idea Work done during isothermal expansion
i.e. ∆G < 0. of an ideal gas is given by the equation.
Spontaneity of a process is decided by the value W = − pext (V2 − V1 )
of ∆G, which can be predicted from the Gibb’s
equation, ∆G = ∆H − T∆S for positive/negative According to the given conditions, the expansion
signs of ∆H and ∆S at any/higher/lower is against constant external pressure. So, the
temperature as: work done is given by following formula;

Thermodynamics 43
W = − pext (V2 − V1 ) The above equation is helpful in predicting the

= − 1 bar (10L − 1L) = −9 L bar spontaneity of the reaction. e.g.
(Q 1L bar = 100 J) (i) If ∆G° < 0, – ∆G ° / RT = + ve
= −9 × 100 J = −0.9 kJ and e − ∆G ° / RT
> 1and hence, K > 1.
8. Enthalpy of sublimation of iodine is It means that the reaction occur

24 cal g −1 at 200°C. If specific heat of I2(s ) and spontaneously in the forward direction or
products predominate over reactants.
I2(vap.) are 0.055 and 0.031 cal g −1 K −1 (ii) If ∆G° > 0; − ∆G ° / RT = − ve and
respectively, then enthalpy of sublimation of
e − ∆G ° / RT < 1 and hence, K < 1. It means that
iodine at 250°C in cal g −1 is
the reaction is non-spontaneous in forward
direction (i.e. product side) but spontaneous
(a) 2.85 (b) 5.7 in reverse direction (i.e. reactants
(c) 22.8 (d) 11.4 predominate over products or the reaction
occurs rarely).
Exp. (c) (iii) When K = 1, then ∆G° = 0. This situation
generally occur at equilibrium.
Key Idea When q is the amount of heat involved
in a system then at constant pressure 10. 0.5 moles of gas A and x moles of gas B exert
q = q p and C p ∆T = ∆H a pressure of 200 Pa in a container of
volume 10m 3 at 1000 K. Given R is the gas
Given reaction :
constant in JK −1 mol−1, x is
I2 (s ) → I2 (g )
2R 4−R
Specific heat of I2 (s ) = 0.055 cal g −1 K −1. (a) (b)
4− R 2R
Specific heat of I2 (vap) = 0.031 cal g –1K –1. 4+ R 2R
(c) (d)
Enthalpy (H1 ) of sublimation of iodine = 24 cal g –1 2R 4+ R
If q is the amount of heat involved in a system [ JEE Main 2019, 9 Jan Shift-I]
then at constant pressure q = q p and
∆H = C p ∆T
Exp. (b)
H2 − H1 = C p (T2 − T1 ) From the ideal gas equation,
H2 = H1 + ∆C p (T2 − T1 ) pV = ΣnRT ...(i)
H2 = 24 + (0.031 − 0.055) (250 − 200) Given: p = 200 Pa, V = 10m3 , T = 1000 K
H2 = 24 + (−0.024) (50) = 24 − 12
. = 22 . 8 nA = 0.5 moles, nB = x moles
cal/g
On substituting the given values in equation (i),
Thus, the enthalpy of sublimation of iodine at 250 we get
is 22.8 cal/g.
200 × 10 = (nA + nB ) × R × 1000
200 × 10
9. The incorrect match in the following is 0.5 + x =
[JEE Main 2019, 12 April Shift-II] R × 1000
(a) ∆G ° < 0, K > 1 (b) ∆G ° = 0, K = 1 1 2 2 1 4−R
+ x= = − =
(c) ∆G ° > 0, K < 1 (d) ∆G ° < 0, K < 1 2 R R 2 2R
Exp. (d) 11. Consider the reversible isothermal expansion

The incorrect match is ∆G ° < 0, K < 1. of an ideal gas in a closed system at two
For an ideal gas ∆G ° = − RT ln K. different temperatures T1 and T2 (T1 < T2 ).
∆G ° The correct graphical depiction of the
∴ ln K = −
RT dependence of work done (W) on the final
and K = e − ∆G ° / RT volume (V) is

|W| T2 |W| T2 K −1kg−1 and 2.0 kJK −1 kg−1; heat of liquid

T1 fusion and vapourisation of water are
T1
334 kJ kg−1 and 2491 kJkg−1 respectively).
(a) (b) (log 273 = 2.436, log 373 = 2.572 ,
log 383 = 2.583)

O ln V O ln V (a) 9.26 kJ kg −1 K−1 (b) 8.49 kJ kg −1 K−1
|W| T2 |W| T2 (c) 7.90 kJ kg −1 K−1 (d) 2.64 kJ kg −1 K−1
T1 [ JEE Main 2019, 9 Jan Shift-II]
T1
(c) (d) Exp. (a)
The conversion of 1 kg of ice at 273 K into
O ln V O water vapours at 383 K takes place as follows:
ln V
[ JEE Main 2019, 9 Jan Shift-I] ∆S1 ∆S2
H2O(s) H2O(l) H2O(l)
Exp. (c) 273K 273K 373K
For isothermal reversible expansion, ∆S3

V V
| W |= nRT ln f = nRT ln H2O(g) H2O(g)
Vi Vi ∆S4
383K 373K
where, V = final volume, Vi = initial final.
or | W | = nRT ln V − nRT ln Vi ∆HFusion 334 kJ kg −1
∆S1 = = = 1.22 kJ kg −1K −1
On comparing with equation of straight line, ∆TFusion 273 K
y = mx + c, we get
∆S 2 = C ln 2 = 4.2 kJ K −1kg −1 ln 
T 373 K 
slope = m = + nRT 
T1  273 K 
intercept = − nRT ln Vi
= 42
. × 2.303 (log 373 − log273) kJ
Thus, plot of|W| withlnV will give straight line in which
slope of 2(T2 ) is greater than slope of 1(T1 ) which is K kg −1 = 42
−1
. × 2.303 (2 .572 − 2 .436)
given in all options. . kJ K −1kg −1
= 131
Now, if Vi < 1 then y intercept (− nRT Vi ) becomes ∆Hvap. 2491 kJ kg −1
positive and if it is positive for one case then it is ∆S 3 = = = 6.67 kJ kg −1K −1
∆Tvap. 373 K
positive for other case also. Thus, it is not possible
= 2 kJ K −1kg −1 ln 
that one y-intercept goes above and other T2 383 K 
∆S 4 = Cln 
y-intercept goes below. Thus, option (b) and (d) are T1  373 K 
incorrect.
If we extent plot given in option (a) it seems to be = 2 × 2.303 (log 383 − log 373) kJ K −1kg −1
merging which is not possible because if they are = 2 × 2.303 (2.583 − 2.572 ) kJ K −1kg −1
merging they give same +ve y-intercept. But they
= 0.05 kJ K −1kg −1
cannot give same y-intercept because value of T is
different. ∆S Total = ∆S1 + ∆S 2 + ∆S 3 + ∆S 4
Now, if we extent the line of T1 and T2 given in option = 1.22 + 1.31 + 6.67 + 0.05
(c) it seems to be touching the origin. If they touch = 9.26kJ kg −1K −1
the origin then y-intercept becomes zero which is not
possible. Thus, it is not the exactly correct answer 13. A process has ∆H = 200 J mol −1 and ∆S = 40
but among the given options it is the most
appropriate one.
JK −1 mol −1. Out of the values given below,
choose the minimum temperature above
12. The entropy change associated with the which the process will be spontaneous
conversion of 1 kg of ice at 273 K to water (a) 20 K (b) 4 K
vapours at 383 K is (Specific heat of water (c) 5 K (d) 12 K
liquid and water vapour are 4.2 kJK −1kg−1 [ JEE Main 2019, 10 Jan Shift-II]

Thermodynamics 45
Exp. (c) ∆ CaO(s ) + SO (g ),

(b) CaSO 4 (s ) → 3
∆G = ∆H − T∆S ∆ng = (1 + 0) − 0 = + 1
The process will be spontaneous, when
So, ∆S = + ve
∆G = − ve, i.e.|T∆S| > |∆ H|
Given : ∆H = 200 J mol −1 (c) In dissolution, ∆S = + ve because
−1 −1 molecules/ions of the solid solute (here,

and ∆S = 40 JK mol
iodine) become free to move in
|∆ H| 200
⇒ T> = = 5K solvated/dissolved state of the solution,
|∆S| 40
I2 (s )  
Water
→ I2 (aq )
So, the minimum temperature for spontaneity of (KI)
the process is 5 K. (d) In sublimation process, molecules of solid
becomes quite free when they become gas,
14. An ideal gas undergoes isothermal CO 2 (s ) → CO 2 (g )
compression from 5 m 3 to 1 m 3 against Dry ice
a constant external pressure of 4 Nm −2. Heat So, ∆S will be positive.
released in this process is used to increase
the temperature of 1 mole of Al. 16. For the chemical reaction, X Y , the -
−1 −1 standard reaction Gibbs energy depends on
If molar heat capacity of Al is 24 J mol K ,
the temperature of Al increases by temperature T (in K) as
3 2 3
(a) K (b)1 K (c) 2 K (d) K ∆ rG ° (in kJ mol –1 ) = 120 − T
2 3 8
[ JEE Main 2019, 10 Jan Shift-II] The major component of the reaction
mixture at T is
Exp. (d) (a) Y if T = 280 K
It is an irreversible isothermal compression of an (b) X if T = 350 K
ideal gas. (c) X if T = 315 K
(i) dE = dq + p(Vf − Vi ) (d) Y if T = 300 K [ JEE Main 2019, 11 Jan Shift-I]
where, dE = Internal energy change
dq = amount of heat released Exp. (c)
⇒ 0 = dq + p(Vf − Vi ) For a given value of T,
[QdE = 0 for an isothermal process] (i) If ∆ r G° becomes < 0, the forward direction will be
⇒ dq = − 4 (1 − 5) = 16 J spontaneous and then the major and minor
(ii) dq = n × C × ∆T (for Al) components will be Y and X respectively.
⇒ 16 J = 1mol × 24 J mol −1 K −1 × ∆T (ii) If∆ r G° becomes > 0, the forward direction will
16 2 be non-spontaneous and then the major and
⇒ ∆T = K= K
24 3 minor components will be X and Y respectively.
3
(a) ∆ r G° = 120 − × 280 = 15
15. The process with negative entropy change is 8
(a) synthesis of ammonia from N2 and H2 i.e. ∆ r G ° > O 0, major component = X;
(b) dissociation of CaSO4 (s) to CaO(s)and SO3 ( g ) 3
(b) ∆ r G° = 120 − × 350 = − 1125 .
(c) dissolution of iodine in water 8
(d) sublimation of dry ice i.e. ∆ r G° < 0, major component = Y
[ JEE Main 2019, 10 Jan Shift-II] 3
(c) ∆ r G° = 120 − × 315 = 1875 .
8
Exp. (a) i.e. ∆ r G° > 0, major component = X
The explanation of all the options are as follows : 3
(d) ∆ r G° = 120 − × 300 = 7.5
(a) N2 (g ) + 3H2 (g ) → 2NH3 (g ), 8
∆ng = 2 − (1 + 3) = − 2 i.e. ∆ r G° > 0, major component = X
So, ∆S is also negative (entropy decreases)

∆ r H°−T∆ r S ° <0
17. Two blocks of the same metal having same Given, ∆ r H° = + 491.1kJ mol − 1,
mass and at temperature T1 and T2
respectively, are brought in contact with ∆ r S ° = 198 JK − 1 mol − 1
each other and allowed to attain thermal ∴ 491.1 × 103 − T × 198 < 0
equilibrium at constant pressure. The 491.1 × 103
change in entropy, ∆S, for this process is T> = 2480.3 K

198
 1
 ∴Above 2480.3 K reaction will become
 (T + T ) 2  T + T2 
(a) 2 C p ln  1 2 (b) 2
C p ln  1  spontaneous.
T1T2   4T1T2 
 
 
19. The standard reaction Gibbs energy for a
 (T + T2 )2  2  T + T2  chemical reaction at an absolute
(c) C p ln  1  (d) C p ln  1 
 2T1T2 
temperatureT is given by, ∆rG º = A − BT
 4T1T2 
Where A and B are non-zero constants.
Which of the following is true about this
Exp. (c) reaction?
At the thermal equilibrium, (a) Endothermic if, A < 0 and B > 0
T + T2
final temperature Tf = 1 (b) Exothermic if, B < 0
2
(c) Exothermic if, A > 0 and B < 0
Tf
⇒ for the 1st block, ∆S I = C p ln (d) Endothermic if, A > 0
T1
[ JEE Main 2019, 11 Jan (Shift-II)]
Tf
⇒ for the 2nd block, ∆S II = C p ln
T2 Exp. (d)
When brought in contact with each other, According to Gibb’s Helmohltz equation,
T
∆ S = ∆S I + ∆S II = C p ln f + C p ln f
T ∆ r G ° = ∆ r H° − T∆ r S °
T1 T2 Given, ∆ r G ° = A − BT
T T   T2  On comparing above two equations, we get,
= C p ln  f × f  = C p ln  f 
 T1 T2   TT
1 2 A = ∆H° and ∆S ° = B
T + T   2 We know that, if ∆H° is negative, reaction is
 1 2
   (T + T2 )2 
exothermic and when it is positive, reaction is
 2  
= C p ln  = C p ln 1 
endothermic.
 TT
1 2   4T1T2  ∴ If A> 0, i.e. positive, reaction is endothermic.
 
 
20. For a diatomic ideal gas in a closed system,
18. The reaction, which of the following plots does not
MgO(s ) + C(s ) → Mg(s ) + CO( g ), for which correctly describe the relation between
∆r H º = + 491.1 kJ mol− 1 and various thermodynamic quantities?
∆r S º = 198.0 JK − 1mol− 1, is not feasible at
298 K. Temperature above which reaction Cp Cv
will be feasible is (a) (b)
(a) 2040.5 K (b) 1890.0 K
(c) 2380.5 K (d) 2480.3 K p T
Exp. (d) (c) U (d) Cv

According to Gibbs-Helmholtz equation,
∆ r G ° = ∆ r H° − T∆ r S ° T V
For a reaction to be feasible (spontaneous)
∆ r G° < 0

Thermodynamics 47
Exp. (a) Exp. (d)

For diatomic ideal gases, Second equation given in this question is wrong.
Hence, No answer in correct. If corrected second
C V = R and C p =  + 1 R
f f
2 2  equation is given, i.e.
1
C(graphite) + O 2 (g ) → CO(g )
where, f = degree of freedom

2
f = translational degree of freedom and if we take the above reaction in consideration
+ degree of freedom then x = y + z will be the answer as:
= 3 + 2 = 5 [at normal temperature] 1
(ii) C(graphite) + O 2 (g ) → CO(g ),
The explanation of various plots are as follows. 2
∆ r H° = y kJ/mol
(a) We know that, C p is heat capacity at constant 1
(iii) CO(g ) + O 2 (g ) → CO2 (g ),
pressure. Thus, it does not vary with the 2
∆ r H° = z kJ/mol
variation in pressure. Hence, plot given in
Summing up both the equation you will get
option (a) is incorrect.
equation (i)
(b) In this plot, C V first increases slightly with
C(graphite) + O 2 (g ) → CO 2 (g ),
increase in temperature and then increases
∆ r H° = x kJ/mol
sharply with temperature. The sharp increase
Hence, x, y and z are related as:
is due to increase in degree of freedom.
x=y+ z
Thus, plot given in option (b) is correct.
(c) For ideal gases, Internal energy (U ) ∝ T 22. The combination of plots which does not
Thus, as temperature increases internal represent isothermal expansion of an ideal
energy also increases. As temperature gas is
increases further degree of freedom also
increases thus, there is slight variation in the
graph. First translational degree of freedom is p p
present followed by rotational and vibrational
degree of freedom. Hence, plot given in
option (c) is also correct. O 1/Vm O Vm
(d) C V is heat capacity at constant volume. Thus, (A ) (B)
it does not vary with variation in volume.
Hence, plot given in option (d) is correct. pVm
U
21. Given :
(i) C(graphite) + O2 ( g ) → CO2 ( g );
r∆ HÈ = x kJ mol − 1 O p O Vm
1
(ii) C(graphite) + O2 ( g ) → CO2 ( g ); (C) (D)
2
∆r H È = y kJ mol− 1 [ JEE Main 2019, 12 Jan Shift-II]
1
(iii) CO( g ) + O2 ( g ) → CO2 ( g ); Exp. (c)
2
∆r H È = z kJ mol− 1 In isothermal expansion, pVm = K (constant)
Based on the above thermochemical This relation is plotted in graph ‘C’
K
equations, find out which one of the Likewise, p =
following algebraic relationships is correct? Vm
(a) y = 2 z − x (b) x = y − z This relation is plotted in graph “A”.
(c) z = x + y (d) x = y + z Thus, graph B and D are incorrect.

For them the correct graphs are:

24. ∆U is equal to [JEE Main 2017 (Offline)]
(a) isochoric work (b) isobaric work
(c) adiabatic work (d) isothermal work
p for graph B
Exp. (c)
Vm According to first law of thermodynamics,

and
∆U = q + W = q − p∆V
In isochoric process (∆V = 0),
for graph D ∆U = q
U
In isobaric process (∆p = 0),
∆U = q
Vm In adiabatic process (q = 0)
∆U = W
23. The combustion of benzene (l ) gives CO2( g ) In isothermal process (∆T = 0) and ∆U = 0
and H2O(l ). Given that heat of combustion ∴ ∆U is equal to adiabatic work.
of benzene at constant volume is
−3263.9 kJ mol −1 at 25° C; heat of combustion 25. Given, C (graphite) + O2 ( g ) → CO2 ( g );
(in kJ mol −1) of benzene at constant pressure
will be (R = 8.314 JK −1 mol −1 ) [JEE Main 2018] ∆r H ° = − 393.5 kJ mol − 1
(a) 4152.6 (b) −452.46 (c) 3260 (d) −32676
. 1
H2 ( g ) + O2 ( g ) → H2O(l );
Exp. (d) 2
∆r H ° = − 285.8 kJ mol − 1
Key Idea Calculate the heat of combustion with
the help of following formula CO2 (g ) + 2 H2O(l) → CH4(g )+2O2 (g );
∆Hp = ∆U + ∆ng RT ∆r H ° = + 890.3 kJ mol − 1
where, ∆Hp = Heat of combustion at constant
pressure Based on the above thermochemical
∆U = Heat at constant volume (It is also called equations, the value of ∆r H ° at 298 K for the
∆E) reaction, [JEE Main 2017 (Offline)]
∆ng = Change in number of moles (In gaseous C (graphite) + 2 H2 ( g ) → CH 4( g ) will be
state).
R = Gas constant; T = Temperature. . kJ mol − 1
(a) + 788 . kJ mol − 1
(b) + 1440
. kJ mol − 1
(c) − 748 (d) −1440. kJ mol − 1
From the equation,
15
C 6H6 ( l ) + O 2 ( g ) → 6CO 2 ( g )+ 3H2O ( l )
Exp. (c)
2
Based on given ∆ r H°
Change in the number of gaseous moles i.e.
15 3 ∆ f H° = HCO
° = − 393.5 kJ mol − 1 …(i)
∆ng = 6 − = − or −15
. 2
2 2 ∆ f H° = HH° 2O = − 285.8 kJ mol − 1 …(ii)
Now we have ∆ng and other values given in the ∆ f H° = HO° = 0.00 (elements) …(iii)
2
question are
∆U = − 3263.9 kJ/mol Required thermal reaction is for ∆ f H° of CH4
T = 25° C = 273 + 25 = 298 K Thus, from III
R = 8.314 JK −1mol −1 890.3 = [ ∆ f H° (CH4 ) + 2 ∆ f H° (O2 )]
So, ∆Hp = (−3263.9) + (−15

. ) × 8.314 − [ ∆ f H° (CO2 ) + 2 ∆ f H° (H2O)]
× 10−3 × 298 = ∆ f H° (CH4 ) + 0] − [− 393.5 − 2 × 285.5]
= − 3267.6 kJ mol −1 ∴ ∆ f H° (CH4 ) = − 74.8 kJ / mol

Thermodynamics 49
26. The heats of combustion of carbon and carbon 28. For the complete combustion of ethanol,
monoxide are − 393.5 and − 283.5 kJ mol−1, C 2H 5OH(l ) + 3O2( g ) → 2CO2( g ) + 3H 2O(l )
respectively. The heat of formation (in kJ) of the amount of heat produced as measured
carbon monoxide per mole is in bomb calorimeter is 1364.47 kJmol −1at
25°C. Assuming ideality, the enthalpy of

(a) 676.5 (b) −676.5 combustion, ∆C H for the reaction will be
(c) −110.5 (d) 110.5 [R = 8.314 JK −1mol −1] [JEE Main 2014]
Exp. (c) (a) −1366.95 kJmol −1 (b) −1361.95 kJmol −1
(c) −1460.50 kJmol −1 (d) −1350.50 kJmol −1
C(s ) +O 2 (g ) → CO 2 (g ) ;
∆H = − 393.5 kJ mol −1 …(i) Exp. (a)
1
CO + O 2 → CO 2 ( g ); C 2H5OH(l ) + 3O 2 (g )→ 2CO 2 (g ) + 3 H2O(l )
2
Amount of heat produced in bomb calorimeter,
∆H = − 283.5 kJ mol −1 …(ii)
∆u = −1364.47 kJmol −1
On subtracting Eq. (ii) from Eq. (i), we get
1 Enthalpy of a combustion reaction is
C(s ) + O2 (g ) → CO(g ); ∆H = ∆u + ∆ng RT
2
∆H = (− 393.5 + 283.5) kJ mol −1 = − 110 kJmol −1 where, ∆u = internal energy
(approx. )
∆ng = moles of gas (products − reactants)
∆R = Gas constant, T = Temperature in K
27. The following reaction is performed at 298K As per equation,
2NO( g ) + O2 ( g ) #2NO ( g ) 2 ∆ng = 2 − 3 = −1
The standard free energy of formation of T = 25° C = 25 + 273 K ⇒ T = 298 K
(−1) × 8.314 × 298 
NO (g) is 86.6 kJ/mol at 298 K. What is the Thus, ∆H = −1364.47 + 
 1000 
standard free energy of formation of NO2( g )
at 298 K? (Kp = 1.6 × 1012 ) ∆H = −1364.47 − 2.477 = −1366.947 kJmol −1
[JEE Main 2015]
Hence, the enthalpy of combustion, ∆c H for the
(a) R(298) ln (1.6 × 1012 ) − 86600
given reaction will be −1366.947 kJmol −1.
(b) 86600+ R(298) In (1.6 × 1012 )
29. A piston filled with 0.04 mole of an ideal gas
In (1.6 × 1012 )
(c) 86600 − expands reversibly from 50.0 mL to 375 mL at
R(298) a constant temperature of 37.0°C. As it does
(d) 0.5 [2 × 86600 − R (298) In (1.6 × 1012 )] so, it absorbs 208 J of heat. The values of q
Exp. (d) and W for the process will be
(R = 8.314 J / mol K, ln 7.5 = 2.01)
For the given reaction, (a) q = + 208 J, W = − 208 J [JEE Main 2013]
2NO(g )+O 2 ( g ) # 2NO (g) 2 (b) q = − 208 J, W = − 208 J
Given, ∆Gf° (NO) = 86.6 kJ / mol (c) q = − 208 J, W = + 208 J
∆Gf° (NO 2 ) = ? K p = 1.6 × 1012 (d) q = + 208 J, W = + 208 J
Now, we have, Exp. (a)

∆Gf° = 2 ∆Gf°( NO ) − [2 ∆Gf°(NO) + ∆Gf°(O 2 ) ] As the process is carrying out at constant
2
temperature, therefore this type of expansion is
=− RT ln K p = 2 ∆Gf°(NO 2 )
− [2 × 86,600 + 0]
called isothermal reversible expansion, for
1 which, ∆u = 0. Hence, q = − W
∆Gf(° NO2 ) = [2 × 86,600 − R × 298 ln (1.6 × 1012 )]
2 i.e., heat absorbed by the system is equal to the
∆Gf(° NO2 ) = 0.5 [2 × 86,600 work done by the system.
− R × (298)ln (1.6 × 1012 )] Thus, q = + 208 J, W = − 208 J

30. The incorrect expression among the Exp. (a)

following is Entropy change for n moles of isothermal
∆G system expansion of an ideal gas from volume V1 to
(a) = −T
∆G total volume V2 is
[AIEEE 2012]
V
(b) In isothermal process, ∆S = 2.303 nR log 2

V V1
W reversible = − nRT ln f
Vi Here, n = 2, V2 = 100 dm3 , V1 = 10 dm3
∆H ° − T∆S ° 100
(c) ln K = = 2.303 × 2 × 8.3143 log
RT 10
(d) K = e − ∆G °/RT = 38.296 J mol –1K –1
Exp. (c) 32. In view of the signs of ∆r G ° for the following

According to Gibbs Helmholtz equation, reactions
∆G = ∆H − T∆S PbO2 + Pb → 2PbO, ∆rG ° < 0
(a) For a system, total entropy change = ∆S total SnO2 + Sn → 2SnO, ∆rG ° > 0
∆Htotal = 0 Which oxidation states are more
∴ ∆Gsystem = − T∆S total characteristic for lead and tin? [AIEEE 2011]
∆Gsystem (a) For lead + 4, for tin + 2
∴ = −T
∆S total (b) For lead + 2 , for tin + 2
Thus, (a) is correct. (c) For lead + 4, for tin + 4
(b) For isothermal reversible process, ∆E = 0 (d) For lead + 2, for tin + 4
By first law of thermodynamics, ∆E = q + W Exp. (d)
Vf
∴ Wreversible = − q = − ∫Vi
p dV PbO 2 + Pb → 2PbO
V Oxidation state +4 0 +2
⇒ Wreversible = − nRT ln f
Vi Since, ∆G° < 0, i.e., it is negative. Therefore, the
Thus, (b) is correct. reaction is spontaneous in the forward direction.
This suggest that Pb 2+ is more stable than Pb 4+ .
(c) ∆G ° = ∆H° − T∆S ° …(i)
SnO 2 + Sn → 2SnO
Also, ∆G ° = − RT In K
− ∆G ° Oxidation state +4 0 +2
In K =
RT Since, ∆ r G° > 0, i.e., it is positive, therefore, the
(∆H°−T∆S ° ) reaction is non-spontaneous in the forward
In K = [from Eq. (i)]
RT direction. But it will be spontaneous in the
Thus, (c) is incorrect. backward direction. This suggests that Sn4+ will
be more stable than Sn2+ . These facts are also
(d) The standard free energy (∆G° ) is related to
supported by the inert pair effect down the group.
equilibrium constant K as
∆G ° = − RT In K 33. The value of enthalpy change ( ∆H ) for the
∆G °
∴ In K = − ⇒ K = e − ∆G ° / RT reaction
RT
Thus, (d) is also correct. C 2H 5OH( l ) + 3O2( g ) → 2CO2( g ) + 3H 2O(l )
31. The entropy change involved in the at 27°C is − 1366.5 kJ mol −1. The value of
isothermal reversible expansion of 2 moles internal energy change for the above
of an ideal gas from a volume of 10 dm 3 to a reaction at this temperature will be
volume of 100 dm 3 at 27° C is [AIEEE 2011] [AIEEE 2011]
(a) 38.3 J mol K −1 −1
(b) 35.8 J mol K −1 −1 (a) − 1371.5 kJ (b) − 1369.0 kJ
(c) 32.3 J mol −1 K −1 (d) 42.3 J mol −1 K −1 (c) − 1364.0 kJ (d) − 1361.5 kJ

Thermodynamics 51
Exp. (c) Bond enthalpy of H2 = 436 kJ mol −1
Relation between ∆H (enthalpy change) and ∆E [+ ve sign is taken because energy is supplied
(internal energy change) is to break the H  H bond into its atoms]
∆H = ∆E + ∆ng RT Similarly, bond enthalpy of N2 = +712 kJ mol −1
where, ∆ng = (moles of gaseous products) ∆ r H =  BE (N2 ) + BE(H2 ) − 3 BE(N  H)

1 3
– (moles of gaseous reactants)  2 2 
−46 =  × 712 + × 436 − 3 BE (N  H)

For the given reaction, 1 3
∆ng = 2 − 3 = − 1  2 2 
⇒ −1366.5 = ∆E − 1 × 8.314 × 10−3 × 300 −46 = (356 + 654) − 3 BE (N  H)

−1 3 BE (N H) = (1010) + 46
∴ ∆E = − 1364.0 kJ mol
3 BE (N  H) = 1056
34. Consider the reaction, BE (N  H) = 1056 / 3 = 352 kJ mol −1
4NO2( g ) + O2( g ) → 2N 2O5( g ),∆r H = − 111 kJ.
If N 2O5(s ) is formed instead of N 2O5( g ) in 36. For a particular reversible reaction, at
the above reaction, the ∆r H value will be temperature T, ∆H and ∆S were found to be
(Given, ∆H of sublimation for N 2O5 is both +ve. If Te is the temperature at
54 kJ mol −1) [AIEEE 2011] equilibrium, the reaction would be
(a) −165 kJ (b) +54 kJ spontaneous when [AIEEE 2010]
(c) +219 kJ (d) − 219 kJ (a) T e > T (b) T > T e
(c) T e is 5 times T (d) T = T e
Exp. (a)
∆H =− 111KJ
Exp. (b)
4N2 (g )+ O 2 (g ) → 2N2O 5 (g ), ∆G = ∆H − T∆S
144 42444 3
Here, ∆G = Gibb’s free energy
∆H = ? + 54KJ
∆H = Enthalpy change
2N2O 5 (s )
∆S = Entropy change
From Hess law, T = Temperature
∆Hf + ∆Hsub = ∆Hreaction As equilibrium, ∆G = 0. Thus, T∆S = ∆H, as ∆H
∆Hf = ∆Hreaction − ∆Hsub and ∆S are + ve, for a reaction to be feasible
= −111 kJ − (54 kJ) (spontaneous), ∆G should be −ve. This can be
= −111 − 54 kJ = −165 kJ possible only when
Thus, the enthalpy of formation, ∆Hf for N2O 5 (s ) T∆S > Te ∆H i.e., T∆S > Te ∆S
is −165 kJ . or T > Te [Te = temperature at equilibrium]
35. The standard enthalpy of formation of NH 3 37. In a fuel cell, methanol is used as fuel and
is −46.0 kJ mol −1. If the enthalpy of formation oxygen gas is used as an oxidiser. The
ofH2 from its atoms is –436 kJ mol −1 and that reaction is
3
of N 2 is −712 kJ mol −1 , the average bond CH 3OH(l ) + O2( g ) → CO2( g ) + 2H 2O(l )
2
enthalpy of N—H bond in NH 3 is
At 298 K standard Gibb’s energies of
[AIEEE 2010]
formation for CH 3OH(l ),H 2O(l ) and CO2 ( g )
(a) – 964 kJ mol −1 (b) +352 kJ mol −1
are –166.2, –237.2 and −394.4 kJ mol −1,
(c) +1056 kJ mol −1 (d) –1102 kJ mol −1
respectively. If standard enthalpy of
Exp. (b) combustion of methanol is –726 kJ mol −1,
1 3 efficiency of the fuel cell will be [AIEEE 2009]
N2 (g ) + H2 (g ) → NH3 (g ),
2 2 (a) 80% (b) 87%
∆ r H = − 46 kJ mol −1
(c) 90% (d) 97%

Exp. (d) 39. Oxidising power of chlorine in aqueous

∆G
Percentage efficiency of the fuel cell = × 100 solution can be determined by the
∆H parameters indicated below
The concerned reaction is
3 1
HΘ
CH3OH(l ) + O 2 (g ) → CO 2 (g ) + 2H2O(l ) 1 2
∆
diss ∆ EA H Θ
2 Cl 2 ( g ) → Cl ( g ) →
∆Gr = [ ∆Gf (CO 2 , g ) + 2 ∆Gf (H2O, l )] 2 ∆ hyd H Θ
3 Cl – ( g ) → Cl – (aq )
[− ∆Gf (CH3OH, l ) − ∆Gf (O 2 , g )]
2
The energy involved in the conversion of
= − 394.4 + 2 (−237.2) − (−166.2) − 0 1
Cl 2 ( g ) to Cl – (aq ) (using the data,
= − 394.4 − 474.4 + 166.2 2
= −702.6 kJ mol −1 ∆ diss H ΘCl = 240 kJ mol −1
2
Percentage efficiency
702.6 ∆ EA H sCl = − 349 kJ mol −1 ,
= × 100 = 9678
. % ≈ 97%
726 ∆ hyd H sCl = − 381 kJ mol –1 ) will be [AIEEE 2008]
38. On the basis of the following (a) +152 kJ mol −1 (b) – 610 kJ mol −1
+
thermochemical data [ ∆ f G ° H (aq ) = 0] (c) – 850 kJ mol −1 (d) + 120 kJ mol −1
H2O(l ) → H+ (aq ) + OH− (aq ); ∆H = 57.32 kJ Exp. (b)

1 1
H 2( g ) +O2( g ) → H 2O(l ); Cl 2 (g ) → Cl – (aq )
2 2
1
∆H = − 286.02 kJ ∆H = ∆Hdiss (Cl 2 ) + ∆HEA Cl + ∆Hhyd (Cl – )
2
The value of enthalpy of formation of OH − 240
ion at 25°C is [AIEEE 2009]
= − 349 − 381= − 610 kJ mol –1
2
(a) –22.88 kJ (b) –228.88 kJ
(c) +228.88 kJ (d) –343.52 kJ 40. Standard entropy of X 2 ,Y 2 and XY 3 are 60, 40
and 50 JK −1 mol −1, respectively. For the
Exp. (b) reaction,
1 3
Consider the heat of formation of H2O. X 2 + Y 2 → XY3 , ∆H = –30 kJ, to be at
2 2
1
H2 (g ) + O 2 (g ) → H2O(l ); equilibrium, the temperature will be
2
(a) 1250 K (b) 500 K [AIEEE 2008]
∆H = − 286.20 kJ
(c) 750 K (d) 1000 K
∆Hr = ∆Hf (H2O, l ) − ∆Hf (H2 , g )
1
− ∆Hf (O 2 , g ) = − 286.20 = ∆Hf (H2O, l ) − 0 − 0
Exp. (c)
2 1 3
X 2 + Y2 → XY3
∆Hf (H2O, l ) = − 286.20 2 2
Now, consider the ionization of H2O ∆Sreaction = Sproducts − Sreactants
H2O(l ) → H+ (aq ) + OH− (aq )
∆Sreaction = 50 −  × 40 + × 60
3 1
∆H = 57.32 kJ 2 2 
∆Hr = ∆Hf (H+ , aq ) + ∆Hf (OH− , aq ) = − 40 J mol −1
− ∆Hf (H2O, l ) ∆G = ∆H − T∆S
57 .32 = 0 + ∆Hf (OH− , aq ) − (− 286.20) At equilibrium as ∆G = 0
Thus, ∆Hf (OH− , aq ) = 57.32 − 286.20 ∴ ∆H = T∆S
= −228.80 kJ. ∆ H 30 × 103
⇒ T= = = 750 K
∆S 40

Thermodynamics 53
41. Assuming that water vapour is an ideal gas, Exp. (d)

the internal energy change ( ∆ E ) when 1 The entropy change can be given as
mole of water is vaporised at 1 bar pressure ∆H
∆S =
and 100°C, (Given : molar enthalpy of T
∆S = 160.2 J / K
vaporisation of water at 1 bar and 373 K

= 41 kJ mol −1 andR = 8.3 J mol −1 K −1) will be ∆H = 179.1 × 103 J / mol
(a) 4.100 kJ mol −1 [AIEEE 2007] 179.1 × 103 J / mol

T=
(b) 3.7904 kJ mol −1 160.2 J / K
(c) 37.904 kJ mol −1 = 1117.97 K ≈ 1118 K
(d) 41.00 kJ mol −1 44. An ideal gas is allowed to expand both
Exp. (c) reversibly and irreversibly in an isolated
system. If Ti is the initial temperature and T f
H2O (l ) → H2O (g ) is the final temperature, then which of the
∆ng = 1 − 0 = 1 following statements is correct ? [AIEEE 2006]
∆E = ∆H − ∆ng RT (a) (T f ) irrev > (T f ) rev
= 41 − (1 × 8.3 × 373 × 10−3 ) (b)T f > Ti for reversible process but T f = Ti for
[R = 8.3 × 10−3 ] irreversible process
(c) (T f )rev = (T f )irrev
= 37.9 kJ mol −1
(d)T f = Ti for both reversible and irreversible
processes
42. Identify the correct statement regarding a
spontaneous process. [AIEEE 2007] Exp. (a)
(a) For a spontaneous process in an isolated In an ideal gas, there are no intermolecular forces
system, the change in entropy is positive of attraction.
(b) Endothermic processes are never Hence, Tf = Ti for both reversible and irreversible
spontaneous processes.
(c) Exothermic processes are always spontaneous 45. ( ∆H − ∆E ) for the formation of carbon
(d) Lowering of energy in the reaction process is monoxide (CO) from its elements at 298 K is
the only criteria for spontaneity (R = 8.314 JK –1 mol –1 ) [AIEEE 2006]
Exp. (a) (a) − 1238.78 J mol −1
(b) 1238.78 J mol −1
In an isolated system where either mass and −1
(c) − 2477.57 J mol (d) 2477.57 J mol −1
energy are not exchanged with surrounding for
that spontaneous process, the change in entropy Exp. (b)
is positive.
Calculate ∆H − ∆E by using the formula,
43. In conversion of limestone to lime, ∆H − ∆E = ∆ng RT
CaCO3(s ) → CaO(s ) + CO2( g ) 1
= × 8.314 × 298 = 1238.78 J mol −1
2
the values of ∆H ° and ∆S ° are
C(s ) + 1 O (g ) → CO(g )
+ 179.1 kJ mol −1 and 160.2 J /K, respectively  2 
2
at 298 K and 1 bar. Assuming that ∆H ° and  1 1 
 ∆ ng = 1 − = 
∆S ° do not change with temperature,  2 2 
temperature above which conversion of
limestone to lime will be spontaneous is 46. The enthalpy changes for the following
processes are listed below
(a) 1008 K (b) 1200 K [AIEEE 2007]
Cl 2( g ) = 2Cl( g ), 242.3 kJ mol −1
(c) 845 K (d) 1118 K
I 2 ( g ) = 2I ( g ), 151.0 kJ mol −1

ICl( g ) = I( g ) +Cl( g ), 211.3 kJ mol −1 Exp. (b)

−1
I 2(s ) = I 2( g ), 62.76 kJ mol According to relationship of ∆H and ∆E,
Given that the standard states for iodine and ∆H = ∆E + ∆ng RT
chlorine are I 2(s ) and Cl 2( g ), the standard ∆H = enthalpy change (at constant pressure)
enthalpy of formation of ICl ( g ) is ∆E = internal energy change (at constant volume)

[AIEEE 2006] (given reaction is exothermic)
(a) − 14.6 kJ mol −1 (b) − 16.8 kJ mol −1 ( ∆ng = moles of gaseous products
(c) + 16.8 kJ mol −1 (d) + 244.8 kJ mol −1 – moles of gaseous reactants)
For the reaction
Exp. (c)
N2 (g ) + 3H2 (g )→ 2NH3 (g )
1 1
I2 (s ) + Cl 2 (g ) → ICl(g ) ∆ng = 2 − 4 = −2
2 2
Thus, ∆H = ∆E − 2 RT
∆H =  ∆H s → g + ∆Hdiss (Cl 2 ) + ∆Hdiss (I2 )
1 1 1
⇒ ∆H < ∆E
 2 2 2 
− ∆H ICl Note Numerical value of ∆H < ∆E in exothermic
reaction and when ∆ng < 0.
=  × 62.76 + × 242.3 + × 151.0 − 211.3
1 1 1
2 2 2 
49. If the bond dissociation energies of XY, X 2
= 228.03 − 211.3
and Y 2 (all diatomic molecules) are in the
. kJ mol −1
∆H = 1673 ratio of 1 : 1 : 0.5 and ∆H f for the formation
of XY is − 200 kJ mol −1. The bond
47. The standard enthalpy of formation ( ∆H °f )
dissociation energy of X 2 will be [AIEEE 2005]
at 298 K for methane, CH 4 ( g ) is
− 74.8 kJ mol −1. The addition information (a) 400 kJ mol −1 (b) 300 kJ mol −1
required to determine the average energy (c) 200 kJ mol −1 (d) None of these
for C—H bond formation would be Exp. (d)
(a) the dissociation energy of H2 and enthalpy of
sublimation of carbon [AIEEE 2006] Formation of XY is shown as
(b) latent heat of vaporisation of methane X 2 + Y2 → 2 XY
(c) the first four ionisation energies of carbon and ∆H = [(BE)X  X + (BE)Y  Y ] − [ 2 (BE)X  Y ]
electron gain enthalpy of hydrogen If (BE) of X  Y = a KJ / mol
(d) the dissociation energy of hydrogen then, (BE) of ( X  X ) = a
molecule, H2
and (BE) of (Y  Y ) =
a Q 1 X + 1 Y → XY 
2  2 2 2 2 
Exp. (a)
∴ ∆Hf ( X  Y ) = − 200 kJ
Carbon is found in solid state. The state of
∴ − 400 (for 2 mol XY ) =  a + − 2 a
substance affects the enthalpy change. a
 2 
C(s ) → C(g ) sublimation,
a
and H2 (g ) → 2H(g ) dissociation are required − 400 = −
2
for C—H bond.
a = + 800 kJ
48. Consider the reaction, The bond dissociation energy of
N 2 + 3H 2 → 2NH 3 carried out at X 2 = 800 kJ mol −1.
constant temperature and pressure. If ∆H
and ∆E are the enthalpy and internal energy 50. For a spontaneous reaction, the ∆G ,
changes for the reaction, which of the equilibrium constant (K ) and E ° cell will be
following expressions is true ? [AIEEE 2005] respectively [AIEEE 2005]
(a) ∆H > ∆E (b) ∆H < ∆E (a) − ve, > 1, − ve (b) − ve, <1, − ve
(c) ∆H = ∆E (d) ∆H = 0 (c) + ve, > 1, − ve (d) − ve, > 1, + ve

Thermodynamics 55
Exp. (d) 53. The enthalpy change for a reaction does not
The standard free energy related to equilibrium depend upon the [AIEEE 2003]
constant K as (a) physical state of reactants and products
∆G ° = − 2 .303 RT log Keq (b) use of different reactants for the same product
∆G ° = − nFE °cell (c) nature of intermediate reaction steps

(d) difference in initial or final temperatures of
If a cell reaction is spontaneous (proceeding in
involved substances
forward side), it means
Keq > 1and E°cell = + ve Exp. (c)
Thus, ∆G° = − ve Enthalpy change is state function and depends
only on initial and final condition do not depend on
51. An ideal gas expands in volume from path or nature of its intermediates.
1 × 10−3 m 3 to 1 × 10−2 m 3 at 300 K against a
constant pressure of 1 × 105 Nm −2. The work
54. The internal energy change when a system
goes from state A to B is 40 kJ/mol. If the
done is [AIEEE 2004] system goes from A to B by a reversible path
(a) − 900 J (b) − 900 kJ and returns to state A by an irreversible
(c) 270 kJ (d) 900 kJ path, what would be the net change in
internal energy? [AIEEE 2003]
Exp. (a)
(a) 40 kJ (b) > 40 kJ (c) < 40 kJ (d) zero
Work done due to change in volume against
constant pressure is Exp. (d)
W = − p (V2 − V1 ) ∆E = 0, in a cyclic process.
−2 −2 −3
= − 1 × 10 Nm
5
(1 × 10 − 1 × 10 ) m3
55. If at 298 K, the bond energies of C—H, C—C,
= − 900 Nm = − 900 J [1 Nm = 1 J] == and H—H bonds are respectively 414,
347, 615 and 435 kJ mol −1 , the value of
52. The enthalpies of combustion of carbon enthalpy change for the reaction,
and carbon monoxide are − 393.5 and
− 283 kJ mol −1, respectively. The enthalpy of H 2C == CH 2( g ) + H 2( g ) → H 3C CH 3 ( g )
formation of carbon monoxide per mole is at 298 K will be [AIEEE 2003]
(a) 110.5 kJ [AIEEE 2004] (a) + 250 kJ (b) − 250 kJ (c) + 125 kJ (d) − 125 kJ
(b) 676.5 kJ Exp. (d)
(c) − 676.5 kJ
CH2 ==CH2 + H2 → CH3 CH3
(d) − 110.5 kJ
∆H = (BE) reactants − (BE) products
Exp. (d) = 4 (BE)C —H + (BE) C == C + (BE) H  H
I C(s ) + O 2 (g ) → CO 2 (g ), ∆H = − 393.5 kJ − [6(BE) C  H + (BE)C H ]
1
II CO(g ) + O 2 (g ) → CO 2 (g ), ∆H = − 283.0 kJ = − 125 kJ
2
[I – II] gives 56. In an irreverible process taking place at
1 constant T and p and in which only
III C(s ) + O 2 (g ) → CO(g ), pressure-volume work is being done, the
2
[∆H = −393.5 + 283.0 kJ] change in Gibbs free energy (dG ) and
∆H = − 110.5 kJ change in entropy (dS ), satisfy the criteria
The equation III also represents formation of one (a) (dS )V , E < 0,(dG )T , p < 0 [AIEEE 2003]
mole of CO and thus, enthalpy change is the heat (b) (dS )V , E > 0,(dG )T , p < 0
of formation of CO (g ). (c) (dS )V , E = 0,(dG )T , p = 0
(d) (dS )V , E = 0,(dG )T , p > 0

Exp. (b) (a) First law of thermodynamics

(b) Second law of thermodynamics
An irreversible process
(c) Joules equivalent law
⇒ spontaneous process
(d) None of the above
⇒(dS )V, E (change in entropy) = + ve > 0
⇒(dG ) T , p (change in Gibbs free energy) Exp. (c)

− ve ⇒ < 0 Joules law suggests
Mechanical work done by the system , W
57. The correct relationship between free J=
Net heat given to the system , Q
energy change in a reaction and the
corresponding equilibrium constant K c is W
Hence, J=
[AIEEE 2003] q1 + q 2
(a) ∆G = RT ln K c (b) − ∆G = RT ln K c Therefore, W = J (q1 + q 2 )
(c) ∆G ° = RT ln K c (d) − ∆G ° = RT ln K c
is constant with Joules law of equivalence.
Exp. (d)
Relationship between free energy and equilibrium
60. A reaction is non-spontaneous at the
constant, freezing point of water but is spontaneous at
− ∆G ° = RT ln Kc
the boiling point of water, then [AIEEE 2002]
∆H ∆S
58. Heat required to raise the temperature of (a) + ve + ve
1 mole of a substance by 1° is called (b) − ve − ve
[AIEEE 2002] (c) − ve + ve
(a) specific heat (b) molar heat capacity (d) + ve − ve
(c) water equivalent (d) specific gravity
Exp. (a)
Exp. (b)
For spontaneity, ∆G = − ve
The amount of heat required to raise the
temperature of one mole of substance through ∆G = ∆H − T ∆S
1°C is called molar heat capacity. ∆H, for endothermic process + ve
q At lower temperature,
C=
T2 − T1 ∆S + ve
Hence, ∆G = + ve
59. A heat engine absorbs heat q1 from a source But at high temperature, T∆S will be greater than
at temperature T1 and heat q 2 from a source ∆H.
at temperature T2. Work done is found to be Hence, ∆G = − ve, spontaneous.
J (q1 + q 2 ). This is in accordance with
[AIEEE 2002]

6
Solutions
1.
Partial pressure
Partial pressure
The vapour pressures of pure liquids A and B
z
are 400 and 600 mmHg, respectively at 298 K. On
mixing the two liquids, the sum of their initial (a) (b) y
z
volumes is equal to the volume of the final y x
mixture. The mole fraction of liquid B is 0.5 in x w w
the mixture. The vapour pressure of the final
(0, 0) Mole fraction (0, 0) Mole fraction
solution, the mole fractions of components A of water of water
and B in vapour phase, respectively are z
z y
Partial pressure
Partial pressure
(a) 450 mmHg, 0.4, 0.6 (b) 500 mmHg, 0.5, 0.5 y xw
(c) 450 mmHg, 0.5,0.5 (d) 500 mmHg, 0.4,0.6 (c) (d)
Exp. (d) x
w
According to Dalton’s law of partial pressure
ptotal = pA + pB (0, 0) Mole fraction (0, 0) Mole fraction
of water of water
= pA° χ A + pB° χ B …(i)
Given, pºA = 400 mm Hg, pºB = 600 mm Hg Exp. (a)
χ B = 0.5, χ A + χ B = 1 According to Henry’s law (at constant temperature)
∴ χ A = 0.5 pgas = KH × χgas (solute) = KH × [1 − χH 2O (solvent) ]
On substituting the given values in Eq. (i). We get, pgas = KH − KH χH 2O
ptotal = 400 × 0.5 + 600 × 0.5 = 500 mm Hg pgas = partial pressure of the gas above its
Mole fraction of A in vapour phase, solution with a liquid (solvent) say water.
pº χ χgas = mole fraction of the gas (solute) in the
p 0.5 × 400
YA = A = A A = = 0.4 solution.
ptotal ptotal 500
χH 2O = mole fraction of water (solvent).
Mole of B in vapour phase,
YA + YB = 1
YB = 1 − 0. 4 = 0.6 pgas pgas
KH KH
2. For the solution of the gases w , x , y and z in
water at 298 K, the Henry’s law constants (K H )
are 0.5, 2, 35 and 40 K bar, respectively. The
correct plot for the given data is χH2O=0 χH2O=0
[JEE Main 2019, 8 April Shift-II] χgas=1 χgas=0

[i.e. pgas = KH ] Higher the value of KH , higher y M = mole fraction of M in vapour phase;
will be the partial pressure of the gas ( pgas ), at a y N = mole fraction of N in vapour phase
given temperature. The plot of pgas vs χH 2O gives xM y M xM y M
a (−ve) slope. (a) > (b) =
xN y N xN y N
pgas = KH − KH × χH 2O
x y
Comparing the above equation with the equation (c) M < M (d) ( x M − y M ) < ( x N − y N )
xN y N
of straight line y = mx + c
Slope = − K H , intercept = KH Exp. (a)
So, (i) Higher the value of KH , more (−ve) will be
the slope and it is for z (KH = 40 K bar) Key Idea For a solution of volatile liquids the
(ii) Higher the value of KH , higher with the value partial vapour pressure of each component of
of intercept, i.e. partial pressure and it is also for z. the solution is directly proportional to its mole
fraction present in solution. This is known as
3. The osmotic pressure of a dilute solution of an Raoult’s law.
ionic compound XY in water is four times that
Liquid M and N form an ideal solution. Vapour
of a solution of 0.01 M BaCl 2 in water.
pressures of pure liquids M and N are 450 and
Assuming complete dissociation of the given 700 mm Hg respectively.
ionic compounds in water, the concentration ∴ pº N > pº M
of XY (in mol L−1 ) in solution is So, by using Raoult’s law
yN > xN …(i)
(a) 4 × 10−2 (b) 16 × 10−4 (c) 4 × 10−4 (d) 6 × 10−2
and xM > yM …(ii)
Multiplying (i) and (ii) we get
Exp. (d)
yN xM > yM xN
Key Idea Osmotic pressure is proportional to xM yM
∴ >
the molarity (C) of the solution at a given xN yN
temperature, π = CRT
Thus, correct relation is (a).
Concentration of BaCl 2 = 0.01 M (Given)
π XY = 4 πBaCl 2 (Given) 5. Molal depression constant for a solvent is
i × CRT = 4 × i × CRT …(i) 4.0 K kg mol −1 . The depression in the freezing
For the calculation of i, point of the solvent for 0.03 mol kg −1 solution
XY → X + + Y − (Here, i = 2) of K 2 SO4 is
BaCl 2 → Ba 2 + + 2Cl − (Here, i = 3) (Assume complete dissociation of the
electrolyte) [JEE Main 2019, 9 April Shift-II]
Putting the values of i in (i)
(a) 0.18 K (b) 0.36 K
2 × [ XY ] = 4 × 3 × [BaCl 2 ]
(c) 0.12 K (d) 0.24 K
2 × [ XY ] = 12 × 0.01
12 × 0.01 Exp. (b)
[ XY ] =
2
So, the concentration of XY = 0.06 mol L−1 Key Idea Depression in freezing point (∆ Tf ) is
given by ∆Tf = iK f m
= 6 × 10−2 mol L−1
i = vant Hoff factor
K f = molal depression constant
4. Liquid M and liquid N form an ideal solution.
m = molality
The vapour pressures of pure liquids M and N
are 450 and 700 mmHg, respectively, at the K f = 4.0 K kg mol −1 (Given)
same temperature. Then correct statement is −1
m = 0.03 mol kg (Given)
∆Tf = ?
x M = mole fraction of M in solution;
For K 2SO 4 , i = 3
x N = mole fraction of N in solution;

Solutions 59
It can be verified by the following equation : Given,

K 2SO 4 - 2K+ + SO 24 − p° = vapour pressure of pure water of 25º C
Using formula = 35 mm Hg
∆Tf = iK f × m χ B = mole fraction of solute (urea)
0.60
∆Tf = 3 × 4 × 0.03 = 0.36 K
nB 60 0.01
= = =
6. What would be the molality of 20% (mass/mass) nA + nB 360 0.60 20 + 0.01
+
aqueous solution of KI? (Molar mass of KI = 166 18 60
g mol −1 ) [JEE Main 2019, 9 April Shift-II] =
0.01
= 0.0005
(a) 1.48 (b) 1.51 (c) 1.35 (d) 1.08 20.01
i = van’t Hoff factor = 1 (for urea)
Exp. (b) Now, according to Raoult’s law, ∆p = χ B × i × pº
Key Idea Molality is defined as number of On substituting the above given values, we get
moles of solute per kg of solvent. ∆p = 0.0005 × 1 × 35 = 0.0175 mm Hg
w2 1000
m = × 8. 1 g of a non-volatile, non-electrolyte solute is
Mw2 w1
dissolved in 100 g of two different solvents A
w2 = mass of solute
and B, whose ebullisocopic constants are in
Mw2 = molecular mass of solute the ratio of 1 : 5. The ratio of the elevation in
w1 = mass of solvent. ∆T ( A )
their boiling points, b , is
The molality of 20% (mass/mass) aqueous solution ∆Tb ( B )
of KI can be calculated by following formula. [JEE Main 2019, 10 April Shift-II]
w × 1000 (a) 5 : 1 (b) 10 : 1 (c) 1 : 5 (d) 1 : 0.2
m= 2
Mw2 × w1
Exp. (c)
20% aqueous solution of KI means that 20 gm of
KI is present in 80 gm solvent. The expression of elevation of boiling point,
20 1000 w × 1000
m= × = 1. 506 ≈ 1. 51 mol/kg ∆Tb = K b × m × i = kb × 2 ×i
166 80 M 2 × w1
7. At room temperature, a dilute solution of urea where, m = molality
is prepared by dissolving 0.60 g of urea in 360 g i = van’t Hoff factor = 1(for
non-electrolyte/non-associable)
of water. If the vapour pressure of pure water at
w2 = mass of solute in g = 1g (present in both of
this temperature is 35 mm Hg, lowering of
the solutions)
vapour pressure will be (Molar mass of urea
M 2 = molar mass of solute in g mol −1 (same
= 60 g mol −1 ) [JEE Main 2019, 10 April Shift-I]
solute in both of the solutions)
(a) 0.027 mmHg (b) 0.031 mmHg
w1 = mass of solvent in g = 100 g (for both of the
(c) 0.017 mmHg (d) 0.028 mmHg solvents A and B)
Exp. (c) K b = ebullioscopic constant
So, the expression becomes,
Key Idea For dilute solution, lowering of vapour ∆Tb ∝ K b
pressure (∆p) = p0 − p and relative lowering of ∆Tb( A) K b( A) 1  K b( A) 1 
∆p ⇒ = = Given = 
vapour pressure = 0 which is a colligative ∆Tb(B) K b(B) 5  K b(B) 5 
p
property of solutions. 9. The mole fraction of a solvent in aqueous
∆p
= χ B × i ⇒ ∆p = χ B × i × p0 solution of a solute is 0.8. The molality
p0 (in mol kg −1 ) of the aqueous solution is
where, p0 = vapour pressure of pure solvent [JEE Main 2019, 12 April Shift-I]
i = van’t Hoff factor . × 10−2
(a) 1388 . × 10−1
(b) 1388
χ B = mole fraction of solute (c) 1388
. . × 10−3
(d) 1388

Exp. (c) 11. A solution of sodium sulphate contains 92 g

Mass of solute (w2 ) × 1000 of Na + ions per kilogram of water. The
Key Idea Molality ( m) =
Molar mass of solute (M 2 ) × molality of Na + ions in that solution in mol
mass of solvent (w1 ) kg−1 is [ JEE Main 2019, 9 Jan Shift-I]
w 1000 (a) 16 (b) 4 (c) 132 (d) 8

m= 2 ×
M2 w1
Exp. (b)
1000
and also, m = n2 × Number of moles of solute
n1 × M1 Molality (m) = × 1000
Mass of solvent (in g)
Xsolvent = 0.8 (Given) It means that Mass of solute (in g) × 1000
=
nsolvent (n1 ) = 0.8 and nsolute(n2 ) = 02
. Molecular weight of solute 
1000  × mass of solvent (in g)
Using formula m = n2 × 
n1 × M1 w + × 1000 92 × 1000
1000 = Na =
= 02. × = 13.88 mol kg −1 MNa + × wH 2O 23 × 1000
0.8 × 18
= 4 mol kg − 1
10. A solution is prepared by dissolving 0.6 g of
urea (molar mass = 60 g mol −1 ) and 12. Which one of the following statements
1.8 g of glucose (molar mass =180 g mol ) in −1 regarding Henry’s law is not correct?
(a) Different gases have different K H (Henry’s law
100 mL of water at 27°C. The osmotic pressure constant) values at the same temperature
of the solution is (R = 0.08206 L atm K −1 mol −1 ) (b) Higher the value of K H at a given pressure,
[JEE Main 2019, 12 April Shift-II] higher is the solubility of the gas in the liquids
(a) 8.2 atm (b) 2.46 atm (c) The value of K H increases with increase of
temperature and K H is function of the nature
(c) 4.92 atm (d) 1.64 atm
of the gas
Exp. (c) (d) The partial pressure of the gas in vapour phase
is proportional to the mole fraction of the gas
Key Idea Osmotic pressure is proportional to in the solution [ JEE Main 2019, 9 Jan Shift-I]
the molarity (C) of the solution at a given
temperature (T). Exp. (b)
Thus, π ∝ C, π = CRT (for dilute solution) At constant temperature, solubility of a gas (S ) varies
n inversely with Henry’s law constant (KH )
π = RT
Pressure P
V KH = =
Solubility of a gas in a liquid S
n
For the relation, π = CRT = RT Thus, higher the value of K H at a given pressure,
V
the lower is the solubility of the gas in the liquid.
Given, mass of urea = 0.6 g
Molar mass of urea = 60 g mol − 1 13. A solution contain 62 g of ethylene glycol in
Mass of glucose = 1.8 g 250 g of water is cooled upto –10º C. If K f for
Molar mass of glucose = 180 g mol − 1 water is 1.86 K kg mol −1, then amount of
water (in g) separated as ice is
[n (urea) + n2 (glucose)]
π= 2 RT [ JEE Main 2019, 9 Jan Shift-II]
V
(a) 32 (b) 48 (c) 64 (d) 16
 0.6 + 18
. 
 
 60 180  Exp. (c)
= × 1000 × 0.0821 × 300
100 Considering the expression of the depression in
= (0.01 + 0.01) × 10 × 0.0821 × 300 freezing point of a solution,
π = 4. 92 atm ∆Tf = K f × m × i

Solutions 61
wB × 1000
Tf° − Tf = K f × ×i …(i) 15. The amount of sugar (C12H22O11 ) required to
M B × wA (in g)
prepare 2 L of its 0.1 M aqueous solution is
Here, Tf° = 0° C, Tf = − 10°C
(a) 17.1 g (b) 68.4 g (c) 136.8 g (d) 34.2 g
wB = mass of ethylene glycol = 62 g
M B = molar mass of ethylene glycol

 
 CH2 — CH2 

Exp. (b)

    Number of moles of solute (n)
  Molarity =
 OH OH 
 Volume of solution (in L)
 

= 62 g mol −1 Also, n=
wB (g)
wA = mass of water in g as liquid solvent, M B (g mol −1 )
i = van’t-Hoff factor = 1 w / MB
∴ Molarity = B
(for ethylene glycol in water) V
K f = 1.86 K kg mol −1 Given, wB = mass of solute (B) in g
On substituting in Eq. (i), we get M B = Gram molar mass of B (C12H22O11 )
62 × 1000 = 342 g mol −1
0 − (− 10) = 186
. × ×1
62 × wA Molarity = 01
. M, Volume (V ) = 2 L
. × 62 × 1000
186 w / 342
⇒ wA = = 186 g ⇒ . = B
01
10 × 62 2
So, amount of water separated as ice (solid ⇒ wB = 01
. × 342 × 2 g = 68.4 g
solvent)
= 250 − wA = (250 − 186) g = 64 g 16. Elevation in the boiling point for 1 molal
solution of glucose is 2 K . The depression in
14. Liquids A andB form an ideal solution in the the freezing point for 2 molal solution of
entire composition range. At 350 K, the glucose in the same solvent is 2 K. The
vapour pressures of pure A and pure B are relation between K b and K f is
7 × 103 Pa and 12 × 103 Pa, respectively. The (a) K b =1.5 K f (b) K b = 0.5 K f
composition of the vapour in equilibrium (c) K b = K f (d) K b = 2 K f
with a solution containing 40 mole percent [ JEE Main 2019, 10 Jan Shift-II]
of A at this temperature is
(a) x A = 0.76; x B = 0.24 (b) x A = 0.28; x B = 0.72 Exp. (d)
(c) x A = 0.4; x B = 06
. (d) x A = 0.37; x B = 063
. Elevation in boiling point (∆Tb ) = K b × m × i
[ JEE Main 2019, 10 Jan Shift-I] Depression is freezing point (∆Tf ) = K f × m × i
where, m = molality
Exp. (b) For the glucose solution (van’t Hoff factor, i = 1),
For ideal solution, ∆Tb1m = ∆Tf2 m = 2 K
p = x′A p° A + x′B p° B
So, Kb × 1 × 1 = Kf × 2 × 1
Q x′A = 0.4, x′B = 0.6
⇒ Kb = 2Kf
p° A = 7 × 103 Pa, p° B = 12 × 103 Pa
On substituting the given values in Eq. (i), 17. The freezing point of a diluted milk sample
we get is found to be −0.2 ° C, while it should have
p = 0.4 × 7 × 103 + 0.6 × 12 × 103
been −0.5°C for pure milk. How much water
= 10 × 103 Pa = 1 × 104 Pa has been added to pure milk to make the
In vapour phase, diluted sample?
p x′ p° 0.4 × 7 × 103 (a) 2 cups of water to 3 cups of pure milk
xA = A = A A = = 028
.
p p 1 × 104 (b) 1 cup of water to 3 cups of pure milk
(c) 3 cups of water to 2 cups of pure milk
∴ xB = 1 − 028
. = 072
. [Q xA + xB = 1] (d) 1 cup of water to 2 cups of pure milk

Exp. (c) Exp. (c)

We know that, Given, Freezing point of 4% aqueous solution of
Depression in freezing points (∆Tf ) X.
T ° f − Tf = K f × m × i = Freezing point of 12% aqueous solution of Y
where, K f = molal depression constant or (∆Tf )X = (∆Tf )Y [Q ∆Tf = Tf° − Tf ]
wsolute × 1000 K f × mX = K f mY
m = molality =
Msolute × wsolvent (in g) where, mX and mY are molality of X and Y,
i = van’t Hoff factor respectively.
For diluted milk or mX = mY
Number of moles of solute (n)
∆Tf1 = K f × m1 × i Now, molality =
wmilk × 1000 Mass of solvent (in kg)
⇒ 0 − (02 . ) ⇒ 02 . = Kf × ×1 Weight
Mmilk × w1(H2O) n=
Molecular mass
For pure milk
wX wY
∆Tf2 = K f × m2 × i =
M X × (wsolvent )1 M Y × (wsolvent )2
wmilk × 1000
⇒ 0 − (−0.5) = 0.5 = K f × ×1
Mmilk × w2 (H2O) Given, wX = 4 and w(solvent )1 = 96
.
02 K wmilk × 1000 M × w2 (H2O) wY = 12 and w(solvent )2 = 88
So, = f × × milk
0.5 K f Mmilk × w1(H2O) wmilk × 1000 MX = A
4 × 1000 12 × 1000
w (H O) ∴ =
= 2 2 M X × 96 M Y × 88
w1(H2O)
12 × 1000 × M X × 96
w2 (H2O) (in pure milk) 2 Thus, MY =
⇒ = 4 × 1000 × 88
w1(H2O) (in diluted milk) 5
96 × 12
i.e. 3 cups of water has to be added to 2 cups of = × A = 3.27A ≈ 3A
4 × 88
pure milk.
18. K 2HgI4 is 40% ionised in aqueous solution. 20. 8 g of NaOH is dissolved in 18 g of H2O.
The value of its van’t Hoff factor (i) is Mole fraction of NaOH in solution and
(a) 1.6 (b) 1.8 (c) 2.2 (d) 2.0 molality (in mol kg− 1) of the solution
[ JEE Main 2019, 11 Jan Shift-II] respectively are
(a) 0.2, 11.11 (b) 0.167, 22.20
Exp. (b) (c) 0.2, 22.20 (d) 0.167, 11.11
The ionisation of K 2HgI4 in aqueous solution is as [ JEE Main 2019, 12 Jan Shift-II]
follows:
K 2 [HgI4 ] - 2K + + [HgI4 ]2 − Exp. (d)
van’t Hoff factor (i) for ionisation reaction is given as, Mole fraction of solute
number of moles of solute + number of moles solvent
i = 1 + α ( n − 1) =
number of moles of solute
where, n = number of ions, n Solute
α = degree of ionisation or dissociation χSolute =
n Solute + nSolvent
From above equation, it is clear that n = 3 w Solute
i = 1 + 0.4 (3 − 1) [Given, % α = 40% or α = 0.4] Mw Solute
= 1.8 =
w Solute w
+ Solvent
19. Freezing point of a 4% aqueous solution of X Mw Solute MwSolvent
is equal to freezing point of 12% aqueous Given, wSolute = wNaOH = 8 g
solution of Y . If molecular weight of X is A, Mw Solute = MwNaOH = 40 g mol − 1
then molecular weight ofY is w Solvent = w H 2O = 18 g
(a) 4A (b) 2A (c) 3A (d) A
Mw Solvent = 18 g mol − 1

Solutions 63
8 On substituting all the given values in Eq. (i), we

40 0.2 0.2 get
∴χSolute = χNaOH = = =
8
+
18 0.2 + 1 1.2 0.6 × 5 × w × 1000
40 18 2= , w = 2.44 g
122 × 30
= 0167
.
Thus, weight of acid (w) is 2.4 g.Molecules of
Moles of solute
Now, molality (m) = benzoic acid dimerise in benzene as:
Mass of solvent (in kg)
w Solute 2(C 6H5COOH) - (C 6H5COOH)2
Mw Solute Now, we know that depression in freezing point
= × 1000 (∆Tf ) is given by following equation:
wSolvent (in g)
i × K f × wsolute × 1000
8 ∆Tf = i × K f × m = ...(i)
.
02 Mwsolute × wsolvent
= 40 × 1000 = . mol kg − 1
× 1000 = 1111
18 18 Given, wsolute (benzoic acid) = w g
Thus, mole fraction of NaOH in solution and wsolvent (benzene) = 30 g
molality of the solution respectively are 0.167 and Mw Solute (benzoic acid) = 122 g mol −1, ∆Tf = 2 K
11.11 mol kg − 1
K f = 5 Kkg mol −1, %α = 80 or α = 0.8
21. Molecules of benzoic acid (C6H5COOH) 2(C 6H5COOH) - (C 6H5COOH)2
dimerise in benzene. ‘w’ g of the acid Initial 1 0
dissolved in 30 g of benzene shows a Final 1− α α/2
depression in freezing point equal to 2 K. If = 1 − 0.8 0.8 / 2 = 0.4
= 0.2
the percentage association of the acid to
form dimer in the solution is 80, thenw is Total number of moles at equilibrium
(Given that K f = 5 K kg mol− 1, molar mass = 0.2 + 0.4 = 0.6
Number of moles at equilibrium
of benzoic acid = 122 g mol− 1) i =
Number of moles present initially
[JEE Main 2019, 12 Jan Shift-II] 0.6
i = = 0.6
(a) 1.8 g (b) 1.0 g (c) 2.4 g (d) 1.5 g 1
On substituting all the given values in Eq. (i), we
Exp. (c)
get
Molecules of benzoic acid dimerise in benzene as:
0.6 × 5 × w × 1000
2(C 6H5COOH) - (C 6H5COOH)2 2= , w = 2.44 g
122 × 30
Now, we know that depression in freezing point
(∆Tf ) is given by following equation: Thus, weight of acid (w) is 2.4 g.
i × K f × wsolute × 1000
∆Tf = i × K f × m = ...(i) 22. For 1 molal aqueous solution of the
Mwsolute × wsolvent
following compounds, which one will show
Given, wsolute (benzoic acid) = w g the highest freezing point? [JEE Main 2018]
wsolvent (benzene) = 30 g (a) [Co(H2O)6 ]Cl 3
Mw Solute (benzoic acid) = 122 g mol − 1, ∆Tf = 2 K (b) [Co(H2O)5 Cl]Cl 2 ⋅ H2O
K f = 5 Kkg mol − 1, %α = 80 or α = 0.8 (c) [Co(H2O)4 Cl 2 ]Cl ⋅ 2H2O
2(C 6H5COOH) (C 6H5COOH)2 (d) [Co(H2O)3 Cl 3 ]⋅ 3H2O
Initial 1
- 0
Final 1− α α/2
Exp. (a)
= 1 − 0.8 = 0.2 0.8 / 2 = 0.4 Key Idea ‘‘Addition of solute particles to a pure
Total number of moles at equilibrium solvent results to depression in its freezing
= 0.2 + 0.4 = 0.6 point.’’
Number of moles at equilibrium
i = All the compounds given in question are ionic in
Number of moles present initially nature so, consider their van’t Hoff factor (i ) to
0.6 reach at final conclusion.
i = = 0.6
1

The solution with maximum freezing point must Putting the values in Eq. (i)
α
∴ 0.45 = 1 −  (512 . )
have minimum number of solute particles. This .
02 1000 
×
generalisation can be done with the help of van’t  2   60 20 
Hoff factor (i ) i.e. α 0.45 × 60 × 20
Number of solute particles ∝ van’t Hoff factor (i ) 1− =
2 512 . × 02 . × 1000
Thus, we can say directly α α

Solution with maximum freezing point will be the ⇒ 1 − = 0.527 ⇒ = 1 − 0.527
2 2
one in which soluste with minimum van’t Hoff
factor is present ∴ α = 0.946
Now, for Thus, percentage of association = 94.6%
Co(H2O)6 ]Cl 3 - [Co(H2O)6 ]3+ + 3Cl − 24. 18 g of glucose (C 6H12O6 ) is added to 178.2 g
van’t Hoff factor (i ) is 4. Similarly for, water. The vapour pressure of water (in torr)
[Co(H O) Cl]Cl ⋅ H O -
2 5 2 2
for this aqueous solution is
2+ − [JEE Main 2016 (Offline)]
[Co(H O) Cl] + 2Cl
2 5 ‘i’ is 3
(a) 76.0 (b) 752.4 (c) 759.0 (d) 7.6
[Co(H O) Cl ]Cl ⋅ 2H O -
2 4 2 2
[Co(H2O)4 Cl 2 ]+ + Cl − ‘i’ is 2 Exp. (b)
and for [Co(H2O)3 Cl 3 ]⋅ 3H2O, ‘i’ is 1 as it does
not show ionisation.
/ Vapour pressure of water ( p° ) = 760 torr
Number of moles of glucose
Hence, [Co(H2O)3 Cl 3 ]⋅ 3H2O have minimum
Mass (g)
number of particles in the solution. =
So, freezing point of its solution will be maximum. Molecular mass (g mol −1 )
18 g
= = 0.1 mol
23. The freezing point of benzene decreases by 180 gmol −1
0.45°C when 0.2 g of acetic acid is added to Molar mass of water = 18 g/mol
20 g of benzene. If acetic acid associates to Mass of water (given) = 178.2g
form a dimer in benzene, percentage Number of moles of water
association of acetic acid in benzene will be Mass of water 178. 2g
(K f for benzene = 5.12 K kg mol − 1) = = = 9.9 mol
Molar mass of water 18 g /mol
[JEE Main 2017 (Offline)] Total number of moles = (01
. + 9.9) moles = 10moles
(a) 64.6 % (b) 80.4 % (c) 74.6 % (d) 94.6 % Now, mole fraction of glucose in solution =
Change in pressure with respect to initial pressure
Exp. (d) ∆p 01 .
i.e. =
Let the degree of association of acetic acid p° 10
(CH3COOH) in benzene is α, then
or ∆p = 0.01p° = 0.01 × 760 = 7.6 torr
2CH3COOH -
(CH3COOH) 2
∴ Vapour pressure of solution = (760 − 7.6) torr
Initial moles1 0
α = 752.4 torr
Moles at equilibrium 1−α
2
α α α 25. The vapour pressure of acetone at 20°C is
∴ Total moles = 1 − α + = 1− or i = 1 − 185 torr. When 1.2 g of a non-volatile
2 2 2
substance was dissolved in 100 g of acetone
Now, depression in freezing point(∆Tf ) is given as
at 20°C, its vapour pressure was 183 torr. The
∆Tf = i K f m K (i)
molar mass ( g mol –1 ) of the substance is
where, K f = molal depression constant or
[JEE Main 2015]
cryoscopic constant.
(a) 32 (b) 64 (c) 128 (d) 488
m = molality
number of moles of solute Exp. (b)
Molality =
weight of solvent (in kg)
Given, po = 185 torr at 20° C
02. 1000
= × ps = 183 torr at 20° C
60 20

Solutions 65
Mass of non-volatile substance, m = 1.2 g 27. K f for water is 1.86 K kg mol −1. If your
Mass of acetone taken = 100 g automobile radiator holds 1.0 kg of water,
M=? then how many grams of ethylene glycol
As , we have (C 2H 6O2 ) must you add to get the freezing
po − ps n point of the solution lowered to –2. 8°C?
=
ps N (a) 72 g (b) 93 g [AIEEE 2012]

Putting the values, we get, (c) 39 g (d) 27 g
1.2
185 − 183 2 1.2 × 58 Exp. (b)
= M ⇒ =
183 100 183 100 × M Coolant is glycol (C 2H6O 2 ) and it is non-electrolyte.
58 ∆Tf = 2.8° C
183 × 12. × 58
∴ M= 1000K f w1
2 × 100 ∆Tf =
m1w2
M = 63.684 ≈ 64 g / mol
1000 × 1.86 × w1
2.8 =
26. Consider the separate solution of 0.500 M 62 × 1000
C 2H 5OH (aq ), 0. 100 M Mg 3(PO4 )2(aq ), ∴ w1 = 93.33 g
0.250 M KBr (aq ) and 0.125 M Na 3PO4 (aq ) at
25°C. Which statement is true about these
28. A 5.2 molal aqueous solution of methyl
alcohol, CH 3OH, is supplied. What is the
solutions, assuming all salts to be strong
mole fraction of methyl alcohol in the
electrolytes? [JEE Main 2014]
solution ? [AIEEE 2011]
(a) They all have same osmotic pressure (a) 0.100 (b) 0.190 (c) 0.086 (d) 0.050
(b) 0.100 M Mg 3 (PO 4 ) 2 (aq) has the highest
osmotic pressure
Exp. (c)
(c) 0.125 M Na 3 PO 4 (aq ) has the highest osmotic 5.2 molal aqueous solution of CH3OH suggests
pressure that 5.2 moles of CH3OH are dissolved in 1000 g of
(d) 0.5000 M C2 H5OH (aq ) has the highest water.
osmotic pressure n1(CH3OH) = 5.2
1000
Exp. (a) n2 (H2O) = = 55.56
18
Osmotic pressure, π = i × MRT
∴ n1 + n2 = 5.20 + 55.56
Where, i = van’t Hoff factor, M = Molarity
= 60.76 mol
R = Gas constant, T = Temperature
∴ X CH 3OH = Mole fraction of CH3OH
For 0. 500 M C 2H5OH (aq ) , i = 1, thus, n1 5.2
= = = 0.086
πC 2H 5 OH (aq ) = 0. 5 RT n1 + n2 60.76
For 0.100 M Mg 3 (PO 4 )2 (aq ), i = 5 29. Ethylene glycol is used as an antifreeze in a
[Q Mg 3 (PO 4 )2 3 3Mg 2 + +2 PO 34 − ] cold climate. Mass of ethylene glycol
Thus, πMg 3 = 5 × 0.1 × RT
which should be added to 4 kg of water to
(PO 4 ) 2 ( aq )
prevent it from freezing at − 6° C will be
= 0. 5 RT
(K f for water = 1.86 K kg mol −1 and molar
For 0.250 M KBr (aq ),
i = 2 [Q KBr 3 K + + Br - ] mass of ethylene glycol = 62 g mol −1)
Thus, πKBr (aq ) = 2 × 0.250 × RT = 0. 5 RT (a) 804.32 g (b) 204.30 g
(c) 400.00 g (d) 304.60 g [AIEEE 2011]
For 0.125 M Na 3PO 4 (aq ), i = 4
Exp. (a)
[Q Na 3PO 4 3 3Na + + PO 34 − ]
∆Tf = Freezing point ofH2O – freezing point of
Thus, πNa 3 PO 4 (aq ) = 4 × 0.125 × RT = 0. 5 RT ethylene glycol solution
Hence, all solutions have same osmotic pressure. = 0 − (−6° ) = 6°

K f = 1. 86 ° K kg mol −1 For unkown substance X,

w1 = Mass of ethylene glycol in grams 1g 10
Concentration = = 10 g / L = mol L −1
w2 = Mass of solvent ( H2O) in grams = 4000 g 100 cm3 M
m1 = Molar mass of ethylene glycol = 62 g mol −1 50 10
Hence, mol L −1 = mol L −1
1000 K f w1 342 M
∆Tf =
m1 w2 342 × 10
⇒ M= ⇒ M = 68. 4 g mol
1000 × 1.86 × w1 50
∴6= −1
62 × 4000
w1 = 800 g
32. The molality of a urea solution in which
30. The degree of dissociation (α ) of a weak 0.0100 g of urea, [(NH 2 )2CO] is added to
electrolyte, A x B y is related to van’t Hoff 0.3000 dm3 of water at STP is [AIEEE 2011]
factor (i ) by the expression [AIEEE 2011] (a) 0.555 m (b) 5.55 × 10−4 m
i −1 i −1 (c) 33.3 m (d) 3.33 × 10−2 m
(a) α = (b) α =
( x + y − 1) x + y +1 Exp. (b)
x + y −1 x + y +1 moles of solute
(c) α = (d) α = Molality =
i −1 i −1 kg of water
0.010
Exp. (a) Moles of urea = mol
60
van’t Hoff factor ( i ) is related to degree of Water at STP ( d = 1g/cm 3 = 1 kg/dm 3 ) = 0.3 dm3
dissociation (α ) as
i −1 = 0.3 kg
α= 0.010
n−1 ∴ Molality = = 5.55 × 10−4 m
Here, n are the moles of an electrolyte ( A − B) 60 × 0.3
dissolved in a solvent.
For A x By , A x By 3 xA + y + yB− x
33. A solution containing 2.675 g of
i −1
CoCl 3 ⋅ 6NH 3 (molar mass = 267.5 g mol −1) is
Therefore, α= passed through a cation exchanger. The
( x + y − 1)
chloride ions obtained in solution were
31. A 5% solution of cane sugar treated with excess of AgNO3 to give 4.78 g of
(molar mass = 342) is isotonic with 1% of a AgCl (molar mass = 143.5 g mol −1 ). The
solution of an unknown solute. The molar formula of the complex is (Atomic mass of
mass of unknown solute in g/mol is Ag = 108 u) [AIEEE 2010]
[AIEEE 2011] (a) [Co(NH3 )6 ]Cl 3 (b) [CoCl 2 (NH3 )4 ]Cl
(a) 136.2 (b) 171.2 (c) 68.4 (d) 34.2 (c) [CoCl 3 (NH3 )3 ] (d) [CoCl(NH3 )5 ]Cl 2
Exp. (c) Exp. (a)
Two solutions are said to be isotonic, if they have 2.675
Mole of CoCl 3 ⋅ 6NH3 = = 0.01 mol
same molar concentration. Therefore, 267.5
−
Concentration of cane sugar AgNO 3 (aq ) + Cl (aq ) → AgCl ↓ (white)
= Concentration of [C12 H22 O11] + NO −3 (aq )
an unknown solute [ X ] 4.78
Moles of AgCl = = 0.03 mol
For C12H22O11, 143.5
5g 50 0.01 mol CoCl 3 ⋅ 6NH3 gives = 0.03 mol AgCl
Concentration = = 50 / L = mol L −1
100 cm3 342 ∴ 1 molCoCl 3 ⋅ 6NH3 ionises to give = 3 molCl −
[Q Molar mass of C12H22O11 = 342 g mol −1] Hence, the formula of compound is
[Co(NH3 )6 ]Cl 3 .

Solutions 67
34. If sodium sulphate is considered to be Exp. (c)

completely dissociated into cations and pT = pA ° X A + pB ° X B
1 3
anions in aqueous solution, the change in 550 = pA ° × + pB ° ×
freezing point of water( ∆T f ), when 0.01 mole 4 4
pA ° + 3 pB ° = 2200
of sodium sulphate is dissolved in 1 kg of Thus, …(i)

water, is (K f = 1.86 K kg mol −1 ) [AIEEE 2010] When 1 mole of Y is further added to the solution,
vapour pressure of a solution becomes 560 mm Hg.
(a) 0.0372 K (b) 0.0558 K 1 4
Thus, 560 = pA ° × + pB ° ×
(c) 0.0744 K (d) 0.0186 K 5 5
Thus, pA ° + 4 pB ° = 2800 …(ii)
Exp. (b) On subtracting Eq. (ii) by Eq. (i), we get
Na 2SO 4 → 2Na + + SO 24 − pB ° = 2800 − 2200 ⇒ pB ° = 600
van’t Hoff factor (i) for Na 2SO 4 = 3 Putting the value of pB ° in Eq. (i)
pA ° + 3 × 600 = 2200
∆Tf = i × K f × m = 3 × 1.86 × 0.01
pA ° = 2200 − 1800 = 400
 0.01 mol -1 
Q m = 1 kg = 0.01 mol kg  37. A binary liquid solution is prepared by
 
mixing n-heptane and ethanol. Which one
= 0.0558 K of the following statements is correct
regarding the behaviour of the solution?
35. On mixing, heptane and octane form an (a) The solution formed is an ideal solution
ideal solution. At 373 K, the vapour
(b) The solution is non-ideal, showing positive
pressures of the two liquid components deviation from Raoult’s law
(heptane and octane) are 105 kPa and 45 (c) The solution is non-ideal, showing negative
kPa, respectively. Vapour pressure of the deviation from Raoult’s law
solution obtained by mixing 25 g of heptane (d) n-heptane shows positive deviation while
and 35 g of octane will be (molar mass of ethanol show negative deviation from
heptane = 100 g mol −1 and of octane Raoult’s law [AIEEE 2009]
= 114 g mol −1 ). [AIEEE 2010] Exp. (b)
(a) 72.0 kPa (b) 36.1 kPa n-heptane and ethanol forms non-ideal solution.
(c) 96.2 kPa (d) 144.5 kPa As a result, n-heptane-ethanol molecular
Exp. (a) interaction is very poor in comparison to
ethanol-ethanol or n-heptane so the resulting
pT = X H ⋅ p H° + X 0 ⋅ p°0 gives positive deviation from Raoult’s law.
25/100 38. At 80°C, the vapour pressure of pure liquid ‘A’
XH = = 0.45
25 /100 + 35/114 is 520 mmHg and that of pure liquid ‘B ’
∴ X 0 = 0.55 is 1000 mmHg. If a mixture solution of ‘A’
pT = 0.45 × 105 + 0.55 × 45= 72 .0 kPa and ‘B ’ boils at 80°C and 1 atm pressure, the
amount of ‘A’ in the mixture is
36. Two liquids X and Y form an ideal solution at (1 atm = 760 mmHg) [AIEEE 2008]
300 K, vapour pressure of the solution (a) 52 mole per cent (b) 34 mole per cent
containing 1 mol of X and 3 mol of Y (c) 48 mole per cent (d) 50 mole per cent
is 550 mmHg. At the same temperature, if
1 mol of Y is further added to this Exp. (d)
solution, vapour pressure of the solution pT = pA° X A + pB° X B
increases by 10 mm Hg. Vapour pressure (in
Mixture solution boils at 1 atm = 760 mm
mmHg) of X and Y in their pure states will be,
= total pressure
760 = 520 X A + 1000 (1 − X A )
(a) 200 and 300 (b) 300 and 400
(c) 400 and 600 (d) 500 and 600 X A = 0.5, mol % of A = 50%

39. The vapour pressure of water at 20°C is 42. Equal masses of methane and oxygen are
17.5 mmHg. If 18 g of glucose (C 6H12O6 ) is mixed in an empty container at 25°C. The
added to 178.2 g of water at 20°C, the vapour fraction of the total pressure exerted by
pressure of the resulting solution will be oxygen is [AIEEE 2007]
2 1 273
[AIEEE 2008] (a) (b) ×

(a) 17.675 mmHg (b) 15.750 mmHg 3 3 298
(c) 16.500 mmHg (d) 17.325 mmHg 1 1
(c) (d)
3 2
Exp. (d)
This problem is related to the relative lowering of
Exp. (c)
vapour pressure as glucose is a non-volatile Suppose the equal mass of methane and oxygen
solute. Thus, according to Raoult’s law, = w = 1g
w / 32
p0 − psolute Mole fraction of oxygen =
= X solute w / 32 + w / 16
p0
1 / 32 1
18 = =
Moles of glucose = = 0.1 3 / 32 3
180
178.2 Let the total pressure = p
Moles of H2O = = 9.9 Pressure exerted by oxygen (partial pressure)
18
1
01
. 01
. = XO 2 × ptotal = p ×
Xglucose = = 3
9.9 + 01. 10
Thus, the fraction of the total pressure exerted by
17.5 − ps 0.1
Thus, = oxygen is 1/3.
17.5 10
So, ps = 17.325 mm Hg 43. A 5.25% solution of a substance is isotonic
with a 1.5% solution of urea (molar mass
40. The density (in g mL−1 ) of a 3.60 M sulphuric = 60 g mol −1 ) in the same solvent. If the
acid solution that is 29% H 2SO4 (molar mass densities of both the solutions are assumed
= 98 g mol −1) by mass will be [AIEEE 2007] to be equal to 1.0 g cm −3 , molar mass of the
(a) 1.64 (b) 1.88 (c) 1.22 (d) 1.45 substance will be [AIEEE 2007]
(a) 90.0 g mol −1 (b) 115.0 g mol −1
Exp. (c)
(c) 105.0 g mol −1 (d) 210.0 g mol −1
10 × density × % by wt. of solute
Molarity =
mol wt. of the solute Exp. (d)
3.60 × 98
Density = = 1.216 gML−1 = 122
. gML−1 Osmotic pressure of isotonic solutions are equal.
10 × 29 Therefore, π1 = π 2
⇒ C1RT = C 2 RT ⇒ C1 = C 2
41. A mixture of ethyl alcohol and propyl
alcohol has a vapour pressure of 290 mm at If densities of both the solutions are equal, then
300 K. The vapour pressure of propyl alcohol 5.25 g of a substance and 1. 5 g of urea are
is 200 mm. If the mole fraction of ethyl dissolved in the same volume of the solvent, thus,
alcohol is 0.6, its vapour pressure (in mm) at 5.25 / M
C1 =
the same temperature will be [AIEEE 2007] V
(a) 350 (b) 300 (c) 700 (d) 360 [Q M = molecular weight of unknown substance]
5.25 / 60
Exp. (a) C2 =
V
According to Raoult’s law, 5.25 / M 1. 5 / 60
∴ =
p = p° A X A + p° B X B V V
290 = 200 × 0.4 + p° B × 0.6 ⇒ M = 210. 0 g mol −1
p° B = 350 mm

Solutions 69
44. Density of a 2.05 M solution of acetic acid in 47. Equimolar solutions in the same solvent
water is 1.02 g /mL. The molality of the have [AIEEE 2005]
solution is [AIEEE 2006] (a) different boiling point and different freezing
(a) 1.14 mol kg −1 (b) 3.28 mol kg −1 point
(c) 2.28 mol kg −1 (d) 0.44 mol kg −1 (b) same boiling point and same freezing point
(c) same freezing point but different boiling point
Exp. (c) (d) same boiling point but different freezing point
M
Molality (m) = × 100 Exp. (b)
1000 d − MM1
Boiling point and freezing point depend on K b
M = Molarity
(molal elevation constant) and K f (molal
M1 = Molecular mass depression constant) of the solvent. Thus,
d = density equimolar solution (of the non-electrolyte), will
2.05 have same boiling point and also same freezing
= × 1000
(1000 × 1.02) − (2.05 × 60) point.
= 2.28 mol kg −1 ∆Tf = K f × molality
∆Tb = K b × molality
45. 18 g of glucose(C 6H 12O6 ) is added to 178.2 g Note In this question, nature of solute has not been
of water. The vapour pressure of water for mentioned. Hence, we have assumed that
this aqueous solution at 100°C is [AIEEE 2006] solute is non-electrolyte.
(a) 759.00 torr (b) 7.60 torr
(c) 76.00 torr (d) 752.40 torr 48. Benzene and toluene form nearly ideal
solutions. At 20°C, the vapour pressure of
Exp. (d)
benzene is 75 torr and that of toluene is
According to Raoult’s law, relative lowering of
22 torr. The partial vapour pressure of
vapour pressure,
p° − ps n benzene at 20°C for a solution containing
= 78 g of benzene and 46 g of toluene in torr is
p° N
760 − ps 18 / 180 [AIEEE 2005]
= (a) 53.5 (b) 37.5
760 18 / 180+178.2 / 18
760 − ps 01 . (c) 25 (d) 50
=
760 10 Exp. (d)
⇒ ps = 760 − 7.6 = 752.40 torr
Mixture contains 78 g benzene = 1 mol benzene
46. Two solutions of a substance and 46 g toluene = 0.5mol toluene
(non-electrolyte) are mixed in the following Total moles of benzene and toluene = 1.5 mol
manner. 480 mL of 1.5 M first solution + 520 1 2
Mole fraction of benzene in mixture = =
mL of 1.2 M second solution. 1.5 3
What is the molarity of the final mixture ? Vapour pressure of benzene pb° = 75 torr
(a) 2.70 M (b) 1.34 M [AIEEE 2005] ∴Partial vapour pressure of benzene = p° b X b
(c) 1.50 M (d) 1.20 M 2
= 75 × = 50 torr
Exp. (b) 3
The molarity of the resulting solution is given by
49. If α is the degree of dissociation of Na 2SO4 ,
M1V1 + M 2 V2
Total molarity = the van’t Hoff factor (i ) used for calculating
V1 + V2
the molecular mass is [AIEEE 2005]
1.5 × 480 + 1.2 × 520 (a) 1 − 2 α (b) 1 + 2 α
= =1.34 M
480 + 520 (c) 1 − α (d) 1+ α

Exp. (b) Exp. (b)

Na 2SO 4 3 2Na +
+ SO 24 − Water and hydrochloric acid; and water and nitric
acid form miscible solutions. They show negative
van’t Hoff factor, i = [1+ ( y − 1) α ] deviation.
where y is the number of ions from one mole
In case ofCH3COCH3 andCHCl 3 , there is interaction

solute, (in this case = 3), α is the degree of between them, thus force of attraction between
dissociation, i = (1+ 2 α ) CH3COCH3 ....CHCl 3 is larger than between
CHCl 3 ....CHCl 3 or CH3COCH3 ....CH3COCH3 and
50. 6.02 × 1020 molecules of urea are present in thus, vapour pressure is less than expected—a
100 mL of its solution. The concentration of negative deviation.
urea solution is [AIEEE 2004] In case of CH3OH , there is association by
(Avogadro constant, N A = 6.02 × 10 23 mol −1 ) intermolecular H-bonding. When benzene is
(a) 0.001 M (b) 0.01 M added to CH3OH, H-bonding breaks and thus,
(c) 0.02 M (d) 0.1 M force of attraction between CH3OH and benzene
molecule is smaller than between CH3OH or
Exp. (b) benzene molecules (in pure state). Vapour
Avogadro’s number, NA pressure of mixture is greater than expected—a
= 6.02 × 1023 molecules = 1mol positive deviation.
CH3 CH3 CH3
∴ 6.02 × 1020 molecules = 0.001 mol in 100 mL  δ+  δ+ 
or (0.1 L) solution O  H ... O  H ... O  H ...
δ− δ− δ− δ+
mol
∴Molar concentration =
volume in litre 53. Which one of the following aqueous
0.001 solutions will exhibit highest boiling point?
= = 0.01 M
0.1 [AIEEE 2004]
(a) 0.01 M Na 2 SO 4 (b) 0.01 M KNO 3
51. To neutralise completely 20 mL of 0.1 M (c) 0.015 M urea (d) 0.015 M glucose
aqueous solution of phosphorous acid Exp. (a)
(H 3PO3 ), the volume of 0.1 M aqueous KOH
The colligative property will be given as
solution required is [AIEEE 2004]
∆Tb = i × kb × m
(a) 10 mL (b) 20 mL (c) 40 mL (d) 60 mL
Where, ∆Tb = Elevation in boiling point
Exp. (c) i = van’t Hoff factor
H 3 PO 3 is a dibasic acid (i .e., contains two K b = molal elevation constant
ionisable protons attached directly to O). m = molality of the solution
H3PO 3 3 2H+ + HPO 24 − From the above equation, it is clear that,
∴ 0.1 M H3PO 3 = 0.2 N H3PO 3 ∆Tb α i
and 0.1 M KOH = 0.1 N KOH This suggests that higher the value of i, larger is
the boiling point of the solution.
N1V1 = N2 V2
(KOH) (H 3 PO 3 ) For 100% dissociation, i = number of ions
0.1 V1 = 0.2 × 20 produced by one
mole of solute
V1 = 40 mL
Thus, for
52. Which of the following liquid pairs shows a (a) Na 2SO 4
positive deviation from Raoult’s law? Na 2SO 4 3 2Na + +SO 2- 4 [3 ions]
(a) Water — hydrochloric acid [AIEEE 2004] ∴ i =3

(b) Benzene — methanol (b) KNO 3
(c) Water — nitric acid KNO 3 3 K + + NO –3 [2 ions]
(d) Acetone — chloroform ∴ i =2

Solutions 71
(c) Urea [(NH 2 CONH 2 ) and (d) glucose are poor Exp. (a)
electrolytes, therefore i for these two solutes
are equal to zero. Let molarity of Ba(OH)2 = M1
∴ Normality = 2 M1
Hence, 0. 01 M Na 2 SO 4 possess highest boiling
point. Molarity of HCl = 0.1 M = 0.1 N2
N1V1 = N2 V2
54. Which one of the following statements is 2 M1 × 25 = 0.1 × 35
false? [AIEEE 2004]
M1 = 0.07 M
(a) Raoult’s law states that the vapour pressure of
a component over a solution is proportional to 56. If liquid A and B form an ideal solution, the
its mole fraction
[AIEEE 2003]
(b) The osmotic pressure ( π ) of a solution is given
(a) enthalpy of mixing is zero
by the equation π = MRT, where M is the
molarity of the solution (b) entropy of mixing is zero
(c) The correct order of osmotic pressure for 0.01 (c) free energy of mixing is zero
M aqueous solution of each compound is (d) free energy as well as the entropy of mixing are
BaCl 2 > KCl > CH3COOH > sucrose each zero
(d) Two sucrose solutions of same molality
prepared in different solvents will have the
Exp. (a)
same freezing point depression For ideal solution, ∆H = 0, ∆V = 0
FA − A = FB − B = FA − B
Exp. (d)
(a) pA = X A pA° true 57. A pressure cooker reduces cooking time for
(b) π = iMRT = MRT
food because [AIEEE 2003]
true [If van’t Hoff factor, i = 1] (a) heat is more evenly distributed in the cooking
space
(c) π α i (b) boiling point of water involved in cooking is
Greater the value of i, larger is the value of π. increased
i, for BaCl 2 (strong electrolyte) is 3. (c) the higher pressure inside the cooker crushes
the food material
[BaCl 2 3 Ba 2+
+ Cl − (2 ions)]
(d) cooking involves chemical changes helped by
i for KCl is 2. [KCl
3 K + +Cl − ] a rise in temperature
i for CH 3 COOH is
2 [CH 3 COOH 3 CH 3 COO − +H + ] Exp. (b)
But CH 3 COOH is weak electrolyte than KCl. Higher pressure inside the cooker increases
i for sucrose is 1 as it is a non-electrocyte. boiling point, thus heat consistently given is used
Thus, up by food material instead in boiling and
constant boiling evaporation.
i (for BaCl 2 ) > KCl > CH3COOH > sucrose
Thus, (c) is also true.
58. In a 0.2 molal aqueous solution of a weak
(d) ∆Tf = K f m. acid HX , the degree of ionisation is 0.3.
K f is dependent on solvent. Taking K f for water as 1.85, the freezing
Thus, freezing points = [T (solvent) − ∆Tf ] are point of the solution will be nearest to
different. [AIEEE 2003]
Thus, (d) is false. (a) − 0.480°C (b) − 0.360°C
(c) − 0.260°C (d) + 0.480°C
55. 25 mL of a solution of barium hydroxide on
titration with 0.1 molar solution of Exp. (a)
hydrochloric acid gave a titre value of 35 mL. HX 3H +
+ X −1
The molarity of barium hydroxide solution
α = 0.3
was [AIEEE 2003]
i = 1 + α = 1.3
(a) 0.07 (b) 0.14 (c) 0.28 (d) 0.35

∆Tf = molality × K f × i Exp. (a)

= 0.2 × 1.85 × 1.3 = 0.481° Negative deviation means lower vapour pressure.
∴ Freezing point = − 0.481° C It suggests high boiling point, thus resultant
intermolecular force should be stronger than
59. Which of the following concentration factor individual one.
is affected by change in temperature?

[AIEEE 2002] 61. For an aqueous solution, freezing point is
(a) Molarity (b) Molality –0.186°C. Elevation of the boiling point of
(c) Mole fraction (d) Weight fraction the same solution is (K f = 1.86° mol −1 kg
andK b = 0.512 ° mol −1 kg) [AIEEE 2002]
Exp. (a) (a) 0.186° (b) 0.0512°
Molarity gets affected as it is the number of moles (c) 1.86° (d) 5.12°
per unit volume (volume increases with increase in
temperature). Exp. (b)
We know that,
60. In a mixture of A and B , components show ∆Tb = mK b , ∆Tf = mK f
negative deviation when [AIEEE 2002]
∆Tb K b 0.512
(a) A  B interaction is stronger than A  A and = =
B  B interaction ∆Tf K f 1.86
(b) A  B interaction is weaker than A  A and ∆Tb =
0.512
× 0.186
B  B interaction 1.86
(c) ∆V mix > 0, ∆S mix > 0 = 0.0512 °
(d) ∆V mix =0, ∆S mix > 0

7
Equilibrium
1. If solubility product of Zr3 (PO4 )4 is denoted The equilibrium constant for the reaction,
by K sp and its molar solubility is denoted by S, 2SO( g ) + O2( g ) - 2SO (g ) is
3
then which of the following relation between [JEE Main 2019, 8 April Shift-II]
S and K sp is correct? (a) 1025 (b) 1077
[JEE Main 2019, 8 April Shift-I] (c) 10154 (d) 10181
1/ 6 1/ 7
K   K 
(a) S =  sp  (b) S =  sp  Exp. (a)
 144   6912 
1/ 9 1/ 7 S + O 2 w SO 2 , K1
K  K  ∴
(c) S =  sp  (d) S =  sp  SO 2 w S + O2 ,
 929   216  K1 ′ =
1
K1
Exp. (b) 1
or, 2SO 2 w 2S + 2O 2 K1 ′ ′ = (K,1 ′ )2 =
K12
Key Idea The concentration of a substance in a … (i)
saturated solution is defined as its solubility(S). ⇒ 2S + 3O 2 w 2SO 3 , K 2 … (ii)
For A x By - xA y + + yBx − ; K sp = [ A y + ] x [Bx − ] y Now, [(i) + (ii)] gives
2SO 2 + O 2 w 2SO 3 , K 3
For, Zr3 (PO 4 )4 ,
The value of equilibrium constant,
Zr3 (PO 4 )4 (s ) - 3Zr 4 + (aq ) + 4PO 34 − (aq ) 1
3SM 4 SM K 3 = K 2 × K1 ′ ′ = K 2 × 2
K1
Ksp = [Zr 4 + ]3 [PO 34 − ]4
1
1 = 10 ×
129
= 10129 − 104
7  K 7 (1052 )2
Ksp = (3S )3 (4S )4 = 6912 S or S =  sp 
 6912  = 1025
Thus, the relation between molar solubility(S) and
1/ 7 3. Molal depression constant for a solvent is 4.0 K
 K 
solubility product (Ksp ) will be S =  sp  kg mol −1 . The depression in the freezing point
 6912 
of the solvent for 0.03 mol kg −1 solution of
K 2 SO4 is (Assume complete dissociation of the
2. For the following reactions, equilibrium
electrolyte) [JEE Main 2019, 8 April Shift-II]
constants are given :
(a) 0.18 K (b) 0.36 K
S(s ) + O2( g )-SO (g ); 2 K 1 = 10 52
(c) 0.12 K (d) 0.24 K
2S(s ) + 3 O ( g ) - 2SO ( g );
2 3 K 2 = 10129

Exp. (b) In statement (II), ionic product of H2O is

temperature dependent.
Key Idea Depression in freezing point (∆ Tf ) is
K w = [H+ ] [OH− ] ≈ 10−14 (mol / L)2 at 25ºC
given by ∆Tf = iK f m
i = vant Hoff factor With increase in temperature, dissociation of H2O
units into H+ and OH− ions will also increase. As a
K f = molal depression constant, m = molality

result, the value of ionic product, [H+ ] × [OH− ] will
K f = 4.0 K kg mol −1 (Given) be increased. e.g.
−1
m = 0.03 mol kg (Given) Temperature K w (mol/L2)
∆Tf = ? 5ºC 0186
. × 10 −14
For K 2SO 4 , i = 3 25ºC 1008
. × 10 −14
It can be verified by the following equation : 45ºC 4.074 × 10 −14
K 2SO 4 - 2K+ + SO 24 −
Hence, the option (b) is correct.
Using formula
In statement (III), for a weak monobasic acid HA
∆Tf = iK f × m
HA w H⊕ + A s
∆Tf = 3 × 4 × 0.03 = 0.36 K
(1 − α) C M α CM α CM
4. Consider the following statements. ⇒ pH of the solution is 5, i.e.

[H+ ] = 10−5 M = αC
I. The pH of a mixture containing 400 mL
of 0.1 M H 2SO4 and 400 mL of 0.1 M αC × αC 10−5 × α
⇒ Ka = =
NaOH will be approximately 1.3. (1 − α )C 1− α
II. Ionic product of water is temperature 10−5 × α
⇒ 10−5 = ⇒ α = 0.5 ⇒α% = 50
dependent. 1− α
III. A monobasic acid with K a = 10−5 has a Hence, the option (c) is correct.
pH = 5. The degree of dissociation of this In statement (IV), Le-Chatelier’s principle is
acid is 50%. applicable to common ion effect. Because, in
presence of common ion (given) by strong
IV. The Le-Chatelier’s principle is not −
applicable to common-ion effect. The electrolyte (say, Na + A), the product of the
correct statements are concentration terms in RHS increases. For the
[JEE Main 2019, 10 April Shift-I] weaker electrolyte, HA (say) the equilibrium shifts
(a) I, II and IV (b) II and III to the LHS, HA - H⊕ + A s .
(c) I and II (d) I, II and III As a result dissociation of HA gets suppressed.
Hence, the option (d) is incorrect.
Exp. (d)
The explanation of given statements are as 5. For the reaction,
follows: 2SO2( g ) + O2 ( g ) → 2SO3 ( g ),
In statement (I), millimoles of H+
= 400 × 01. × 2 = 80 ∆H = − 57.2 kJ mol− 1 and K c = 1.7 × 1016 . Which
Millimoles of OH− = 400 × 01 . = 40 of the following statement is incorrect?
(Limiting reagent) [JEE Main 2019, 10 April Shift-II]
∴ Millimoles of H+ left = 80 − 40 = 40 (a) The equilibrium constant decreases as the
40 40 1 temperature increases
[H+ ] = = M= M
400 + 400 800 20 (b) The addition of inert gas at constant volume
will not affect the equilibrium constant
pH = − log[H+ ] = − log 
1
⇒
 20  (c) The equilibrium will shift in forward direction
as the pressure increases
= − log 1 + log 2 + log 10
(d) The equilibrium constant is large suggestive of
= −0 + 0.301 + 1 ⇒ 1.30 reaction going to completion and so no
Hence, the option (a) is correct. catalyst is required

Equilibrium 75
Exp. (d) 7. What is the molar solubility of Al(OH)3 in 0.2 M

The explanation of given statements are as follows: NaOH solution? Given that, solubility product
(a) For the given equilibrium, ∆H is negative, so the of Al(OH)3 = 2.4 × 10 −24
equilibrium constant will decrease with
increase in temperature and the equilibrium will [JEE Main 2019, 12 April Shift-I]
shift in the backward direction. (a) 3 × 10−19 (b) 12 × 10−21

Thus, statement (a) is correct. (c) 3 × 10−22 (d) 12 × 10−23
(b) When inert gas is added at constant volume
and constant temperature, an equilibrium Exp. (c)
remains undisturbed.
Thus, statement (b) is correct. Key Idea Concentration of substance in a
(c) For the equilibrium, saturated solution is defined as its solubility (S).
∆ng = 2 − (2 + 1) = − 1, i.e. (− ve) Its value depends upon the nature of solvent
So, increase in pressure will shift the and temperature. For reaction,
equilibrium in the forward direction. AB - A + + B−
Thus, statement (c) is correct. K sp = [ A + ] [B− ]
(d) The reaction takes place in the presence of a
catalyst which is V2O 5 (s ) in contact process or -
Al(OH)3 Al 3 + + 3OH −
NO(g ) in chamber process. Initially 1 0 0
Thus, statement (d) is incorrect. At equilibrium 1− S S 3S + 0.2
NaOH → Na + + OH−
6. The pH of a 0.02 M NH4Cl solution will be 0.2 0.2
[Given K b (NH4 OH) = 10 −5 and log 2 = 0.301] Ksp of Al(OH)3 = 2.4 × 10−24 (Given)
[JEE Main 2019, 10 April Shift-II] Ksp = [Al 3 + ] [OH− ]3
(a) 4.65 (b) 2.65 (c) 5.35 (d) 4.35
2 .4 × 10−24 = [S ] [3S + 02
. ]3 . >> S ]
[Q 02
Exp. (c) 2 .4 × 10−24 = [S ] [0.008]
Key Idea NH4Cl is a salt of weak base (NH4OH) [S ] = 3 × 10−22
and strong acid (HCl). On hydrolysis, NH4Cl will
produce an acidic solution (pH < 7) and the 8. . × 10 −5 m
The molar solubility of Cd (OH)2 is184
expression of pH of the solution is
in water. The expected solubility of Cd(OH)2 in
1 a buffer solution of pH =12 is
pH = 7 − ( pK b + log C )
2 [JEE Main 2019, 12 April Shift-I]
Given, K b (NH4OH) = 10−5 2.49
. × 10−9 M
(a) 184 (b) × 10−9 M
−5
∴ pK b = − log K b = − log(10 ) = 5 .
184
C = concentration of salt solution = 0.02 M (c) 6.23 × 10−11 M (d) 2.49 × 10−10 M
= 2 × 10−2 M
1
Exp. (d)
Now, pH = 7 − ( pK b + log C )
2 Key Idea The concentration of substance in a
On substituting the given values in above saturated solution is defined as its solubility (S).
equation, we get Its value depends upon the nature of solvent
1
= 7 − [5 + log(2 × 10−2 )] and temperature.
2 A x By - xA y + + yBx −
1 Ksp = [ A y + x
] [B x − ] y
= 7 − [5 + log 2 − 2 ]
2
1
= 7 − [5 + 0.301 − 2 ] Solubility of Cd(OH)2 (S) = 1.84 × 10− 5 M
2 Given, pH = 12 [for Cd(OH)2 in buffer solution]
= 7 − 165
. = 5.35 So, pOH = 2 (QpH + pOH = pK w )

12 + pOH = 14 (d) 2NO(g ) N2 ( g ) + O 2 ( g )

-
pOH = 14 − 12 = 2 ∆ng = nproduct − nreactant = 2 − 2 = 0
∴ [OH− ] = 10− 2 in buffer solution. ∆ng = 0 ⇒ So, K p = Kc
For reaction Cd(OH)2 → Cd 2 + + 2OH− 10. 20 mL of 0.1 M H2SO4 solution is added to
S S2
Ksp = [Cd 2 + ] [OH− ]2 30 mL of 0.2 M NH 4OH solution. The pH of

the resultant mixture is [pK b ofNH 4OH = 4.7]
Ksp = (S )(2S ) = 4S2 3
(a) 9.3 (b) 5.0 (c) 9.0 (d) 5.2
. × 10− 5 )3
= 4(184 [ JEE Main 2019, 9 Jan Shift-I]
Ksp = 24.9 × 10− 15 Exp. (a)
Ksp
[Cd 2 + ] = (a) The reaction takes place when H2SO 4 is added
[OH− ]2 to NH4OH is as follows :
24.9 × 10− 15 H 2SO 4 + 2NH 4OH → (NH 4 )2SO 4
[Cd 2 + ] = −2 2 + 2H 2O
(10 ) Strong acid Weak base Salt of strong
= 24.9 × 10− 15 × 10 + 4 acid
+ weak base
⇒ = 24.9 × 10− 11 M Millimoles at t = 0 20 × 0.1 = 2 30 × 0.2 = 6 0
[Cd 2 + ] ⇒2.49 × 10− 10 M Millimoles at t = t 0 2 2
The expected solubility of Cd(OH)2 in a buffer So, the resulting solution is a basic buffer
solution of pH = 12 is 2.49 × 10− 10 M. [NH4OH + (NH4 )2 SO 4 ].
According to the Henderson’s equation,
9. In which one of the following equilibria, [(NH4 )2 SO 4 ]
K p ≠ Kc ? [JEE Main 2019, 12 April Shift-II] pOH = pK b + log
[NH4OH]
c
(a) 2C(s ) + O2 (g ) 2CO(g ) 2
= 47. + log = 4.7
(b) 2HI(g ) c H2 (g ) + I2 (g )
⇒
2
pH = 14 − pOH = 14 − 4.7 = 9.3
(d) 2NO(g ) cc
(c) NO2 (g ) + SO2 (g ) NO(g ) + SO3 (g )
N2 (g ) + O2 (g )
11. Consider the following reversible chemical
Exp. (a) reactions,
K1
A 2( g ) + B 2 ( g ) -2AB (g ) …(i)
Key Idea The relationship between Kp and Kc is
∆n g K2
Kp = Kc (RT ) 6AB ( g ) - 3A ) + 3B 2 ( g ) …(ii)
2 (g
where, ∆ng = nproducts − nreactants
If ∆ng = 0 then Kp = Kc The relation between K 1 and K 2 is
(a) K 2 = K 13 (b) K 1 K 2 = 3
If ∆ng = + ve then Kp > Kc
1
If ∆ng = − ve then Kp < Kc (c) K 2 = K 1− 3 (d) K 1 K 2 =
3
Consider the following equilibria reactions [ JEE Main 2019, 9 Jan Shift-II]
(a) 2C(s ) + O2 (g ) - 2CO(g ) Exp. (c)
∆ng = nproduct − nreactant = 2 − (1) = 1
[ AB]2
∆ng ≠ 0 ⇒ So, K p ≠ Kc (i) A2 (g ) + B2 (g ) c 2 AB(g ) K1 =
[ A2 ] [B2 ]
(b) 2HI(g ) - H2 ( g ) + I 2 ( g )
(ii) 6 AB(g ) c 3 A2 (g ) + 3B2 (g );
∆ng = nproduct − nreactant = 2 − 2 = 0
[ A2 ]3 [B2 ]3 1 1
∆ng = 0 ⇒ So, K p = Kc K2 = = = 3,
[ AB]6  [ AB]  2
3
K1
(c) NO 2 (g ) + SO 2 (g ) - NO(g ) + SO 3 (g )  
∆ng = nproduct − nreactant = 2 − 2 = 0  [ A2 ][B2 ]
∆ng = 0 ⇒ So, K p = Kc ⇒ K 2 = K1−3

Equilibrium 77
Kp Exp. (b)
12. The values of for the following reactions
KC The reaction involved is as follows :
at 300 K are, respectively (At 300 K, Ca(OH)2 + Na 2SO 4 → CaSO 4 + 2OH− + 2Na +
T = 24.62 dm 3 atm mol −1 ) Millimoles 100
2 × 1000
= 14 0 0 0
at t = 0 142
N 2 ( g ) + O2 ( g )=2NO(g ) Milimoles 86 0 14 28
N 2O4( g )=2NO (g ) 2 at t = t s [Limiting reagent]
N 2 ( g ) + 3H 2 ( g )
=2NH (g ) 3 Weight
No. of moles =
(a) 1, 24.62 dm 3 atm mol −1 , Molecular mass
606.0 dm 6 atm 2 mol −2 14
∴ Mass of CaSO 4 = × 136 = 1 . 9 g
(b) 1, 24.62 dm 3 atm mol −1 , 1000
1.65 × 10−3 dm −6 atm −2 mol 2 No. of moles of solute
Also, Molarity =
(c) 24.62 dm 3 atm mol −1 , 606.0 dm 6 atm −2 Volume of solution (in L)
mol 2 , 1.65 × 10−3 dm−6 atm −2 mol 2
∴ Molarity of OH– ,
(d)1, 4.1× 10−2 dm −3 atm −1 mol,
28 1000
606 dm 6 atm 2 mol −2 [OH– ] = × = 0.28mol L−1
1000 100
= 0.28 M
Exp. (b)
14. 5.1 g NH4 SH is introduced in 3.0 L evacuated
We know that, the relationship between K p and
KC of a chemical equilibrium state (reaction) is flask at 327°C. 30% of the solid NH 4 SH
∆n Kp ∆n
decomposed to NH3 and H 2S as gases. The
K p = KC (RT ) g ⇒ = (RT ) g Kp of the reaction at 327°C is
KC
(R = 0.082 atm mol −1 K −1 , molar mass of
∆ng = ΣnProducts − ΣnReactants
where,
S = 32 g mol −1 , molar mass of N = 14 g mol −1 )
c
(i) N2 (g ) + O 2 (g ) 2NO(g )
⇒ (RT )2 − ( 1 + 1) = (RT )0 = 1
(a) 0. 242 × 10−4 atm 2 (b) 0. 242 atm 2
(c) 4. 9 × 10−3 atm 2 (d)1 × 10−4 atm 2
(ii) N2O 4 (g )c 2NO 2 (g )
⇒ (RT )2 − 1 = RT = 24.62 dm3 atm mol −1 [ JEE Main 2019, 10 Jan (Shift-I)]
c
(iii) N2 (g ) + 3H2 (g ) 2NH3 (g )
⇒(RT )2 − ( 3 + 1) = (RT )− 2
Exp. (b)
Molar mass of NH4SH = 18 + 33 = 51g mol −1
1
= Number of moles of NH4SH introduced in the
(24.62 dm atm mol −1 )2
3
−3 −2
vessel
= 1.649 × 10 dm –6
atm mol 2
Weight 5⋅1
= = = 01
. mol
Molar mass 51
13. A mixture of 100 mmol of Ca(OH)2 and 2 g of
sodium sulphate was dissolved in water and NH4SH(s ) c NH3 (g ) + H2S(g )
the volume was made upto 100 mL. Number of 0.1 0 0
moles at t = 0
The mass of calcium sulphate formed and the
At t = t eq . ( − 0.03)
011 30% of 30% of 0.1
concentration of OH− in resulting solution, . = 0.03
01 = 0.03
respectively, are : (Molar mass of
Active mass 0.03 0.03
Ca(OH)2 , Na 2SO4 and CaSO4 are74, 143 and = 0.01 = 0.01
136 g mol −1 , respectively; K sp of Ca(OH)2 is (mol L −1) 3 3
5.5 × 10 −6 ) [ JEE Main 2019, 10 Jan Shift-I] KC =

[NH3 ] [H2S] 0.01 × 0.01
= = 10−4 (mol L −1) 2
(a) 136
. g, 0.28 mol L −1 [NH4HS(s )] 1
(b) 1.9 g, 0.28 mol L −1 ⇒ K p = KC (RT )
∆n g
(c) 13.6 g, 0.14 mol L −1

[where, ∆ng = Σnproduct − Σnreactant ] = 2 − 0 = 2
(d) 1.9 g, 0.14 mol L −1

∴ K p = KC (RT )2 Exp. (a)

= 10− 4 × [0.082 × (273 + 327 )]2 atm2 According to Nernst equation,
= 0.242 atm2 Ecell = E °cell −
2.303 RT
log Q
nF
15. Consider the reaction,
2.303 RT
Given, = 0.059 V
N 2 ( g ) + 3H 2 ( g ) =2NH (g ) 3 F
0.059
The equilibrium constant of the above ∴ Ecell = E ° cell − log Q
reaction is K p. If pure ammonia is left to n
dissociate, the partial pressure of ammonia At equilibrium, Ecell = 0
0.059
at equilibrium is given by (Assume that E ° cell = log KC
n
p NH3 < <p total at equilibrium)
For the given reaction, n = 2
33/ 2 K 1p/ 2 P 2 33/ 2 K 1p/ 2 P 2 Also, KC = 10 × 1015 [given]
(a) (b)
4 16 0.059
∴ E° cell = log (10 × 1015 )
2
K p 1/ 2 P 2 K p 1/ 2 P 2
(c) (d) = 0.472 V ≈ 0.473 V
16 4
[ JEE Main 2019, 11 Jan Shift-I] 17. For the equilibrium,2H2O H3O+ + OH − ,
-
Exp. (b) the value of ∆G º at 298 K is approximately
(a) − 80 kJ mol − 1 (b) 100 kJ mol − 1
N2 ( g ) + 3H2 (g ) =2NH3 (g )
(c) 80 kJ mol − 1 (d) − 100 kJ mol − 1
At equilib. pN 2 = P, pH 2 = 3P, pNH 3 = 2 P
⇒ p( total ) = pN 2 + pH 2 + pNH 3 ~
− pN 2 + pH 2
Exp. (c)
[Q p( total ) >> pNH 3 ]
We know that, ∆G° = − 2.303 RT log K
= p + 3p = 4p
2
pNH Also, given equilibrium is
p2NH 3
Now, Kp = = 3 –
pN 2 × pH3 2 p × (3 p)3 2H2O - H3O + + OH
2
pNH 2
pNH [H+ ][OH− ] = 10−14 or K = 10− 14
= 3
= 3
[Q P = 4 p] ∴ ∆G° = − 2.303 × 8.314 JK –1mol −1 × 298K
27 × p4 4
27 ×  
P
× log10−14
 4
2
pNH × 44 = 79881.8 J mol − 1
Kp = 3
= 79.8 kJ ≈ 80 kJ mol − 1
32 × 3 × P 4
32 × 3 × P 4 × K p 18. Two solids dissociate as follows:
⇒ 2
pNH =
3
3 × 31/ 2
44
× P × K1p/ 2
2
33 / 2 × P 2 × K1p/ 2
-B (g ) + C(g );K
A (s ) p1 = x atm 2
⇒ pNH 3 = = D(s ) -C( g ) + E ( g ); K = y atm 2
42 16 p
2
16. Given the equilibrium constant The total pressure when both the solids
(K C ) of the reaction : dissociate simultaneously is
(a) x + y atm (b) x 2 + y 2 atm
Cu(s ) + 2 Ag+ (aq ) → Cu2 + (aq ) + 2 Ag(s )
(c) ( x + y ) atm (d) 2( x + y ) atm
° of this reaction
is10 × 1015 , calculate the E cell [ JEE Main 2019, 12 Jan Shift-I]
 RT  Exp. (d)
at 298 K. 2.303 at 298 K = 0.059 V
 F  The equilibrium reaction for the dissociation of two
(a) 0.4736 V (b) 0.04736 mV solids is given as:
(c) 0.4736 mV (d) 0.04736 V A(s ) e B(g ) + C(g )
[ JEE Main 2019, 11 Jan Shift-II] p1 p1 + p 2

Equilibrium 79
At equilibrium
20. If K sp of Ag2CO3 is 8 × 10− 12, the molar
K p1 = x = pB ⋅ pC = p1( p1 + p2 ) …(i)
Similarly, D(s) e C(g ) + E(g )
solubility of Ag2CO3 in 0.1 M AgNO3 is
(a) 8 × 10− 12 M (b) 8 × 10− 13 M
At equilibrium p1 + p2 ⋅ p2
− 10
K p 2 = y = pC ⋅ pE =( p1 + p2 ) p2 (c) 8 × 10 M (d) 8 × 10− 11 M
…(ii)
On adding Eq. (i) and (ii), we get. [ JEE Main 2019, 12 Jan Shift-II]
Exp. (c)
K p1 + K p 2 = x + y = p1( p1 + p2 ) + p2 ( p1 + p2 )
Let the solubility of Ag 2CO 3 is S. Now,
= ( p1 + p2 )2 0.1 M of AgNO 3 is added to this solution after
or x + y= p1 + p2 …(iii) which let the solubility of Ag 2CO 3 becomes S ′.
Now, total pressure is given as ∴ [Ag + ] = S + 0.1 and [CO 23 − ] = S ′
pT = pB + pC + pE Ksp = (S + 0.1)2 (S ′ ) ...(i)
= p1 + ( p1 + p2 ) + p2 − 12
Given, Ksp = 8 × 10
= 2 ( p1 + p2 ) …(iv)
On substituting the value of p1 + p2 from Eq. (iii) to Q K sp is very small, we neglectS ′ againstS in Eq. (i)
Eq. (iv), we get ∴ K sp = (0.1)2 S ′
pT =2 x + y or 8 × 10− 12 = 0.01 S ′
19. In a chemical reaction, A + 2B

K
- 2C + D, or S ′ = 8 × 10− 12 × 102 = 8 × 10− 10 M
the initial concentration ofB was 1.5 times of Thus, molar solubility of Ag 2CO 3 in 0.1 M
the concentration of A, but the equilibrium AgNO 3 is 8 × 10− 10 M.
concentrations of A and B were found to be
equal. The equilibrium constant (K ) for the 21. Which of the following lines correctly show
aforesaid chemical reaction is the temperature dependence of equilibrium
[ JEE Main 2019, 12 Jan Shift-I] constant, K , for an exothermic reaction?
1 [JEE Main 2018]
(a) (b)16 (c) 1 (d) 4
4 In K A
B 1
Exp. (d) (0, 0) T(K)
For the given chemical reaction, ××
××
A + 2B w 2C + D ××
××
C
××
At, t = 0 a0 1.5a0 0 0 ××
D
t = t eq a0 − x 1.5a0 − 2 x 2x x
(a) A and B (b) B and C
[x = degree of dissociation]
(c) C and D (d) A and D
Given, at equilibrium.
[ A] =[B] Exp. (a)
a0 − x = 15. a0 − 2 x From thermodynamics,
x = 0.5a0 −∆H° ∆S °
lnk = + …(i)
∴ [A] = a0 − x = a0 − 0.5a0 = 0.5a0 RT R
[B] = 15
. a0 − 2 x = 15 . a0 − 2 × 0.5a0 = 0.5a0 Mathematically, the equation of straight line is
[C] = 2 x = 2 × 0.5a0 = a0 y = c + mx …(ii)
[D] = x = 0.5a0 After comparing Eq. (ii) with (i) we get,
[C]2 [D] − ∆H° ∆S °
Now, K = slope = and intercept =
[ A] [B]2 R R
Now, substituting the values in above equation, Now, we know for exothermic reaction ∆H is
we get negative (−)ve. But here,
(a )2 × (0.5a0 ) −∆H°
Slope = is positive
K= 0 =4 R
(0.5a0 ) × (0.5a0 )

So, lines A and B in the Exp. (c)

graph represent ln K
A
temperature Its given that the final volume is 500 mL and this
dependence of B final volume was arrived when 50 mL of 1 M
equilibrium constant K
1 Na2SO4 was added to unknown Ba2 + solution.
(0, 0) T(K)
So, we can interpret the volume of unknown Ba2 +
for an exothermic
reaction as shown solution as 450 mL i.e.
below 450mL + 50mL → 500mL
Ba 2+ Na 2SO 4 BaSO 4
solution solution solution
22. An aqueous solution contains 0.10 M H2S
and 0.20 M HCl. If the equilibrium constants From this we can calculate the concentration of
SO24 − ion in the solution via
for the formation of HS− from H2S is
M1V1 = M 2 V2
1.0 × 10−7 and that of S2− from HS− ions is
1 × 50 = M 2 × 500
1.2 × 10−13 then the concentration of S2− ions (as 1M Na2SO4 is taken into consideration)
in aqueous solution is : [JEE Main 2018] 1
M2 = = 01. M
(a) 5 × 10−8 (b) 3 × 10−20 (c) 6 × 10−21 (d) 5 × 10−19 10
Now for just precipitation,
Exp. (b) Ionic product = Solubility product (Ksp )
Given i.e. [Ba 2+ ][SO 24 − ] = Ksp of BaSO 4
[H2S] = 010
. M Given Ksp of BaSO 4 = 1 × 10−10
. M So, [H+ ] = 020
[HCl] = 020 . M
So, [Ba 2+ ][0.1] = 1 × 10−10
H2S- H+ + HS− , K1 = 1.0 × 10−7
− or [Ba 2+ ] = 1 × 10−9 M
HS -H +
. × 10−13
+ S2 − , K 2 = 12
Remember This is the concentration of Ba 2 + ions
It means for, in final solution.
H2S -2H +
+ S2 − Hence, for calculating the [Ba 2+ ] in original
K = K1 × K 2 solution we have to use
. × 10−7 × 1.2 × 10−13
= 10 M1V1 = M 2 V2
= 1.2 × 10−20 as M1 × 450 = 10−9 × 500
K × [H2S] so, M1 = 1.1 × 10−9 M
Now [S2 − ] =
[H+ ]2
[according to the final equation] 24. Which of the following are Lewis acids?
1.2 × 10−20 × 0.1 M [JEE Main 2018]
=
(0.2M)2 (a) PH3 and BCl 3
−20 −1 (b) AlCl 3 and SiCl 4
1.2 × 10 × 1 × 10 M
= (c) PH3 and SiCl 4
4 × 10−2 M
(d) BCl 3 and AlCl 3
= 3 × 10−20 M
Exp. (d)
23. An aqueous solution contains an unknown
concentration of Ba 2 + . When 50 mL of a 1 M / Lewis acids are defined as,
solution of Na 2SO 4 is added, BaSO 4 just ‘‘Electron deficient compounds which have
begins to precipitate. The final volume is the ability to accept atleast one lone pair.’’
500 mL. The solubility product of BaSO 4 is The compound given are
1 × 10−10 . What is the original concentration PH3 Octet complete although P has vacant
of Ba 2+ ? [JEE Main 2018] 3d-orbital but does not have the tendency to
accept lone pair in it. Hence, it cannot be
(a) 5 × 10−9 M (b) 2 × 10−9 M
considered as Lewis acid.
. × 10−9 M
(c)11 . × 10−10 M
(d)10

Equilibrium 81
BCl3 Incomplete octet with following orbital picture. Al(CN)3 and Pb(CH3 COO)2 are the salts of weak
2p acid and weak base.
1s 2s Vacant
p- orbital CH3 COOK is the salt of strong base and weak
B- acid.
Hence, the solution of CH3COOK will be most
Used in bond basic because of the following reaction.

formation with
Cl having one electron
each from B and Cl
CH3COOK + H2O -CH3COOH + KOH
(Weak acid) (Strong base)
Hence, vacant p-orbital of B can accept one lone 26. An alkali is titrated against an acid with
pair thus it can be considered as Lewis acid. methyl orange as indicator, which of the
AlCl 3 -Similar condition is visible in AlCl 3 as well following is a correct combination?
i.e. Al ( Valence orbital only) = [JEE Main 2018]
Vacant p-orbital Base Acid End point
3s 3p 3d vacant
(a) Weak Strong Colourless to pink
(b) Strong Strong Pinkish red to yellow
Used in bond
formation with Cl (c) Weak Strong Yellow to pinkish red
(d) Strong Strong Pink to colourless
Hence this compound can also be considered
as Lewis acid.
SiCl 4 - Although this compound does not have
Exp. (c)
incomplete octet but it shows the tendency to Methyl orange show Pinkish colour towards more
accept lone pair of electrons in its vacant acidic medium and yellow orange colour towards
d-orbital. This tendency of SiCl 4 is visible in basic or less acidic media. Its working pH range is
following reaction. 3.9 –4.5
Pinkish Yellow
Cl Cl Red orange
H
O Weak base have the pH range greater than 7.
Si + H2O Si
When methyl orange is added to this weak base
Cl Cl Cl Cl H
Cl Cl solution it shows yellow orange colour.
Now when this solution is titrated against strong
Lone pair acceptance
acid the pH move towards more acidic range
in d-orbital
and reaches to end point near 3.9 where yellow
Cl orange colour of methyl orange changes to
Pinkish red resulting to similar change in colour
Si OH + HCl of solution as well.
Cl
Cl 27. pK a of a weak acid (HA) and pK b of a weak
Thus option (b) and (d) both appear as correct base (BOH) are 3.2 and 3.4, respectively. The
but most suitable answer is (d) as the condition pH of their salt (AB) solution is
of a proper Lewis acid is more well defined in
BCl 3 and AlCl 3 .
(a) 7.2 (b) 6.9 (c) 7.0 (d) 1.0
25. Which of the following salts is the most basic
in aqueous solution? [JEE Main 2018]
Exp. (b)
(a) Al(CN)3 (b) CH3COOK For a salt of weak acid and weak base,
(c) FeCl 3 (d) Pb(CH3COO)2 1 1
pH = 7 + pK a − pK b
2 2
Exp. (b)
Given, pK a (HA) = 3.2, pK a (BOH) = 3.4
Among the given salts 1 1
∴ pH = 7 + (3.2) − (3.4)
FeCl3 is acidic in nature i.e., have acidic solution 2 2
as it is the salt of weak base and strong acid.
= 7 + 1.6 − 1.7 = 6.9

28. The equilibrium constant at 298 K for a 30. For the reaction,
reaction, A + B C + D is 100. If the initial
- 1
SO2 ( g ) + O2 ( g ) SO3 ( g ),
e
concentrations of all the four species were 1 2
M each, then equilibrium concentration of if K P = K C (RT )x where the symbols have
D (in mol L−1 ) will be [JEE Main 2016 (Offline)]
usual meanings then, the value of x is

(a) 0.818 (b) 1.818 (c) 1.182 (d) 0.182 (assuming ideality). [JEE Main 2014]
Exp. (b) 1 1
(a) −1 (b) − (c) (d) 1
2 2
A + B - C + D
Initially at t = 0 1 1 1 1 Exp. (b)
At equilibrium 1− x 1− x 1+ x 1+ x By using this formula, Equilibrium constant,
[C ][D] (1 + x)(1 + x) (1 + x)2 K P = Kc (RT )
∆n g
Keq = = =
[ A][B] (1 − x)(1 − x) (1 − x)2
where ∆ng = (no. of moles of products) − (no. of
2
 1 + x 1+ x moles of reactants)
or 100 =   or 10 = For the given reaction,
1 − x 1− x
1
or 10 − 10 x = 1 + x ⇒ 10 − 1 = x + 10 x SO 2 ( g ) + O 2 (g ) SO 3 (g )
1
2
9
9 = 11 x ⇒ x = = 0.818 ∆ng = 1 −  + 1 = 1 −   = −
1 3 1
11  2   2  2
∴ [D] = 1 + x = 1 + 0.818 = 1818
.
31. How many litres of water must be added to 1
29. The standard Gibbs energy change at 300K L of an aqueous solution of HCl with a pH of
for the reaction, 2 A B + C is 2494. 2 J. At
# 1 to create an aqueous solution with pH of 2?
a given time, the composition of the (a) 0.1 L (b) 0.9 L [JEE Main 2014]
1 1
reaction mixture is[ A] = ,[ B] = 2 and[C ] = . (c) 2.0 L (d) 9.0 L
2 2
The reaction proceeds in the Exp. (d)
[R = 8.314 JK / mol, e = 2.718] [JEE Main 2015] pH = 1
(a) forward direction because Q > Kc
∴ [H+ ] = 10−1 = 0.1M
(b) reverse direction because Q > Kc
pH = 2
(c) forward direction because Q < Kc
(d) reverse direction because Q < Kc ∴ [H+ ] = 10−2 = 0.01M
For dilution of HCl,
Exp. (b) M1V1 = M 2 V2
Given, ∆G° = 2494.2J 0.1 × 1 = 0.01 × V2
[ B][C] 2 × (1 /2 ) V2 = 10 L
Q= = 2
=4
[ A]2  1 Volume of water to be added = 10 − 1= 9 L
 
 2
∴ We know, 32. The equilibrium constant (K c ) for the
∆G = ∆G ° + RT ln Q reaction N 2 ( g ) + O2 ( g ) → 2 NO ( g ) at
= 24942. + 8.314 × 300 ln 4 temperature T is 4 × 10−4 .
= 28747.27 J = positive value The value of K c for the reaction
Also, we have 1 1
Q NO( g ) → N 2 ( g ) + O2 ( g ) at the same
∆G = RT ln 2 2
K temperature is [AIEEE 2012]
if ∆G is positive, Q > K.
(a) 0.02 (b) 2.5 ×102 (c) 4 × 10−4 (d) 50.0
Therefore, reaction shifts in reverse direction.

Equilibrium 83
Exp. (d) 34. A vessel at 1000 K contains CO2 with a

N2 (g ) + O 2 (g ) → 2NO(g ) pressure of 0.5 atm. Some of the CO2 is
converted into CO on the addition of
[NO]2
Kc = = 4 × 10−4 graphite. If the total pressure at equilibrium
[N2 ][O 2 ]
is 0.8 atm, the value of K p is [AIEEE 2011]

For the reverse reaction, (a) 1.8 atm (b) 3 atm (c) 0.3 atm (d) 0.18 atm
2NO(g ) → N2 (g ) + O 2 (g )
Exp. (a) CO 2 (g) + C(s ) j2CO(g)
1 [N ][O ] 1 104 Initial 0.5 atm —
Kc ′ = = 2 22 = =
Kc [NO] 4 × 10−4 4 At equilibrium (0.5 − p) 2 p atm
On dividing the reverse reaction by 2 This is a case of heterogeneous equilibrium.

1 1 C(s) being solid is not considered.
NO(g ) → N2 ( g ) + O 2 ( g )
2 2 Total pressure of CO 2 and CO gases.
[N ]1/ 2 [O 2 ]1/ 2 pCO 2 + pCC = ptotal
Kc ′ ′ = 2 = Kc ′
[NO] 0.5 − ( p + 2 p) = 0.8, p = 0.3 atm
∴ pCO 2 = 0.5 − 0.3 = 0.2 atm
104 100
= = = 50 pCO = 2 p = 0.6 atm
4 2
p2CO 0.6 × 0.6
33. The pH of a 0.1 molar solution of the acid Kp = = = 18
. atm
pCO 2 0.2
HQ is 3. The value of the ionisation constant,
K a of the acid is [AIEEE 2012]
(a) 3 × 10−1 (b) 1 × 10−3
35. The K sp for Cr(OH)3 is 1.6 × 10−30. The molar
solubility of this compound in water is
(c) 1 × 10−5 (d) 1 × 10−7
[AIEEE 2011]
Exp. (c) (a) 2 1.6 × 10−30 (b) 4 1.6 × 10−30
H Q = H+ + Q − (c) 4 1.6 × 10−30 / 27 (d)1.6 × 10−30 / 27
[H+ ] = K aC by Ostwald’s dilution law
[H+ ] = 10−pH = 10−3 M
Exp. (c)
C = 0.1 M Let molar solubility of Cr(OH)3 = s mol L−1
3+
Thus, 10−3 = K a × 0.1 Cr(OH)3 (s ) 1 Cr (aq ) + 3OH− (aq )
s 3s
10−6 = K a × 0.1 −30
Ksp = 1.6 × 10
∴ K a = 10−5
= [Cr 3+ ] [OH− ]3 = (s )(3s )3 = 27 s 4
Alternate method
+
+ Q− 1. 6 × 10−30
HQ 1H ∴ s4 =
Initial concentration 0.1 M 0 0 27
Given, pH = 3, this suggests [H+ ] = 10−3 M at 1. 6 × 10−30
∴ s= 4
equilibrium. 27
Thus, [Q − ] at equilibrium = 10−3 M 36. An acid HA ionises as HA + A− jH +
Hence, [HQ ] = 0.1M - 10 M -3

The pH of 1.0 M solution is 5. Its dissociation
≈ 0.1M [Q10−3 M <<< 0.1 M] constant would be [AIEEE 2011]
K a for the above reaction is given by (a)1 × 10−10 (b) 5 (c) 5 × 10−8 (d)1 × 10−5
[H+ ] [Q − ] [10−3 ] [10−3 ] Exp. (a)
Ka = =
[HQ ] [0.1] pH of a solution = 5
K a = 1 × 10−5 ∴ [H+ ] = 10−pH = 10−5

HA (a weak acid) ionises as

+
39. Solubility product of silver bromide is
+ A−
HA rH 5.0 × 10−13 . The quantity of potassium
1.0 0 0
bromide (molar mass taken as 120 g mol −1 )
(1 − 10 −5 ) 10 −5 10 −5
to be added to 1 L of 0.05 M solution of silver
[H+ ] [ A – ] 10−5 × 10−5 10−10
Ka = = = nitrate to start the precipitation of AgBr is

[HA] (1 − 10−5 ) 1 [AIEEE 2010]
[Q 1 >>> 10 ] −5 (a) 1.2 × 10−10 g (b) 1.2 × 10−9 g
= 1 × 10−10 M (c) 6.2 × 10−5 g (d) 50. × 10−8 g
Exp. (b)
37. Three reactions involving H 2PO–4 are given
below [AIEEE 2010] [AgBr] = [Ag + ] = 0.05 M
I. H 3PO4 + H 2O → H 3O+ + H 2PO4– Ksp [AgBr] = [Ag+ ] [Br − ]
II. H 2PO4– + H 2O → HPO42– + H 3O+ Ksp (AgBr )
⇒ [Br − ] =
III. H 2PO4– + OH → H 3PO4 + O
– 2– [Ag+ ]
5.0 × 10-13
In which of the above does H 2PO–4 act as an = = 10−11 M [mol L −1]
0.05
acid? Moles of KBr needed to precipitate AgBr
(a) II only (b) I and II
= [Br − ] × V = 10−11 mol L −1 × 1L = 10−11 mol
(c) III only (d) I only
Therefore, amount of KBr needed to precipitate
Exp. (a) AgBr
= 10−11 mol × 120 g mol −1 = 1.2 × 10−9 g
Only in reaction (II), H2PO 4– , gives H+ to H2O.
Thus, behaves as an acid.
40. At 25°C, the solubility product of Mg(OH) 2 is
38. In aqueous solution, the ionisation 1.0 × 10−11 . At which pH, will Mg 2+ ions start
constants for carbonic acid are [AIEEE 2010] precipitating in the form of Mg(OH) 2 from a
K 1 = 4.2 × 10−7 and K 2 = 4.8 × 10−11 solution of 0.001 M Mg 2+ ions? [AIEEE 2010]
Select the correct statement for a saturated (a) 9 (b) 10 (c) 11 (d) 8
0.034 M solution of the carbonic acid. Exp. (b)
(a) The concentration of CO 23 − is 0.034 M 2+
Mg(OH)2 r Mg + 2OH−
(b) The concentration of CO 23 − is greater than that
Ksp = [Mg 2+ ] [OH– ]2
of HCO −3
(c) The concentration of H+ and HCO −3 are Ksp 1 × 10−11
approximately equal [OH− ] = 2+
=
[Mg ] 0.001
(d) The concentration of H+ is double that ofCO 23 −
pOH = − log [OH ] = − log [10−4 ]
−1
Exp. (c) pOH = 4 and pH = 10

−
H2CO 3 +
r H + HCO ; 3 K1 = 4.2 × 10−7 ∴ pH = 14 − pOH = 14 − 4 = 10
HCO −3 +
r H + CO ; 2−
3 K 2 = 4.8 × 10−11
41. Solid Ba(NO3 )2 is gradually dissolved in a
K1 >> K 2
∴ [H+ ] = [HCO −3 ] 1.0 × 10−4 M Na 2CO3 solution. At what
[H+ ][CO 23 ] concentration of Ba 2+ , will a precipitate
K2 = begin to form?
[HCO 3− ]
K sp for BaCO3 = 5.1 × 10−9 ) [AIEEE 2009]
So, [CO 23 − ] = K 2 = 4.8 × 10−11
(a) 4.1 × 10−5 M (b) 5.1 × 10−5 M
(c) 8.1 × 10−8 M (d) 8.1 × 10−7 M

Equilibrium 85
Exp. (b) Since, strong acid has a weak conjugate base.

Thus, the basic strength of the conjugate bases of
Na 2 CO 3 a2Na +
+ CO 23 − the given acid is opposite to their acidic
[Na 2 CO 3 ] = [CO 23 − ] = 1 × 10 −4
M strength.The basic strength of the conjugate
bases of the given acids follows the order
BaCO 3 a Ba CO 23 −
2+
HSO −3 < H2O <SO 24 − < CO 23 −
Ksp ( BaCO 3 ) = [Ba 2+ ] [CO 23 - ]

Hence, the acidic strength follows the order
[Ba 2+
]=
Ksp (BaCO 3 ) HSO 3 F > H3O+ > HSO −4 > HCO −3
[CO 23 − ]
44. The equilibrium constants K p 1 and K p 2 for
5.1 × 10-9
[Ba 2+ ] = the reactions X 2Y and Z
a P +Q , a
1 × 10−4 respectively are in the ratio of 1 : 9. If the
[Ba 2+ ] = 5.1 × 10−5 M degree of dissociation of X and Z be equal,
Hence, at 5.1 × 10−5 M concentration of Ba 2+ , a then the ratio of total pressure at these
precipitate will begin to form.
equilibria is [AIEEE 2008]
(a) 1 : 36 (b) 1 : 1 (c) 1 : 3 (d) 1 : 9
42. For the following three reactions I, II and III,
equilibrium constants are given [AIEEE 2008]
Exp. (a)
Let the total pressure at equilibrium for the given
I. CO ( g ) + H2O( g ) a CO ( g ) + H ( g ); K 1
2 2 two reactions are p1 and p2 , respectively.
II. CH4 ( g ) + H2O( g ) a CO ( g ) +3H ( g ); K 2 1 For first reaction,
III. CH4 (g) + 2H2O( g) a CO ( g) 2
X a2 Y
+ 4H2 (g ); K 3 Initial 1 mol 0
Which of the following relations is correct? At equilibrium (1 − α ) 2α
(a) K 1 K 2 = K 3 (b) K 2 K 3 = K 1 Total moles = (1 − α ) + 2α
(c) K 3 = K 1 K 2 (d) K 3 K 23 = K 12 [Here, α is the degree of dissociation]
= (1 + α )
Exp. (c) 1− α
px = p1
As equation ‘III’ is obtained on adding equation ‘I’ 1+ α
and equation ‘II’, so K 3 = K1 ⋅ K 2 .
[Q Partial pressure = (Total no. of moles)
× (Total pressure)]
43. Four species are listed below 2α
py = p1
I. HCO–3 II. H 3O+ 1+ α
III. HSO–4 IV. HSO3F  2α 
2
 p1 
Which one of the following is the correct 1 + α  4α 2
K p1 = = P1 = 4α 2 P1
sequence of their acid strength? [AIEEE 2008] 1− α  1 − α2
 p1 
(a) IV < II < III < I 1 + α 
(b) II < III < I < IV [Qα 2 <<< 1]
(c) I < III < II < IV
For second reaction
(d) III < I < IV < II
Z aP + Q
Exp. (c) Initial 1 mol 0 0
Conjugate bases of the given species are At equilibrium 1− α α α
Species Conjugate base Total moles = 1 − α + α + α = (1 + α )
HCO −3 CO 2− 1− α α
3 pz = P2 , pP = P2
H 3O+ H 2O 1− α 1+ α
HSO −4 SO 2− α
4
and pQ = P2
HSO 3 F HSO −3 1+ α

 α   α 
 P2   P2  47. The pK a of a weak acid (HA) is 4.5. The pOH
1 + α  1 + α  α 2 P2
K P2 = = = α 2 P2 of an aqueous buffered solution of HA in
1 + α  1 − α2 which 50% of the acid ionised is [AIEEE 2007]
 P2 
1 + α  (a) 4.5 (b) 2.5 (c) 9.5 (d) 7.0
[Qα 2 <<< 1]
K P1 4α 2 P1 1 4P1 P 1 Exp. (c)

= ⇒ = ⇒ 1 =
K P2 α 2 P2 9 P2 P2 36 When HA is 50% ionised, [HA] = [ A − ]
Buffer solution of weak acid HA → acidic buffer
45. The pK a of a weak acid, HA is 4.80. The pK b [ A− ]
of a weak base, B OH, is 4.78. The pH of an pH = pK a + log
[HA]
aqueous solution of the corresponding salt,
BA, will be [AIEEE 2008]
or pH = pK a = 4.5
(a) 9.58 (b) 4.79 (c) 7.01 (d) 9.22 pOH = pK w − pH
Exp. (c) pOH = 14 − 4.5 = 9.5
For salt of weak acid and weak base 48. The first and second dissociation constants
1
pH = − [log K a + log K w − log K b ] of an acid H 2 A are 1.0 × 10−5 and 5.0 × 10−10 ,
2 respectively. The overall dissociation
1 1 1 constant of the acid will be [AIEEE 2007]
= pK a + pK w − pK b
2 2 2 (a) 5.0 × 10−5 (b) 5.0 × 1015
1 1
= × 4. 80 + 7 − × 4.78 = 7.01 (c) 5.0 × 10−15 (d) 0.2 × 105
2 2
Exp. (c)
46. In a saturated solution of the sparingly
soluble strong electrolyte AgIO3 (molecular The overall dissociation constant of the acid is
mass = 283) the equilibrium which sets in is K = K1 × K 2
AgIO3(s ) Ag + (aq ) + IO−3 (aq )
r = 1.0 × 10−5 × 5.0 × 10−10 = 5 × 10−15
If the solubility product constant, K sp of AgIO3 49. The equilibrium constantK c for the reaction
at a given temperature is1.0 × 10 −8 , what is the
mass of AgIO3 contained in 100 mL of its
SO3 ( g ) r SO (g ) + 21 O (g )
2 2
saturated solution? [AIEEE 2007] −2

is 4.9 × 10 . The value of K c for the reaction
(a) 28.3 × 10−2 g (b) 2.83 × 10−3 g
2SO2 ( g ) + O2 ( g ) r 2SO 3 (g )
(c) 1.0 × 10−7 g . × 10−4 g
(d) 10
will be [AIEEE 2006]
Exp. (b) (a) 416 (b) 2.40 × 10−3
AgIO 3 (s ) r Ag (aq ) + IO (aq )
+ − (c) 9.8 × 10−2 (d) 4.9 × 10−2
3
Let the solubility of AgIO 3 be S Exp. (a)
Ksp = [Ag+ ] [IO 3− ] Equilibrium constant for the reaction,
1.0 × 10−8 = S 2 or S = 1 × 10− 4 mol / L 1
SO 2 (g ) + O 2 (g ) rSO 3 (g )
2
In 1000 mL moles of AgIO 3 dissolved 1
Kc =
= 1 × 10− 4 moles 4.9 × 10−2
In 100 mL moles of AgIO 3 dissolved and for 2SO 2 ( g ) + O 2 ( g ) r 2SO ( g ) 3
= 1 × 10−5 moles 2
 1  104
Kc =  −2 
=
Mass of AgIO 3 in 100 mL  4.9 × 10  (4.9)2
= 1 × 10−5 mol × 283 g mol −1
= 416.490 ≈ 416
= 2.83 × 10−3 g

Equilibrium 87
50. Phosphorus pentachloride dissociates as 52. For the reaction,

follows, in a closed reaction vessel, 2NO2 ( g ) r 2NO(g ) + O (g ) 2
PCl 5 ( g )r PCl 3 ( g ) + Cl 2 ( g ) [K c = 1.8 × 10 −6
at 184° C,
If total pressure, at equilibrium, of the R = 0.00831 kJ/(mol K)]
reaction mixture is p and degree of

dissociation of PCl 5 is x, the partial pressure When K p and K c are compared at 184°C it is
of PCl 3 will be [AIEEE 2006] found that [AIEEE 2005]
 x   2x  (a) whether K p is greater than, less than or equal
(a)  p (b)  p to K c depends upon the total gas pressure
 x + 1 1 − x 
(b) K p = K c
 x   x  (c) K p is less than K c
(c)  p (d)  p
 x −1 1 − x  (d) K p is greater than K c
Exp. (a) Exp. (d)

Initially
PCl 5 (g ) r PCl (g ) + Cl (g )
3 2
2NO 2 ( g )r 2NO(g ) + O 2 (g )
1 0 0
At equilibrium (1 − x) x x Kc = 1.8 × 10−6 at 184° C (= 457 K)
Total number of moles at equilibrium R = 0.00831kJ mol −1 K −1

∆n g
= (1 − x) + x + x = 1 + x K p = Kc (RT )
 x  where,
pPCl 3 =   p
1 + x  ∆ng = (gaseous products − gaseous reactants)
= 3−2 =1
51. An amount of solid NH 4HS is placed in a ∴ K p = 1.8 × 10−6 × 0.00831 × 457
flask already containing ammonia gas at a
certain temperature and 0.50 atm pressure. = 6.836 × 10−6 > 1.8 × 10−6
Ammonium hydrogen sulphide decomposes Thus, K p > Kc .
to yield NH 3 and H 2 S gases in the flask.
When the decomposition reaction reaches 53. The exothermic formation of ClF3 is
equilibrium, the total pressure in the flask represented by the equation
rises to 0.84 atm . The equilibrium constant
Cl 2 ( g ) + 3F2 ( g ) r2ClF (g ); ∆H
3 r = − 329 kJ
for the decomposition of NH 4 HS at this
temperature is [AIEEE 2005] Which of the following will increase the
(a) 0.11 (b) 0.17 (c) 0.18 (d) 0.30 quantity of ClF3 in an equilibrium mixture of
Cl 2 , F2 and ClF3 ? [AIEEE 2005]
Exp. (a) (a) Adding F2
NH4HS(s ) r NH3 (g ) + H2S(g ) (b) Increasing the volume of the container
Initially 1 0.5 0 (c) Removing Cl 2
At equilibrium (1− x ) ( 0.5 + x ) x (d) Increasing the temperature
Total pressure at equilibrium
= p NH 3 + p H 2S Exp. (a)
= 0.5 + x + x = 0.84 Reaction is exothermic. By Le-Chatelier principle,
∴ x = 0.17 atm a reaction is spontaneous in forward side (in the
∴ p NH 3 = 0.50 + 0.17 = 0.67 atm direction of formation of more ClF3 ). If F2 is added,
temperature is lowered and ClF3 is removed.
p H 2S = 0.17 atm
∴ K p = pNH 3 ⋅ pH 2S 54. What is the conjugate base of OH − ?
= 0.67 × 0.17 = 0.114 atm (a) O 2 − (b) O − [AIEEE 2005]
(c) H2Os (d) O 2

Exp. (a)
58. For the reaction,
Conjugate base is formed by loss of H+ .
CO( g ) + Cl 2 ( g ) r COCl (g ), the K 2 p / Kc
OH− → O 2 − + H+ is equal to [AIEEE 2004]
Conjugate
base (a) 1/ RT (b) RT (c) RT (d) 1.0
O 2 − is the conjugate base of OH− .
Exp. (a)
55. The solubility product of a salt having ∆n g
K p = Kc (RT )
general formula MX 2 , in water is 4 × 10− 12 .
∆ng = (Sum of coefficients of gaseous products)
The concentration of M 2+ ions in the
– (Sum of coefficients of gaseous reactants)
aqueous solution of the salt is [AIEEE 2005]
CO(g ) + Cl 2 (g ) → COCl 2 (g )
(a) 4.0 × 10−10 M (b) 1.6 × 10−4 M
∴ ∆ng = 1 − 2 = − 1
(c) 1.0 × 10−4 M (d) 2.0 × 10−6 M
∴ K p = Kc (RT )−1
2+ −
Exp. (c) MX 2 rM + 2X Kp 1
S 2S ∴ = (RT )−1 =
2+
Ksp = [M ] [ X − ]2 Kc (RT )
If solubility be S, then
59. The conjugate base of H 2PO–4 is
Ksp = (S ) (2 S )2 = 4 S 3 [AIEEE 2004]
−12 (a) PO 34 − (b) P2O 5 (c) H3 PO 4 (d) HPO 24 −
4 S = 4 × 10
3
∴ S = 1 × 10−4 M Exp. (d)

∴ [M 2 + ] = S = 1 × 10−4 M
H 3 PO 4 is a tribasic acid, thus ionises in three steps
56. Hydrogen ion concentration in mol/L in a I : H3PO 4 r H+ + H2PO 4−
solution of pH = 5.4 will be [AIEEE 2005] II : H2PO 4− r H+ + HPO 24 −
(a) 3.98 × 10−6 . × 10−6
(b) 368 III : HPO 24 − rH +
+ PO 34 −
. × 106
(c) 388 (d) 3.98 × 108 Conjugate base is formed when an acid loses its
proton. Thus, HPO 24 − is the conjugate base of
Exp. (a)
H2PO 4− (which is an acid in step II, but is the
pH = 5.4
conjugate base of H3PO 4 in step I).
∴ [H+ ] = 10−5.4 = 10−6 ⋅ 100.6
Antilog of 0.6 is ≈ 3.98 60. The molar solubility (in mol L−1) of a
∴ [H+ ] ≈ 3.98 × 10−6 M sparingly soluble salt MX 4 is S. The
corresponding solubility product is K sp . S is
57. What is the equilibrium expression for the given in terms of K sp by the relation.
reaction (a) S = ( K 1/ 4
(b) S = ( K 1/ 4
sp /128) sp /128)
P4 (s ) + 5 O2 ( g ) rPO 4 10 (s )? [AIEEE 2004]
(c) S = ( K sp / 256)
1/ 5
(d) S = ( K sp / 256)1/ 5
[P4O10 ] [P4O10 ]
(a) K c = (b) K c = [AIEEE 2004]
[P4 ] [O 2 ] 5 5[P4 ] [O 2 ] 5
1 Exp. (c)
(c) K c = [O 2 ] 5 (d) K c = 4+
[O 2 ] 5
MX 4 rM + 4X −
Exp. (d) Ksp = [M 4+
] [4 X ]− 4
In the expression for equilibrium constant Ksp = (S ) (4S) 4

(K p or Kc ), species in solid state are not written
(i.e., their molar concentrations are taken as 1) ⇒ Ksp = 256 S 5
P4 (s ) + 5O 2 (g ) P4O10 (s )
r 1/ 5
K sp K 
1 S5 = ⇒ S =  sp 
Thus, Kc = 256  256 
[O 2 ] 5

Equilibrium 89
of electrons than O, S and P due to their smaller

61. For the reaction equilibrium, size and low electronegativity.
N 2O4 ( g ) r 2NO (g ) 2 Thus, NH3 possess the highest proton affinity. On
the concentrations of N 2O4 and NO2 at the other hand, due to higher electronegativity of
equilibrium are 4.8 × 10 −2 and O, it cannot donate their electron pair easily while
−2 −1 P possess a larger size, becomes less basic in

1.2 × 10 mol L , respectively. The value of K c
nature.
for the reaction is [AIEEE 2003]
(a) 3.3 × 102 mol L−1 (b) 3 × 10−1 mol L−1 64. The solubility in water of a sparingly soluble
(c) 3 × 10−3 mol L−1 (d) 3 × 103 mol L−1 salt AB 2 is 1.0 × 10−5 mol L−1 . Its solubility
product will be [AIEEE 2003]
Exp. (c)
(a) 4 × 10−15 (b) 4 × 10−10
[NO 2 ]2 (1.2 × 10−2 )2 −15
Kc = = = 3 × 10−3 mol L−1 (c) 1 × 10 (d) 1 × 10−10
[N2O 4 ] 4.8 × 10−2
Exp. (a)
62. Consider the reaction equilibrium 2+
AB2 rA + 2 B−
2SO2 ( g ) + O2 ( g ) r2SO (g )3 S 2S
∆H ° = −198 kJ Ksp = [ A 2 + ] [B− ]2 = (S ) (2 S )2 = 4 S 3
[AIEEE 2003]
= 4 (1 × 10−5 )3 = 4 × 10−15
On the basis of Le-Chatelier’s principle, the
condition favourable for the forward 65. Which one of the following statements is not
reaction is true? [AIEEE 2003]
(a) lowering of temperature as well as pressure (a) The conjugate base of H2 PO −4 is HPO 24 −
(b) increasing temperature as well as pressure
(b) pH + pOH =14 for all aqueous solutions
(c) lowering the temperature and increasing the
pressure (c) The pH of1 × 10− 8 M HCl is 8
(d) any value of temperature and pressure (d) 96,500 C of electricity when passed through a
CuSO4 solution deposits 1g equivalent of
Exp. (c) copper at the cathode
∆ng = − ve ∆H ° = − ve Exp. (c)

Takes place with Takes place with In 1 × 10−8 M HCl solution, H2O is also present
decrease in number of evolution of heat or which also undergoes self ionisation.
moles or pressure, increase in temperature, H2O H+ + OH−
r
hence increase in hence decrease in −7
10 M at 25°C
pressure shifts temperature shifts this
equilibrium in forward equilibrium in forward [Concentration of water (H2O)]
side. side. If it is taken simply even without common ion
effect, higher concentration must be considered
63. Which one of the following substances has which is 10−7 M but H+ from HCl decreases self
the highest proton affinity ? [AIEEE 2003] ionisation of water and hence [H+ ] from H2O.
(a) H2O (b) H2 S (c) NH3 (d) PH3 Hence, net concentration must be smaller than
10−7 M.
Exp. (c)
The tendency to accept the proton by the donation
66. For the following reaction in gaseous phase
1
of their lone pairs of electron is called proton CO + O2 → CO2. K c /K p is
affinity. This proton affinity is also called basicity. 2 [AIEEE 2002]
Therefore, the molecule which donates their lone
pairs electron more readily, is said to be more (a) ( RT )1/ 2 (b) ( RT )−1/ 2
basic. Since, N can easily donate their lone pairs (c) ( RT ) (d) ( RT )−1

Exp. (a) 69. Solubility of Ca(OH)2 is S mol L−1. The

According to the relationship of K p and Kc , solubility product (K sp ) under the same
∆n g
K p = Kc (RT ) condition is [AIEEE 2002]
∆ng = 1 − 1.5 = − 0.5 (a) 4 S 3 (b) 3S 4 (c) 4 S 2 (d) S 3
K p = Kc (RT )−1/ 2 Exp. (a)

Kc
= Ca(OH)2 r Ca 2+
+ 2OH−
(RT )1/ 2
Kc K sp = [Ca 2+ ] [OH− ]2
∴ = (RT )1/ 2
Kp = (S ) ( 2 S )2 = 4S 3
67. One of the following equilibria is not 70. An aqueous solution of 1M NaCl and 1M
affected by change in volume of the flask HCl is [AIEEE 2002]
[AIEEE 2002] (a) not a buffer but pH < 7
r PCl ( g ) + Cl ( g )
(a) PCl 5 ( g ) 3 2
(b) not a buffer but pH > 7
(b) N ( g ) + 3H ( g ) r 2NH ( g ) (c) a buffer with pH < 7
2 2 3
(d) a buffer with pH > 7
(c) N ( g ) + O ( g ) r 2NO( g )
2 2
(d) SO Cl ( g ) r SO ( g ) + Cl ( g )
2 2 2 2 Exp. (a)
Exp. (c) NaCl is salt of strong acid and strong base. Its not
the case of buffer.
Change in volume affects number of moles per NaCl + H2O r NaOH + HCl
unit volume and move in the direction which undo
Aqueous NaCl, itself exact neutral solution.
the change.
HCl + H2O r H3O+ + Cl −
N2 ( g ) + O 2 ( g ) 2NO(g ) r makes solution acidic.
Number of moles of reactants and products are
equal.
71. pH of 0.005 M calcium acetate (pK a of
68. Which one of the following species acts as CH 3COOH = 4.74) is [AIEEE 2002]
both Bronsted acid and base? [AIEEE 2002] (a) 7.04 (b) 9.37 (c) 9.26 (d) 8.37
(a) H2 PO –2
(b) HPO 23 –
Exp. (a)
(c) HPO 24 − Calcium acetate is a salt of weak acid and weak
base.
(d) All of the above
0.005 M calcium acetate, (CH3COO)2 Ca
Exp. (c) (CH3COO)2 Ca → Ca 2+ + 2CH3COO −
0.005 M (2 × 0.005 = 0.01)
According to Bronsted Lowry concept of acids
and bases, an acid is a proton donor whereas a ∴ [CH3COO − ] = 0.01 M
base is a proton acceptor. CH3COO − + H2O r CH COOH + OH
3
–
Thus, according to this concept, HPO 24 − can Alkaline

pK a log C
easily donate a proton and also accepts a proton pH = 7 + +
on reaction with water. 2 2
HPO 24 − + H2O PO 34 − + H3O+ log 0.01
r = 7 + 2.37 +
2
HPO 24 − + H O r H PO 2−
+ OH−
2 2 4
= 7 + 2.37 − 2.30 = 7.06

8
Redox Reactions and

Electrochemistry
(a) x + 2 y − 3z (b) x − y
1. Given, that E Os 2 /H 2 O = +1.23V ;
(c) x + y − z (d) x − z
E sS 2− 2− = 2.05V ;
2 O 8 /SO 4
s
Exp. (a)
E Br = +1.09V ,
2
/Br s
Fe 2+(aq ) + Ag+(aq ) → Fe 3+(aq ) + Ag(s )
s
E = +1.4V ∴ º
Ecell = Eº − Eº
Au 3 + /Au Ag + / Ag Fe 3+ /Fe 2 +
The strongest oxidising agent is = xV − Eº … (i)

Fe 3+ /Fe 2 +
Now, for two half-cells
(a) Au 3 + (b) O 2 (c) S 2O 28 − (d) Br2
(i) Fe 2+ + 2e − → Fe; EFe
º
2+
/Fe
= E1º = yV
Exp. (c)
Higher the standard reduction potential ∆Gº2 = − 2 FE1º
(Eº M n + / M ), better is oxidising agent. Among the
(ii) Fe 3+ + 3e − → Fe ; EFe
º
3+
/Fe
= Eº2 = zV
given, ES° 2O 2− /SO 2− is highest, hence S2O 2−
8 is the
8 4
∆Gº2 = − 3FEº2
strongest oxidising agent.
The decreasing order of oxidising agent among So, Fe 3+ + e – → Fe 2+ ; Eº = Eº3 = ?
Fe 3+ /Fe 2 +
the given option is as follows:
S2O 28 − > Au3 + > O 2 > Br2 ; ∆Gº3 = − 1 × FEº3
Again, ∆Gº3 = ∆Gº2 − ∆G1º
2. Calculate the standard cell potential ⇒ − FEº3 = − 3FEº2 − (− 2 FE1º )
(in V) of the cell in which following reaction
⇒ − Eº3 = 2 E1º − 3Eº2
takes place
⇒ Eº3 = 3Eº2 − 2 E1º
Fe2+ (aq ) + Ag+ (aq ) → Fe3 + (aq ) + Ag(s )
⇒ Eº = (3 z − 2 y) V
Given that, E ° Ag + / Ag = x V, E ° Fe 2+ / Fe = y V Fe 3+ /Fe 2 +
E ° Fe3 + / Fe = z V So, from equation (i)

º
Ecell = xV − (3 z − 2 y) V = ( x − 3 z + 2 y) V

Number of equivalents = Number of moles ×

3. The standard Gibbs energy for the given cell number of electrons.
−1
reaction in kJ mol at 298 K is . = Number of moles × 2
01
Zn(s ) + Cu (aq ) → Zn2+ (aq ) + Cu(s ),
2+
∴Number of moles of Ni =
.
01
= 0.05
2
E ° = 2 V at 298 K
5. Consider the statements S1 and S 2 :
(Faraday’s constant, F = 96000 C mol−1)
[JEE Main 2019, 9 April Shift-I] S1 : Conductivity always increases with
(a) 384 (b) 192 (c) −384 (d) −192 decrease in the concentration of
electrolyte.
Exp. (c) S 2 : Molar conductivity always increases
with decrease in the concentration of
Key Idea Gibbs energy of the reaction is related electrolyte.
to E° cell by the following formula
∆Gº = − nFE ° cell The correct option among the following is
∆Gº = Gibbs energy of cell [JEE Main 2019, 10 April Shift-I]
nF = amount of charge passed (a) S1 is correct and S2 is wrong
E = EMF of a cell (b) S1 is wrong and S2 is correct
(c) Both S1 and S2 are wrong
Given reaction is, (d) Both S1 and S2 are correct
Zn + Cu2 + → Zn2 + + Cu
Exp. (b)
Eºcell = 2.0 V
The explanation of statements (S1 and S2 ) are as
F = 96000 C
follows :
n=2
In conductivity cell, conductivity (κ ) is equal to
To find the value of ∆Gº (kJ mol), we use the the sum of ionic conductances (c), of an
formula electrolytic solution present is unit volume of the
∆Gº = − nFEºcell solution enclosed by two electrodes of unit area
(a ≠ 1) separated by a unit length (l = 1.)
∆Gº = −2 × 96000 × 2 l
κ =c× ⇒ κ = c when l = 1, a = 1
= −384000 J/mol a
−384000 So, with decrease in the concentration of
In terms of kJ/mol, ∆Gº =
1000 electrolyte, number of ions in the given unit
= −384 kJ/mol volume also decreases, i.e. κ [conductivity] also
decreases.
4. A solution of Ni(NO3 )2 is electrolysed Thus, statement S1 is wrong. S 2 : Molar
conductivity (λ m ) is defined as the conducting
between platinum electrodes using
power of all the ions present in a solution
0.1 Faraday electricity. How many mole ofNi containing 1 mole of an electrolyte.
will be deposited at the cathode? 1000
λ m = κ × VmL = κ ×
[JEE Main 2019, 9 April Shift-II] M
(a) 0.20 (b) 0.10 (c) 0.15 (d) 0.05 where, VmL = volume in mL containing 1 mole
of electrolyte
Exp. (d) m = molar concentration (mol/L)
A solution of Ni(NO 3 )2 is electrolysed between So, in a conductivity cell
platinum electrodes using 0.1 Faraday electricity. 1
It means that 0.1 equivalent of Ni 2+ will be λm ∝
M
discharged.
i.e. molar conductivity increases with decrease in
Electrolysis of Ni(NO 3 )2 gives the concentration (M) of electrolyte.
Ni 2+ + 2e − → Ni (Atomic mass of Ni = 58.7) Thus, statement S 2 is correct.

Redox Reactions and Electrochemistry 93
6. Which one of the following graphs between 7. An example of a disproportionation reaction

molar conductivity (Λ m ) versus C is is [JEE Main 2019, 12 April Shift-I]
correct? [JEE Main 2019, 10 April Shift-II] (a) 2MnO −4 + 10 I− + 16H+ →
2Mn 2 + + 5I2 + 8H2O
Na
(b) 2NaBr + Cl 2 → 2NaCl + Br2

Cl
KC
l
(a) Λm (b) Λm (c) 2KMnO 4 → K 2 MnO 4 + MnO 2 + O 2
Na
(d) 2CuBr → CuBr2 + Cu
KC
Cl
l
Exp. (d)
√C √C In disproportionation reactions, same element
KC
undergoes oxidation as well as reduction.

l
e.g.
(c) Λm (d) Λm Reduction
+1 +2 0
Na
Na
KC
Cl 2CuBr CuBr2 +Cu

Cl
Oxidation
√C √C
Here, CuBr get oxidised to CuBr2 and also it get
Exp. (c) reduced to Cu. Other given reactions and their
NaCl and KCl are strong electrolytes. So, the types are given below.
Reduction
study of their molar conductances (λ m ) can be
+7
experimentally verified by Debye-Huckel 2
–
MnO4 –
+10I + 16 H
+
2Mn
+2
+ 5I2 + 8H2O
Onsagar equation,
Λcm = Λ0m − B C Oxidation
In the given reaction, MnO −4 get oxidised to

Λcm = molar conductance at concentration.
Mn2+ and I− get reduced to I2 . It is an example of
Λ0m = molar conductance at infinite dilution.
redox reaction. The reaction takes place in acidic
i.e. C → 0 medium.
B = Debye-Huckel Onsagar constant. 2KMnO 4 → K 2MnO 4 + MnO 2 + O 2
For (both NaCl and
The given reaction is an example of
KCl) a strong binary
decomposition reaction. Here, one compound
electrolyte like AB, the
split into two or more simpler compounds,
nature of the plot of Λm
Λm atleast one of which must be in elemental form.
vs C will be
2NaBr + Cl 2 → 2NaCl + Br2
Size of Na ⊕ is being √C
smaller than K ⊕ and The given reaction is an example of
Na ⊕ will remain in more hydrated state, i.e. displacement reaction. In this reaction, an atom
larger sized in aqueous solution. As a result, (or ion) replaces the ion (or atom) of another
ionic mobility as well as ionic conductance of element from a compound.
Na ⊕
(or NaCl as Cl È is common to NaCl and KCl) will 8. Given,
be lower than K ⊕ (or KCl). Thus, the plot of Λm Co 3+ + e − → Co 2+ ; E ° = + 1.81 V
vs C for NaCl and KCl is as follows :
Pb 4 + + 2e − → Pb 2+ ; E ° = + 1.67 V
Ce 4 + + e − → Ce 3+ ; E ° = + 1.61 V
KC
l
Na Bi3+ + 3e − → Bi; E ° = + 0.20 V
Λm Cl
Oxidising power of the species will increase
√C in the order [JEE Main 2019, 12 April Shift-I]

(a) Ce4 + < Pb4 + < Bi 3 + < Co 3 + The correct order of acidic strength and electrical
(b) Bi 3 + < Ce4 + < Pb4 + < Co 3 + conductivity is as follows:
(c) Co 3 + < Ce4 + < Bi 3 + < Pb4 + HCOOH > PhCOOH > CH3COOH
A C B
(d) Co 3 + < Pb4 + < Ce4 + < Bi 3 + 10. The anodic half-cell of lead-acid battery is
Exp. (b) recharged using electricity of 0.05 Faraday.

The amount of PbSO4 electrolysed in g
Key Idea Negative E ° means that redox couple during the process is (Molar mass of
is weaker oxidising agent than H+ / H2 couple. PbSO4 = 303g mol −1)
Positive E° means that redox couple is a stronger (a) 11.4 (b) 7.6 (c) 15.2 (d) 22.8
oxidising agent than H+ / H2 couple
Given, Co 3 + + e − → Co 2 + ; E ° = +1.81 V
Exp. (b)
Pb 4 + + 2e − → Pb 2 + ; E ° = + 1.67 V
Ce 4 + + e − → Ce 3 + ; E ° = + 1.61 V Key Idea This question is based upon
Faraday’s first law which states that “Mass of
Bi 3+ + 3e − → Bi; E ° = + 0.20 V any substance deposited or liberated at any
Oxidising power of the species increases in the electrode is directly proportional to the quantity
order of Bi 3+ < Ce 4 + < Pb 4 + < Co 3 + . of electricity passed.”
Higher the emf value, stronger the oxidising During charging:
power. The maximum value of emf is possessed Pb + SO 24 − → PbSO 4 + 2e −
by Co 3+ . Hence, it has maximum oxidising
power. Whereas Bi 3+ possess the lowest emf ⇒ 1 F ≡ 1g-equiv. of PbSO 4
value. Hence, it has minimum oxidising power. 1 303
= mol of PbSO 4 ⇒ g PbSO 4
2 2
9. The decreasing order of electrical 303
∴ 0.05 F ≡ × 0.05 g of PbSO 4
conductivity of the following aqueous 2
solution is = 7.575 g of PbSO 4
0.1 M formic acid (A),
0.1 M acetic acid (B),
11. If the standard electrode potential for a cell
is 2V at 300 K, the equilibrium constant (K)
0.1 M benzoic acid (C ). for the reaction,
[JEE Main 2019, 12 April Shift II]
Zn(s ) + Cu 2+ (aq ) - Zn 2+
(aq ) + Cu(s )
(a) A > C > B (b) C > B > A
(c) A > B > C (d) C > A > B at 300 K is approximately
Exp. (a) (R = 8 JK −1mol −1 , F = 96000 C mol −1 )
Electrical conductivity of the given aqueous (a) e −160 (b) e 160 (c) e −80 (d) e 320
solutions depends on the degree of ionisation. [ JEE Main 2019, 9 Jan Shift-II]
Degree of ionisation is directly proportional to the Exp. (b)
acidic strength. Electron withdrawing groups
(EWGs) increases the stability of the carboxylate The relationship between standard electrode
ion by dispersing the negative charge through potential (E° ) and equilibrium constant (K ) of the
resonance effect on the conjugate while electron cell reaction,
donating groups (EDGs) decreases the stability of Zn(s) + Cu2+(aq) 1 Zn2+(aq) + Cu(s)
the carboxylate ion by intensifying the negative
can be expressed as,
charge.
RT
O O
E° = ln K ⇒ K = e nFE ° / RT
nF
EWG C s EDG C s
Given, n = 2, F = 96000 C mol −1
O O
Acidity of carboxylic Acidity of carboxylic E° = 2 V, R = 8 JK −1mol −1, T = 300 K
acids increases due acids decreases due
to the presence of 2 × 96000 × 2
to the presence of electron
8 × 300
withdrawing groups (EWGs) electron donating groups ∴ K =e = e160

12. Consider the following reduction processes: Exp. (b)

Zn 2+ −
+ 2e → Zn(s ); E ° = − 076
. V It is an electrochemical cell. The overall cell
reaction can be written, as
Ca 2 + + 2e − → Ca(s ); E ° = − 2.87 V
H2(g ) + 2AgCl(s ) → 2HCl(aq ) + 2 Ag(s)
Mg 2 + + 2e − → Mg(s ); E ° = − 2.36 V (1 bar) (10−6 M)
Ni 2 + + 2e − → Ni(s ); E ° = − 025

. V (i) According to Nernst equation,
° ° 2.303 × RT
The reducing power of the metals increases Ecell = (Ecathode − Eanode )−
n×F
in the order
(a) Zn < Mg < Ni < Ca (b) Ni < Zn < Mg < Ca [HCl]2 [Ag]2
log
(c) Ca < Zn < Mg < Ni (d) Ca < Mg < Zn < Ni pH 2 [AgCl]2
Here, (i) Ec° = EAgCl
°
/ Ag, Cl −
°
= Ecathode
Exp. (b)
° °
Reducing power of an element (ii) Eanode = E2H +
/H
= 0.00 V (Standard
2
1
∝ hydrogen electrode)
Standard reduction potential
(10−6 )2 × 12
Here, E ° values of the given metals are as, ⇒ 0.92 = (Ec° − 0) − 0.06 × log
M2 + / M 1 × 12
Metals Ni Zn Mg Ca = Ec° + 0.06 × 6 × 2
E°(V) − 025
. − 076
. − 2.36 − 2.87 ⇒ Ec° = 0.92 − 072
. = 020
. V
→
Reducing power
Note 10−6 molal HCl is a very dilute solution.
Thus, the correct order of increasing reducing So, 10−6 m ~
− 10−6 M
power of the given metal is,
Ni < Zn < Mg < Ca. 14. For the cell,Zn(s )|Zn2+ (aq )||M x+ (aq )|M (s ),
13. In the cell, different half cells and their standard
Pt(s) H 2 ( g ,1bar) HCl(aq ) |AgCl(s ) electrode potentials are given below.
Ag(s ) Pt(s ) the cell potential is 0.92 V when a Au 3 + (aq)/ Ag + (aq)/ Fe 3 + (aq)/ Fe 2 + (aq)
10−6 molal HCl solution is used. The M x + (aq)/M(s) Au(s) Ag(s) Fe 2 + (aq) /Fe(s)
standard electrode potential of E ° Mx + /M /V 1.40 0.80 0.77 − 0.44
( AgCl/ Ag,Cl− ) electrode is
 2.303RT  If E ° Zn 2 + /Zn = − 0.76 V, which cathode will
Given, = 0.06 V at 298 K
 F  give a maximum value of E ° cell per electron
(a) 0.40 V (b) 0.20 V (c) 0.94 V (d) 0.76 V transferred? [JEE Main 2019, 11 Jan Shift-I]
[ JEE Main 2019, 10 Jan Shift-II] Ag + Fe2 + Au 3 + Fe3 +
(a) (b) (c) (d)
Ag Fe Au Fe2 +
Exp. (a)
Cell E °cell (SRP) = E °C − E ° A E°cell free e transfer
Anode (A) Cathode (C)
Zn Ag 156
.
0.80 − ( −076 . V for 2e −
. ) = + 156 + = + 078
. V
1. [Zn + 2Ag+ → Zn2+ + 2Ag] 2
Zn Fe 0.32
. ) = + 0.32 V for 2e −
− 0.44 − ( − 076 + = + 016
. V
2. [Zn + Fe 2 + → Zn2+ + Fe] 2
Zn Au 2.16
. ) = + 2.4 V for 6e −
1.40 − ( −076 + = + 0.36 V
3. [3Zn + 2Au3 + → 3Zn2 + + 2Au] 6
Zn Fe . − ( −076
077 . V for 2e −
. ) = + 153 153
.
4. [3Zn + 2Fe 3 + → Zn2 + + 2Fe 2+ ] + = + 0765
. V
2

15. The standard electrode potential E O− and its Exp. (d)

 dE −
O  According to Kohlrausch’s law, the molar
temperature coefficient   for a cell are conductivity of HA at infinite dilution is given as,
 dT  Λ°m (HA) = [Λ°m (H+ ) + Λ°m (Cl − )]
2V and − 5 × 10−4 VK −1 at 300 K respectively. + [Λ°m (Na + ) + Λ°m ( A − )] − [Λ°m (Na + ) + Λ°m (Cl − )]
The cell reaction is = 425.9 + 100.5 − 126.4

Zn(s ) + Cu2+ (aq ) → Zn2+ (aq ) + Cu(s )
= 400S cm 2 mol − 1
−
The standard reaction enthalpy (∆r H O ) at Also, molar conductivity at given concentration is
300 K in kJ mol −1 is, [Use, R = 8 JK −1 mol−1 given as,
1000 × κ
and F = 96,000 C mol−1] Λm =
M
(a) − 412.8 (b) − 384.0 Given, κ = conductivity ⇒ 5 × 10− 5 S cm − 1
(c) 206.4 (d) 192.0
M = Molarity ⇒ 0.001 M
1000 × 5 × 10− 5 S cm−1
∴ Λm =
Exp. (a) 10− 3 M
dE ° 
Given, E° = 2V,  −4
 = − 5 × 10 VK
−1 = 50S cm 2 mol − 1
 dT 
Therefore, degree of dissociation (α), of HA is,
T = 300 K, R = 8 JK −1mol −1,
Λ 50 S cm2mol − 1
α = °m = =0.125
F = 96000 Cmol −1 Λm 400 S cm2mol − 1
According to Gibbs-Helmholtz equation,
∆G = ∆H − T∆S …(i) 17. How long (approximate) should water be
Also, ∆G = − nFE °cell …(ii) electrolysed by passing through 100
On substituting the given values in equation (ii), we amperes current so that the oxygen released
get can completely burn 27.66 g of diborane?
∆G = − 2 × 96000 C mol −1 × 2 V (Atomic weight of B = 10.8 µ) [JEE Main 2018]
(a) 6.4 hours (b) 0.8 hours
[Q n = 2 for the given reaction]
(c) 3.2 hours (d) 1.6 hours
= − 4 × 96000 J mol −1
= − 384000 J mol −1 Exp. (c)
dE °  Given that, i = 100 amp. also, 27.66 g of
Now, ∆S = nF  
 dT  diborane (B 2H6 )
or ∆S = 2 × 96000C mol −1 × (−5 × 10−4 VK −1 ) Molecular mass of B 2H6 = 10.8 × 2 + 6 = 27.6
Number of moles of B 2H6 in 27.66 g
= − 96 JK −1 mol −1 Given mass 27.66
= = ≈1
Thus, on substituting the values of ∆G and ∆S in Molar mass 27.6
Eq. (i), we get − 384000 J mol −1 Now consider the equation
= ∆H − 300 K × (−96 JK −1mol −1 ) B 2H6 + 3O 2 → B 2O 3 + 3H2O
∆H = − 384000 − 28800 J mol −1 From the equation we can interpret that 3 moles
of oxygen is required to burn 1 mole (i.e. 27.6 g)
= − 412800 J mol −1 = − 412.800 kJ mol −1
B 2H6 completely.
Also consider the electrolysis reaction of water i.e.
16. Λ°m for NaCl, HCl and NaA are 126.4, 425.9
H2O s 2H+ + O −−
and 100.5 S cm 2 mol− 1, respectively. If the +2e −
conductivity of 0.001 M HA is 2H+ → 2H → H2 ↑
Cathode
5 × 10− 5 S cm − 1, degree of dissociation of HA −− Anode 2 such
O →
−
O → O 2 ↑
is [ JEE Main 2019, 12 Jan Shift-II] −2e atoms
(a) 0.25 (b) 0.50 (c) 0.75 (d) 0.125

From the above equation it can be easily Exp. (b)

interpreted that in electrolysis of water for the
Zinc metal is the most stable metal to cover iron
production of 1 mole of oxygen from 1 mole of
surfaces. The process of coating the iron surface
H2O at anode 4 moles electrons are required.
by zinc is called galvanisation.
Likewise for the production of 3 moles of O2
12(3 × 4) moles of electrons will be needed. 21. Two Faraday of electricity is passed through
So, the total amount of charge required to a solution of CuSO 4. The mass of copper
produce 3 moles of oxygen will be deposited at the cathode is (at. mass of
12 × F or 12 × 96500 Cu = 63.5 u) [JEE Main 2015]
We know (a) 0g (b) 63.5g (c) 2g (d) 127g
Q = it
So, 12 × 96500 = 100 × t in seconds Exp. (b)
12 × 96500 Given, Q = 2F
or = t in hours = 32
. hours
100 × 3600 Atomic mass of Cu = 63.5 u
Valency of the metal Z = 2
18. Which of the following reactions is an
We have,
example of a redox reaction?
CuSO 4 → Cu2+ + SO 2–
4
(a) XeF4 + O 2 F2 → XeF6 + O 2 Cu2+ + 2 e – → Cu
1mol 2 mol 1mol = 63.5 g
(b) XeF2 + PF5 → [XeF] +
PF6− 2F
E 2 ×63.5
(c) XeF6 + H2O → XeOF4 + 2HF Alternatively, W = ZQ = ⋅ 2 F = 2E =
F 2
(d) XeF6 + 2H2O → XeO 2 F2 + 4HF
= 63.5
Exp. (a) 22. Resistance of 0.2 M solution of an electrolyte
The reaction in which oxidation and reduction is 50 Ω. The specific conductance of the
occur simultaneously are termed as redox reaction. solution is 1.4 Sm −1. The resistance of 0.5 M
+4 + 1 + 6 0
( X ) eF4 + O 2 ( F2 ) → X eF6 + O 2
solution of the same electrolyte is 280 Ω. The
Since, Xe undergoes oxidation while O undergoes
molar conductivity of 0.5 M solution of the
reduction. So, it is an example of redox reaction. electrolyte in S mol −1 is [JEE Main 2014]
(a) 5 × 10−4 (b) 5 × 10−3 (c) 5 × 103 (d) 5 × 102
19. Given, E ° Cl 2 / Cl −
° 3+
= 1.36 V, E Cr = − 0.74 V
/ Cr Exp. (a)
°
E Cr ° −
= 1.33 V , E MnO = 1.51 V For 0.2 M solution, R = 50 Ω
2− 3+
2 O 7 /Cr /Mn 2 + 4 . S m−1 = 14
κ = 14 . × 10−2 Scm−1
Among the following, the strongest reducing The resistivity of the solution is related to specific
agent is [JEE Main 2017 (Offline)] conductance by
1 1
(a) Cr (b) Mn 2 + (c) Cr 3 + (d) Cl − ρ= = Ω cm
κ 14 . × 10−2
Exp. (a) It is known that, R = ρ
l
⇒
R
=
l
The substances which have lower reduction a ρ a
potentials are stronger reducing agents. l 1
⇒ = R × = 50 × 14 . × 10−2 cm
° 3 + /Cr = − 0.74 V) is the strongest
Therefore, Cr (ECr a ρ
reducing agent among all the other given options. For 0.5 M solution,
R = 280 Ω
20. Galvanisation is applying a coating of κ =?
[JEE Main 2016 (Offline)] l
. × 10−2 cm
= 50 × 14
(a) Cr (b) Cu (c) Zn (d) Pb a

−1 0
The specific conductance of the solution is given by (2) H2 O 2 − 2e − → O 2 + 2H+
1 1 l
κ= = × In this reaction, H2O 2 undergoes oxidation as
ρ R a
it shows decrease in oxidation number. Thus,
1
κ= . × 10−2 = 2.5 × 10−3 S cm−1
× 50 × 14 H2O 2 acts as a reducing agent.
280 −1 −2
Now, the molar conductivity of the solution is given (3) H2 O 2 + 2e − → 2 OH−

by In this reaction, H2O 2 undergoes reduction.
κ × 1000 2.5 × 10−3 × 1000 −1 0
Λm = = (4) H2 O 2 + 2OH− − 2e − → O 2 + 2H2O
M 0.5
= 5.5 cm 2 mol −1 = 5 × 10−4 S m2 mol −1 In this reaction, H2O 2 undergoes reduction.
Thus, acts as a reducing agent.
Hence, the molar conductivity of 0.5 M solution of
25. The metal that cannot be obtained by the
the electrolyte is 5 × 10−4 S m2 mol −1.
electrolysis of an aqueous solution of its
salts is [JEE Main 2014]
23. The equivalent conductance of NaCl at (a) Ag (b) Ca (c) Cu (d) Cr
concentrationC and at infinite dilution are λ c
and λ ∞ , respectively. The correct relationship Exp. (b)
between λ c and λ ∞ is given as [JEE Main 2014] Higher the position of element in the
(a) λc = λ ∞ + ( B )C (b) λc = λ ∞ − ( B )C electrochemical series, more difficult is the
(c) λc = λ ∞ − ( B ) C (d) λc = λ ∞ + ( B ) C reduction of its cation. Thus, among all the given
elements, only calcium on electrolysis yields H2
Exp. (c) gas at cathode while other yields pure metals at
cathode. In case of Ca 2+ ion, water is reduced in
Debye-Huckel Onsager equation can be written as
λc = λ ∞ − (B) C preference to calcium.
Where, For Cr
At cathode, Cr 3 + + 3 e − → Cr
λc = Molar conductivity of the solution at certain
concentration For Ag
At cathode, Ag + + e − → Ag
λ ∞ = Limiting molar conductivity For Cu
C = Concentration At cathode, Cu2 + + 2e − → Cu
B = Constant that depends on temperature, For Ca 2 +
1
charges on the ions and dielectric constant At cathode, H2O + e − → H2 + OH−
as well as viscosity of the solution 2
24. In which of the following reactionsH 2O2 acts 26. Given below are the half-cell reactions
as a reducing agent? [JEE Main 2014] Mn 2+ + 2e − → Mn , E ° = −1.18V
1. H 2O2 + 2H + + 2e − → 2H 2O
2( Mn 3+ + e − → Mn 2+ ), E ° = +1.51V
2. H 2O2 − 2e − → O2 + 2H +
3. H 2O2 + 2e − → 2OH − The E ° for 3Mn 2+ → Mn + 2 Mn 3+ will be
(a) −2.69V, the reaction will not occur
4. H 2O2 + 2OH − − 2e − → O2 + 2H 2O
(b) −2.69 V the reaction will occur
(a)1, 2 (b) 3, 4 (c)1, 3 (d) 2 , 4 (c) −0.33V , the reaction will not occur
Exp. (d) (d) −0.33 V, the reaction will occur [JEE Main 2014]
The reducing agent oxidises itself by undergoing Exp. (a)
oxidation through the loss of electrons. Thus, Mn2 + + 2e − → Mn, E ° = −118
. V …(i)
reducing agent reduces other molecules by
2 (Mn3 + + e − → Mn2 + ), E ° = +151
. V …(ii)
supplying electrons to them.
−2 Subtracting Eq. (ii) from Eq. (i), we get
(1) H2O −21 + 2H+ + 2e − → 2H2 O
3 Mn2 + → Mn + 2Mn3 +
In this reaction, H2O 2 undergoes reduction as
O shows increase in oxidation number. E° = −118
. − (+151
. ) = − 2.69 V

Since, the value of E° is −ve, therefore the reaction Based on the data given above, strongest
is non-spontaneous. oxidising agent will be [AIEEE 2013]
Alternate method (a) Cl (b) Cr 3 + (c) Mn 2 + (d) MnO −4
Mn2 + + 2e − → Mn, E ° = −118
. V …(i)
−
Exp. (d)
∆G ° = − nFE ° [here, n = number ofe involved in
the reaction] Higher the SRP (Standard Reduction Potential),

stronger is the oxidising agent Among the given,
∆G1° = −2 F(−118. ) = 2.36 F
electrode potentials, E° – 2+ is highest.
2Mn3 + + 2e − → 2Mn2 + , E ° = +151
MnO 4 /Mn
. V …(ii)
Hence, MnO –4 is the strongest oxidising agent.
∆G2° = −2 F[151
. ] = −3.02 F
Subtracting Eq. (ii) from Eq. (i), we get 29. The standard reduction potentials for
Zn 2+ / Zn, Ni2+ /Ni and Fe 2+ / Fe are – 0.76,
3 Mn2 + → Mn + 2Mn3 + , [n = 2 ]
– 0.23 and – 0.44 V, respectively. The
∆G3° = −2 FE °
reaction X + Y 2+ → X 2+ + Y will be
∆G30 = ∆G10 − ∆G20 = 5.38 F spontaneous when [AIEEE 2012]
⇒ −2 FE ° = 5.38 F ⇒ E° = −2.69 V (a) X = Ni, Y = Fe (b) X = Ni, Y = Zn
(c) X = Fe, Y = Zn (d) X = Zn, Y = Ni
27. Consider the following reaction,
xMnO−4 + yC 2O24− + zH + → xMn 2+
Exp. (d)
z A cell reaction is spontaneous, if ∆G° < 0.
+2 yCO2 + H 2O
2 Since, °
∆G ° = − nFEcell
The values of x, y and z in the reaction are, Thus, ° > 0, Ecell
Ecell ° = Eox
° + Ered
°
Red
(a) 5, 2 and 16 (b) 2, 5 and 8
X + Y 2 + → X 2 + + Y
(c) 2, 5 and 16 (d) 5, 2 and 8 Oxi
Exp. (c) (a) X = Ni, Y = Fe
The half equations of the reaction are Ni + Fe 2 + → Ni 2 + + Fe
MnO –4 → Mn2 +
E° = + 0. 23 V
Ni /Ni 2+
C 2O 2–
4 → CO 2
E° = − 0.44 V
The balanced half equations are Fe 2 + /Fe
(MnO –4 + 8 H+ + 5 e − → Mn2+ + 4H2O) × 2 Thus, ° = E°

Ecell
Ni /Ni 2+
+ E°
Fe 2 + /Fe
−
(C 2O 2–
4 → 2CO 2 + 2e ) × 5 = − 0.21 V
Equating number of electrons, we get ° <0
Ecell
2MnO –4 + 16 H+ + 10 e − → 2Mn2+ + 8H2O ⇒ Reaction is non-spontaneous.
5C 2O 2–
4 → 10CO 2 + 10 e − (b) X = Ni, Y = Zn
On adding both the equations, we get Ni + Zn2+ → Ni 2+ + Zn
2MnO –4 + 5C 2O –4 + 16 H+ → 2Mn2 + E° = 0.23 V
Ni /Ni 2+
16
+ 2 × 5 CO 2 +
H2O E° = − 0.76 V
2 Zn 2+ / Zn
Thus, x, y and z are 2, 5 and 16, respectively. ∴ ° = 0.23 + (−0.76) = − 0.53 V
Ecell
28. Given, °
E Cr = − 0.74 V;
3+
/Cr ° <0
Ecell
° = 1.51 V
E MnO −
/Mn 2+ ⇒ Non-spontaneous reaction.
4
°
E Cr = 1.33 V; (c) X = Fe, Y = Zn
2− 3+
E°
2O 7 /Cr
− = 1.36 V Fe + Zn2+ → Fe 2+ + Zn
Cl /Cl

° = E°
Ecell
Fe /Fe 2+
+ E°
Zn 2+ / Zn
31. Resistance of 0.2 M solution of an electrolyte
is 50 Ω. The specific conductance of the
= 0.44 − 0.76 = − 0.32 V solution is 1.3 S m −1. If resistance of the 0.4M
° <0
Ecell solution of the same electrolyte is 260 Ω, its
⇒ Non-spontaneous reaction. molar conductivity is [AIEEE 2011]
(a) 6250 S m 2 mol −1

(d) X = Zn, Y = Ni
(b) 6.25 × 10−4 S m 2 mol −1
Zn + Ni 2+ → Zn2+ + Ni (c) 625 × 10−4 S m 2 mol −1
(d) 62.5 S m 2 mol −1
° = E°
Ecell
Zn/ Zn 2+
+ E ° 2+
Ni /Ni
= 0.76 − 0.23 = 0.53 V Exp. (b)

° >0
Ecell For 0.2 M solution,
Specific conductance (κ )
⇒ Spontaneous reaction.
= Conductance   × Cell constant (l / a)
1
30. The reduction potential of hydrogen  R
half-cell will be negative if [AIEEE 2011]
⇒ κ=
1 l
× = 13 . S m−1
(a) p(H2 ) = 1 atm and [H+ ] = 2.0 M 50 a
l
(b) p(H2 ) = 1 atm and [H+ ] = 1.0 M ⇒ . × 50 m−1
= 13
a
(c) p(H2 ) = 2 atm and [H+ ] = 1.0 M
l
(d) p(H2 ) = 2 atm and [H+ ] = 2.0 M . × 50 × 10−2 cm−1
= 13
a
Exp. (c) For 0.4 M solution, R = 260 Ω
l
For hydrogen electrode, R =ρ
a
1
H+ (aq ) + e − → H2 (g ) ⇒
1
=κ= ×
1 l
2 ρ R a
1/ 2
0.0591 ( p H 2 ) 1
E = E °− log κ= . × 50 × 10−2 S cm−1
× 13
n [H+ ] 260
Here, n = number of electrons involved in the Molar conductivity of the solution is given by
reaction κ × 1000
Λm =
0.0591 ( pH2 )1/ 2 M
E = E °− log
1 [H+ ] 1 . × 50 × 10−2 × 1000
13
= ×
( p H 2 )1/ 2 260 4
E = −0.0591log = 6.25 S cm2 mol −1
[H+ ]
[Q E° = 0 for H − electrode] = 6.25 × 10−4 S m2 mol −1
( p H 2 )1/ 2
⇒ E will be −ve when is + ve. 32. The Gibbs energy for the decomposition of
[H+ ] Al 2O3 at 500°C is as follows [AIEEE 2010]
i.e., ( pH2 )1/ 2 > [H+ ] 2 4
Al 2O3 → Al + O2, ∆rG = +966 kJ mol −1
3 3
(pH2 )1/2
p H2 [H+ ] Ered The potential difference needed for
[H + ]
electrolytic reduction of Al 2O 3 at 500°C is at
(a) 1 atm 2.0 M 0.25 + ve
(b) 1 atm 1.0 M 1.0 0
least
(c) 2 atm 1.0 M 2.0 −ve (a) 4.5 V (b) 3.0 V (c) 2.5 V (d) 5.0 V
(d) 2 atm 2.0 M 0.50 + ve
Exp. (c)
+ 2 4
Hence, when p(H2 ) is 2 atm and [H ] is 10
. M, Ered Al 2O 3 → Al + O 2
is negative. 3 3

2
Thus, × 3 (O 2 − ) (a) 0.26 V (b) 0.399 V
3 (c) – 0.339 V (d) – 0.26 V
i.e., 2 O 2 − → O 2 + 4 e −1 [Q n = 4]
Exp. (a)
−1
∆G = + 966 kJ mol = 966 × 10 J mol −1
3
Cr | Cr 3+ (0.1 M) || Fe 2+ (0.01 M) |Fe
∆G = − nFEcell
Oxidation half cell

966 × 103 = − 4 × 96500 × Ecell
Cr → Cr 3 + + 3 e – × 2
Ecell = 2.5 V
Reduction half cell
° 3+
33. Given,E Fe = − 0.036V, E Fe
° 2+ = − 0.439V
/Fe / Fe
Fe 2+ + 2e – → Fe × 3
The value of standard electrode potential for
Net cell reaction
the charge, [AIEEE 2009]
2Cr + 3Fe 2+ → 2Cr 3+ +3Fe; n = 6
Fe 3+ (aq ) + e − → Fe 2+ (aq ) will be
° = E ° + E ° = 0.72 − 0.42 = 0.30V
Ecell
(a) – 0.072 V (b) 0.385 V oxi red
(c) 0.770 V (d) – 0.270 V ° 0.0591 [Cr 3 + ]2

Ecell = Ecell − log
n [Fe 2+ ]3
Exp. (c)
0.0591 . )2
(01
It is given that, = 0.30 − log
6 (0.01)3
Fe 3 + + 3e − → Fe, E1 ° = − 0.036 V …(i)
2+ − 0.0591 10−2
Fe + 2e → Fe, E2 ° = − 0.439 V …(ii) = 0.30 − log −6
6 10
We need to calculate 0.0591
Fe 3 + + e − → Fe 2 + , E3 ° = ? …(iii) = 0.30 − log 104
6
Equation (iii) can be obtained by subtacting Eq. (ii) Ecell = 0.2606 V
from (i) but E0 being an intensive property, cannot
be calculated by this way. In order to calculate E3° , 35. The equivalent conductances of two strong
concept of ∆G° is used . electrolytes at infinite dilution in H2O
∆G10 for Eq. (i) is given by (where ions move freely through a solution)
∆G10 = −3 × F × (−0.036) at 25°C are given below
⇒ ∆G10 = + 0108
. F Λ ° CH 3 COONa = 91.0 S cm 2 /equiv
∆G20 for Eq. (ii) is given by Λ ° HCl = 426.2 S cm 2 /equiv
∆G20 = −2 × F × (−0.439) ⇒ ∆G2° = 0.878F What additional information/quantity one
∆G30 for Eq. (iii) is given by needs to calculate Λ ° of an aqueous
solution of acetic acid ? [AIEEE 2007]
∆G3° = −1 × F × E3°
(a) Λ° of NaCl
∆G3° = ∆G1° − ∆G2° (b) Λ° of CH3COOK
(c) The limiting equivalent conductance of
⇒ −1 × F × E3° = 0108
. F − 0.878 F
H+ ( λ° H + )
⇒ E3° = 0770
. V (d) Λ° of chloroacetic acid (ClCH2COOH)
34. Given, E ° 3+ = 0.72 V, Exp. (a)

Cr /Cr
Molar conductivity of aqueous CH3COOH solution
E°
can be calculated from Kohlraush’s law as
Fe 2+ /Fe
= −0.42 V.
λ°CH 3 COOH = λ °CH 3COONa + λ °HCl − λ °NaCl
The potential for the cell
Hence, for determining the molar conductivity of
Cr | Cr 3+ (0.1M) || Fe 2+ (0.01M) | Fe is
CH3COOH solution, λ°NaCl is required.
[AIEEE 2008]

36. The cell, Zn| Zn 2+ (1M) ||Cu 2+ (1M)|Cu 39. Resistance of a conductivity cell filled with a
(E ° cell = 1.10 V), was allowed to be solution of an electrolyte of concentration
completely discharged at 298 K. The relative 0.1 M is 100 Ω. The conductivity of this
solution is1.29 S m −1. Resistance of the same
 [Zn 2+ ]
concentration of Zn 2+ to Cu 2+   is
cell when filled with 0.2 M of the same

2+ 
[Cu ] solution is 520 Ω. The molar conductivity of
(a) antilog (24.08) (b) 37.3 [AIEEE 2007] 0.2 M solution of the electrolyte will be
(c) 1037.3 (d) 9.65 × 104 (a) 124 × 10−4 S m 2 mol −1 [AIEEE 2006]
(b) 1240 × 10−4 S m 2 mol −1
Exp. (c) (c) 1.24 × 10−4 S m 2 mol −1
Cell is completely discharged. It means equilibrium (d) 12.4 × 10−4 S m 2 mol −1
gets established, Ecell = 0
Zn|Zn2+ (1 M) || Cu2+ (1 M) | Cu Exp. (d)
2+ 2+ For 0.1 M solution
Cell reaction : Zn + Cu r Zn + Cu
[Zn 2+
] R = 100 Ω,
K eq =
[Cu2+ ] 1  l
κ=  
0.0591 R  a
We know, Ecell = E °cell − log Keq
l
n (cell constant) = 1.29 × 100 m−1
0.0591 a
E °cell = log Keq
n For 0.2 M solution
0.0591
or 1.10 = log K eq Given, R = 520 Ω; C = 0.2 M
2
µ (molar conductivity ) = ?
[Zn2+ ] 2.20
Keq = = antilog = antilog 37.3 κ × 1000
[Cu2+ ] 0.0591 Molar conductivity, Λm =
M
[ κ can be calculated as κ =   , now cell
1 l
37. What products are expected from the
disproportionation reaction of R  a
hypochlorous acid ? [AIEEE 2006] constant is known]
1 1000
(a) HClO 3 and Cl 2O (b) HClO 2 and HClO 4 Hence, Λm = × 129 × × 10−6 m3
(c) HCl and Cl 2O (d) HCl and HClO 3 520 0.2
= 12.4 × 10−4 Sm2 mol −1
Exp. (d)
3HOCl → 2HCl + HClO 3 40. The molar conductivities Λ ° NaOAc and Λ ° HCl
at infinite dilution in water at 25°C are 91.0
38. Which of the following chemical reactions and 426.2S cm 2 /mol, respectively. To
depicts the oxidising behaviour of H2SO4 ? calculate Λ ° HOAc , the additional value
(a) 2HI + H2 SO 4 → I2 + SO 2 + 2H2O required is
(b) Ca(OH)2 + H2 SO 4 → CaSO 4 + 2H2O (a) Λ° H 2 O (b) Λ° KCl [AIEEE 2006]
(c) NaCl + H2 SO 4 → NaHSO 4 + HCl (c) Λ° NaOH (d) Λ° NaCl
(d) 2PCl 5 + H2 SO 4 → 2POCl 3 + 2HCl Exp. (d)
+ SO 2Cl 2 [AIEEE 2006] According to Kohlrausch’s law
O
Exp. (a)

−1 + 6 0
2HI +H2SO 4 → I2 +SO 2 + 2H2O
+ 4
[NaOAc = CH3 C O −Na + ]
H2SO 4  Reduced to → SO 2 λ °CH 3 COOH = λ °CH – + λ° ...(i)

3 COO H+
Oxidising λ°HCl = λ ° + λ °Cl – ...(ii)
agent H+

λ °CH 3 COONa = λ °CH – + λ° ....(iii) Exp. (a)

3 COO Na+
Thus, on adding Eqs. (ii) and (iii), if λ° and Cr2O 27 − + 14H+ + 6I− → 2Cr 3+ + 7H2O + 3I2
Na+
λ°Cl – are subtracted, we can obtained the value of Cr2O 2− 3+
7 is reduced to Cr .
Thus, final state of Cr is + 3.

λ°HOAc . Thus, additional value required is λ°NaCl .
44. The highest electrical conductivity from the

41. Given the data at 25°C, following aqueous solutions is of
Ag + I − → AgI + e − ; E ° = 0.152 V (a) 0.1 M difluoroacetic acid [AIEEE 2005]
−
Ag → Ag + e ; +
E ° = − 0.800 V (b) 0.1 M fluoroacetic acid
(c) 0.1 M chloroacetic acid
What is the value of log K sp for AgI ?
(d) 0.1 M acetic acid
 RT 
2.303 = 0.059 V  [AIEEE 2006] Exp. (a)
 F 
Fluoro group causes negative inductive effect
(a) − 8.12 (b) + 8.612 (c) −37.83 (d) −16.13
increasing ionisation. Thus, 0.1 M difluoroacetic
Exp. (d) acid has highest electrical conductivity.
AgI(s ) + e − r Ag(s) + I ; −
E1° = − 0.152 H O
 
Ag(s ) → Ag+ + e − ; E2° = − 0.8 F ←C ←C ←O ←H
↓
AgI(s ) → Ag+ + I− ; E° = − 0.952 F
[E ° = E1° + E2° ]
0.059 45.
E °cell = log Ksp
n
Electrolyte KCl KNO3 HCl NaOAc NaCl
0.059
− 0.952 = log Ksp ∞
1 Λ
(S cm2 mol −1 ) 149.9 145.0 426.2 91.0 126.5
− 0.952
log Ksp = = − 16.135
0.059
Calculate Λ∞HOAc using appropriate molar
+ conductances of the electrolytes listed
42. The oxidation state of Cr in[Cr(NH 3 )4 Cl 2] is
(a) 0 (b) + 1 [AIEEE 2005]
above at infinite dilution in H2O at 25°C.
(a) 217.5 (b) 390.7 [AIEEE 2005]
(c) + 2 (d) + 3
(c) 552.7 (d) 517.2
Exp. (d) Exp. (b)
[Cr(NH3 )4 Cl 2 ]+ Λ∞AcOH = Λ∞AcONa + Λ∞HCl − Λ∞NaCl
Let the oxidation state of Cr = x = 91.0 + 426.2 − 126.5 = 390.7
NH3 = 0
Cl = − 1 46. Aluminium oxide may be electrolysed at
1000°C to furnish aluminium metal (atomic
Net charge = + 1
mass = 27 u; 1 Faraday = 96,500 C). The
∴ [Cr(NH3 )4 Cl 2 ]+ cathode reaction is
x + 4 × 0 + 2 (− 1) = + 1 Al 3+ + 3e − → Al 0
∴ x=3
To prepare 5.12 kg of aluminium metal by
43. The oxidation state of chromium in the final this method would require [AIEEE 2005]
product formed by the reaction between KI (a) 5.49 × 101 C of electricity
and acidified potassium dichromate (b) 5.49 × 104 C of electricity
solution is [AIEEE 2005] (c) 1.83 × 107 C of electricity
(a) + 3 (b) + 2 (c) + 6 (d) + 4 (d) 5.49 × 107 C of electricity

Exp. (d) 49. In a hydrogen-oxygen fuel cell, combustion

Al 3+ + 3e − → Al of hydrogen occurs to [AIEEE 2004]
w = zQ (a) generate heat
where, w = amount of metal (b) create potential difference between the two
= 5.12 kg = 5.12 × 10 3 g electrodes
z = electrochemical equivalent (c) produce high purity water

equivalent weight (d) remove adsorbed oxygen from electrode
= surfaces
96500
atomic mass 27 Exp. (b)
= =
electrons × 96500 3 × 96500
Any cell (like fuel cell), works when potential
27
5.12 × 103 = ×Q difference is developed.
3 × 96500
5.12 × 103 × 3 × 96500
50. The E °M 3 + /M 2 + values for Cr, Mn, Fe and Co
Q= C are − 0.41, + 1.57, + 0.77 and + 1.97 V,
27
= 5.49 × 10 C
7 respectively. For which one of these metals,
the change in oxidation state from + 2 to + 3
47. Among the properties ( A ) reducing, (B ) is easiest ? [AIEEE 2004]
oxidising and (C ) complexing, the set of (a) Cr (b) Mn (c) Fe (d) Co
properties shown by CN − ion towards metal Exp. (a)
species is [AIEEE 2004]
E° 3+ 2+ = − 0.41 V
Cr /Cr
(a) A , B (b) B , C (c) C , A (d) A , B , C E° 3+ 2+ = + 1.57 V
Mn /Mn
Exp. (c) E° 3+ 2+ = + 0.77 V
Fe /Fe
CN− is a better complexing agent (C ) as well as a E° 3+ 2+ = + 1.97 V
Co /Co
reducing agent ( A). More negative value of E°red indicates better
Thus, properties ( A) and (C ) are shown reducing agent. Thus, easily oxidised. Hence,
Property (C ) : oxidation of Cr 2+ to Cr 3+ is the easiest.
Ni 2+ + 4CN− → [Ni(CN)4 ]2 − 51. Consider the following E ° values :

Property ( A) : E ° Fe 3 + /Fe 2 + = + 0.77 V
CuCl 2 + 5KCN → K 3 [Cu(CN)4 ] E ° Sn 2 + / Sn = − 0.14 V
II I
1 Under standard conditions, the potential for
+ (CN)2 + 2KCl
2 the reaction
[CN reduces Cu2+ to Cu+ ]
Sn(s) + 2Fe 3+ (aq ) → 2Fe 2+ (aq ) + Sn 2+ (aq )
48. The limiting molar conductivities Λ ° for is [AIEEE 2004]
NaCl, KBr and KCl are 126, 152 and (a) 1.68 V (b) 1.40 V (c) 0.91 V (d) 0.63 V
150 S cm 2 mol −1, respectively. The Λ ° for
NaBr is [AIEEE 2004] Exp. (c)
2 −1 2 −1 Sn (s ) + 2Fe 3+(aq ) → 2Fe 2+(aq ) + Sn2+(aq )
(a) 128 S cm mol (b) 176 S cm mol
(c) 278 S cm 2 mol −1 (d) 302 S cm 2 mol −1 E °cell = E °oxi + E °red = E ° + E°
Sn/Sn 2+ Fe 3+ /Fe 2+
Exp. (a) Given, E° = − 0.14 V

Sn 2+ /Sn
By Kohlrausch’s law. ∴ E° = + 0.14 V
Sn/Sn 2+
Λ°NaBr = Λ°NaCl + Λ°KBr − Λ°KCl E° = 0.77 V
3+
Fe /Fe 2+
= 126 + 152 − 150 ∴ E°cell = 0.14 + 0.77
= 128 S cm2 mol −1 = 0.91 V

0.0591
52. In a cell that utilises the reaction 0.591 = log Keq
1
Zn (s ) + 2H + (aq ) → Zn 2+ (aq ) + H 2( g )
∴ log Keq = 10
addition of H 2SO4 to cathode compartment ∴ Keq = 1 × 1010
will [AIEEE 2004]
(a) lower the E and shift equilibrium to the left 54. Several blocks of magnesium are fixed to the
(b) lower the E and shift the equilibrium to the bottom of a ship to [AIEEE 2003]
right (a) keep away the sharks
(c) increase the E and shift the equilibrium to the (b) make the ship lighter
right (c) prevent action of water and salt
(d) increase the E and shift the equilibrium to the (d) prevent puncturing by under sea rocks
left Exp. (c)
Exp. (c) Magnesium usually have a thin layer of MgO over
its surface which prevents the underneath of metal
Zn (s ) + 2H +
→ Zn (aq ) + H2 (g )
2+
from reacting with moisture. Thus, several blocks
[Zn2+ ] of magnesium are fixed to the bottom of a ship to
Reaction quotient, Q =
[H+ ]2 prevent action of water and salt.
Corresponding cell is 55. When during electrolysis of a solution of
Zn | Zn2+(C1 ) || H+ (aq ) | Pt(H2 ) AgNO3 , 9650 C of charge pass through the
− + electroplating bath, the mass of silver
Anode Cathode
deposited on the cathode will be [AIEEE 2003]
0.0591
and Ecell = E °cell − log K (a) 1.08 g (b) 10.8 g (c) 21.6 g (d) 108 g
2
0.0591 [Zn2+ ] Exp. (b)
= E °cell − log + 2
2 [H ] Ag+ + e − → Ag
[H+ ]2 9650 1
= E °cell +
0.0591
log Number of moles of Ag = = moles
96500 10
2 [Zn2+ ]
Ag+ + e − → Ag
If H2SO 4 is added to cathodic compartment,
1
(towards reactant side), then Q decrease (due to ∴ Mass of Ag produced = × 108 = 10.8 g
increase in H+ ). 10
Hence, equilibrium is displaced towards right and 56. Standard reduction electrode potentials of
Ecell increases.
three metals A , B and C are + 0.5 V, − 3.0 V
53. The standard emf of a cell, involving one and − 1.2 V, respectively. The reducing
electron change is found to be 0.591 V at 25° power of these metals are [AIEEE 2003]
C. The equilibrium constant of the reaction (a) B > C > A (b) A > B > C
is (F = 96500 C mol −1) [AIEEE 2004] (c) C > B > A (d) A > C > B
(a) 1.0 × 101 (b) 1.0 × 105 Exp. (a)
(c) 1.0 × 1010 (d) 1.0 × 1030 More negative value of E° means higher reducing
power.
Exp. (c)
° is
Relation between Keq and Ecell
57. For the redox reaction
Zn (s ) + Cu 2+ (0.1 M) → Zn 2+ (1 M) + Cu (s )
2.303 RT
E °cell = log Keq
nF taking place in a cell, E ° is 1.10 V. E for the
0.0591  RT 
E °cell = log Keq (at 298 K) cell will be  2.303 = 0.0591
n  F  [AIEEE 2003]
(a) 2.14 V (b) 1.80 V (c) 1.07 V (d) 0.82 V

Exp. (c) Changes in oxidation number respectively,

By using Nernst equation, are [AIEEE 2002]
0.0591 (a) 1, 3, 4, 5 (b) 5, 4, 3, 2
Ecell = E °cell − log Q
n (c) 5, 1, 3, 4 (d) 2, 6, 4, 3
Cu2+ + Zn → Zn2+ + Cu
0.1 M 1M Exp. (c)

2+ + 7
[Zn ] 1
Q= = = 10 MnO 4− → Mn2+ change 5
[Cu2+ ] 0.1 + 6
0.0591 → MnO 24 − change 1
Ecell = 1.10 − log 10 + 4
2
→ MnO 2 change 3
= 1.10 − 0.0295 = 1.0705 V + 3
→ Mn2O 3 change 4
58. For a cell reaction involving a two electron
change, the standard emf of the cell is found 61. Which of the following is a redox reaction ?
to be 0.295 V at 25°C. The equilibrium (a) NaCl + KNO 3 → NaNO 3 + KCl
constant of the reaction at 25°C will be [AIEEE 2002]
[AIEEE 2003] (b) CaC2O 4 + 2HCl → CaCl 2 + H2C2O 4
(a) 1 × 10−10 (b) 29.5 × 10−2
(c) Ca(OH)2 + 2NH4Cl → CaCl 2 + 2NH3
(c) 10 (d) 1 × 1010 + 2H2O
Exp. (d) (d) 2K [Ag(CN)2 ] + Zn → 2Ag + K 2 [Zn(CN)4 ]
The standard emf of the cell,
2 .303 RT
Exp. (d)
E °cell = log Keq +1−1 + 1 −1 + 1 −1 + 1− 1
nF (a) Na Cl + K NO 3 → Na NO 3 + K Cl
0.0591 +2 −2 + 1− 1 + 2 −1 + 1 −2
0.295 = log Keq (b) Ca C 2 O 4 + 2 H Cl → Ca Cl 2 +H2 C 2 O 4
2
+2 −1 − 3+1− 1 + 2 −1 −3 + 1
∴ log Keq = 10 (c) Ca(OH)2 +2NH4 Cl → Ca Cl 2 +2NH3
∴ Keq = 1 × 1010 + 1 −2
+ 2H2 O
In all these cases during reaction, there is no
59. Oxidation number of Cl in CaOCl 2 change in oxidation state of ion or molecule or
(bleaching powder) is [AIEEE 2002] constituent atom. These are simply ionic
reactions.
(a) zero, since it contains Cl 2
(b) −1, since it contains Cl − (d) 2K[Ag(CN)2 ] + Zn → 2Ag + K 2 [Zn(CN)4 ]
(c) + 1, since it contains ClO − Ag+ → Ag gain of e − , reduction
Zn → Zn2+ loss of e − , oxidation
(d) +1and −1, since it contains ClO − and Cl −
Exp. (d) 62. Conductivity (Seimen’s S) is directly

proportional to area of the vessel and the
CaOCl2 is written basically as Ca(OCl)Cl.
concentration of the solution in it and is
OCl − → Cl has + 1 oxidation state inversely proportional to the length of the
Cl − → Cl has − 1oxidation state vessel, then constant of proportionality is
expressed in [AIEEE 2002]
60. MnO−4 is a good oxidising agent in different (a) S m mol −1 (b) S 2 m 2 mol −2
medium changing to (c) S m 2 mol −1 (d) S 2 m 2 mol
MnO−4 → Mn 2+ → MnO24− → MnO2 Exp. (c)
→ Mn 2O3

S ∝ area (m2 ) ∝ conc (mol / m3 ) ∝

1
(m−1 ) Pt(H 2 )|H + (aq) |Pt(H 2 )
length p1 1M p2
mol −1
S = κm 2
m emf is given by [AIEEE 2002]
m3
−1 RT p RT p
κ = S mol m2
(a) loge 1 (b) loge 1
F p2 2F p2
63. Which of the following reaction is possible RT p RT p
at anode ? [AIEEE 2002] (c) loge 2 (d) loge 2
F p1 2F p1
(a) Fe2 + 2 e − → 2F −
1
(b) 2H+ + O 2 + 2e − → H2O
Exp. (b)
2 LHS half cell
(c) 2Cr23 + + 7H2O → Cr2O 27 − + 14H+ + 6e−
H2 (g ) → 2H+ (1 M) + 2e −
(d) None of the above p1
Exp. (c) RHS half cell

2H+ (1 M) + 2e – → H2 (g )
Oxidation takes place at anode. Hence, (a), (b) p2
is not feasible as these are reduction reactions. H2 (g ) → H2 (g )
But Cr 3+ is oxidised to Cr 6+(Cr2O 27 − ) under given p1 p2
condition.
p2
E°cell = 0.00 V, K = ,n=2
64. For a cell given below p1
Ag | Ag + || Cu 2 + | Cu
– + RT
Ecell = E °cell − loge K
−
+
Ag + e → Ag ; E°= x nF
− p
Cu 2+
+ 2e → Cu; E°=y =0−
RT
loge 2
2F p1
E ° cell is [AIEEE 2002]
(a) x + 2 y (b) 2x + y RT p
Ecell = loge 1
(c) y − x (d) y − 2 x 2F p2
Exp. (c) 66. Consider the following reactions at 1100°C

At LHS (oxidation) 2 × (Ag → Ag+ + e − ); (I) 2C + O2 → 2CO, ∆G ° = − 460 kJ mol −1
E °oxi = − x
(II) 2Zn + O2 → 2ZnO, ∆G ° = − 360 kJ mol −1
−
At RHS (reduction) Cu 2+
+ 2e → Cu
Based on these, select correct alternative.
E °red = + y
(a) zinc can be oxidised by CO [AIEEE 2002]
2Ag + Cu2+ → Cu + 2Ag+, E °red = ( y − x) (b) zinc oxide can be reduced by carbon
(c) Both (a) and (b)
Note E° values remain constant when half-cell (d) None of the above
equation is multiplied/divided.
Exp. (b)
65. For the following cell with hydrogen ZnO + C → Zn + CO,
electrodes at two different pressures p1 and
∆G° = − ve
p2
Hence, this is spontaneous.

9
Chemical Kinetics and

Surface Chemistry
The logarithm equation of Freundlich adsorption
1. Adsorption of a gas follows Freundlich isotherm is
adsorption isotherm. x is the mass of the gas x 1
log = log K + log p
adsorbed on mass m of the adsorbent. The m n
x On comparing the above equation with straight
plot of log versus log p is shown in the
m line equation, ( y = mx + c )
x we get
given graph. is proportional to 1
m m = slope =
n
and c = log K
From the given plot,
y − y1 1 2
m= 2 = =
x
log — x2 − x1 n 3
2
m x
3 ∴ = Kp2 / 3
m
log p 2. For the reaction, 2A + B → C , the values of

2 /3 3/ 2
(a) p (b) p initial rate at different reactant
(c) p 3 (d) p 2 concentrations are given in the table below.
The rate law for the reaction is
Exp. (a) [JEE Main 2019, 8 April Shift-I]
−1
Key Idea According to Freundlich, [A](mol L ) [B](mol L−1 ) Initial rate
x
= Kp1 / n [n > 1] (mol L−1s−1 )
m 0.05 0.05 0.045
where, m = mass of adsorbent, x = mass of 0.10 0.05 0.090
x
the gas adsorbed, = amount of gas 0.20 0.10 0.72
m
adsorbed per unit mass of solid adsorbent, (a) rate = k [A ][B ]
2
(b) rate = k [A ]2[B ]2
p = pressure, K and n = constants. (c) rate = k [A ][B ] (d) rate = k [A ]2[B ]

Chemical Kinetics and Surface Chemistry 109
Exp. (a) 4. The aerosol is a kind of colloid in which

Let the rate equation be k [ A]x [B]y [JEE Main 2019, 9 April Shift-I]
From Ist values, (a) gas is dispersed in liquid
0.045 = k[0.05]x [0.05]y …(i) (b) gas is dispersed in solid
From 2nd values, (c) liquid is dispersed in water

0.090 = k[010
. ]x [0.05]y …(ii) (d) solid is dispersed in gas
From 3rd values,
Exp. (d)
. = k[020
072 . ]x [010
. ]y …(iii)
The aerosol is a kind of colloid in which solid is
On dividing equations (i) by (ii), we get
x
dispersed in gas. e.g. smoke, dust.
0.045  0.05 
=
0.09  010
.  5. The given plots represent the variation of
1 x the concentration of a reaction R with time
 0.05  =  0.05 
 010
.   010
.  for two different reactions (i) and (ii). The
respective orders of the reactions are
∴ x=1
Similarly on dividing Eq. (ii) by (iii) we get
0.09  01 .   0.05 
x y (i) (ii)
=
072
.  02
.   010
. 
In [R] [R]
y
.  0.05 
0.01 01
=
.  01
0.08 02 . 
y time time
. =
0.05 
025
 010
.  (a) 1, 1 (b) 0, 2 (c) 0, 1 (d) 1, 0
. = [0.5]
025 y
Exp. (d)
[0.5]2 = [0.5]y In first order reaction, the rate expression
∴ y=2 depends on the concentration of one species
Hence, the rate law for the reaction only having power equal to unity.
Rate = k [ A] [B]2 nr → products
−d [r ]
1 k k2 = k [r ]
3. For a reaction scheme, A → B → C , if the dt
rate of formation of B is set to be zero then On integration, − ln[r ] = kt − ln[r0 ]
the concentration of B is given by or ln(r ) = ln(r0 ) − kt
[JEE Main 2019, 8 April Shift-II] y = c + mx
m = slope = −k (negative)
k 
(a) k1k 2 [A ] (b)  1  [A ] c = intercept = ln (r0 )
k2  The graph for first order reactions is
(c) (k1 − k 2 )[A ] (d) (k1 + k 2 )[A ]
Exp. (b)
K K
A → 1
B → 2
C ln (r)
Rate of formation of B is
d [B]
= k1[ A] − k2 [B]
dt
0 = k1[ A] − k2 [B] Q Given, = 0
d [B] t
⇒
 dt  In zero order reaction,
⇒ k2 [B] = k1[ A] [r ] → product
k1 −d [r ]t
⇒ Concentration of B, [B] = [ A] ∴ = k or −d [r ]t = kdt
k2 dt

On integrating, −[r ]t = kt + c (iii) Fe (Iron) is used as catalyst in Haber’s

If t = 0,[r ]t = [r ]0 process for the manufacture of ammonia.
Fe(s)
∴ −[r ]t = kt − [r ]0 N2 (g ) + 3H2 (g ) → 2NH3 (g )
[r ]t = [r ]0 − kt (iv) Pd (Palladium) is used to prepare ethanal.
Thus, the graph plotted between [r ]t and t gives Reaction involved is

a straight line with negative slope (−k ) and H2C ==CH2 + O 2 →
2 2 PdCl /CuCl
CH3CHO
intercept equal to [r ]0 . H 2O
The graph for zero order reaction is This reaction is also known as Wacker’s
process.
7. Consider the given plot of enthalpy of the

[r]
following reaction between A and B.
A + B → C+D
Identify the incorrect statement.
t
20
6. Match the catalysts Column I with products
Column II. Enthalpy 15
(kJ mol–1)10
D
Column I Column II 5
(Catalyst) (Product) A +B
C
(A) V2O5 (i) Polyethlyene Reaction
coordinate
(B) TiCl 4 / Al(Me) 3 (ii) Ethanal
(a) D is kinetically stable product.
(C) PbCl 2 (iii) H2SO 4
(b) Formation of A and B from C has highest
(D) Iron oxide (iv) NH3 enthalpy of activation.
(c) C is the thermodynamically stable product.
[JEE Main 2019, 9 April Shift-I] (d) Activation enthalpy to form C is 5 kJ
(a) (A)-(ii), (B)-(iii), (C)-(i), (D)-(iv) mol −1 less than that to form D.
(b) (A)-(iv), (B)-(iii), (C)-(ii), (D)-(i)
(c) (A)-(iii), (B)-(i), (C)-(ii), (D)-(iv)
Exp. (d)
(d) (A)-(iii), (B)-(iv), (C)-(i), (D)-(ii) Only statement (d) is incorrect. Corrected
statement is ‘‘Activation enthalpy to form C is 15
Exp. (c) kg mol −1 more than 5 kg mol −1 that is required to
form D.’’ It can be easily explained by following
Correct match is
graph.
(A) → (iii); (B) → (i); (C) → (ii); (D) → (iv)
(i) TiCl 4 + AlCl 3 (Ziegler- Natta catalyst) is used
20
to prepare polyethylene from ethene.
15
Zieglar-Natta Activation
catalyst Enthalpy
n CH2 CH2 CH2 CH2 n (kJ mol–1) 10 D enthalpy
Ethene Polyethylene 5
A+B
(ii) V2O 5 (Vanadium pentoxide) is used as
Reaction C
catalyst to prepare H2SO 4 from contact
process. Reaction involved is coordinate
V 2O 5 Activation enthalpy (or energy) is the extra
2SO 2 (g ) + O 2 (g ) → 2SO 3 (g ) energy required by the reactant molecules that
result into effective collision between them to
It is the key step in the manufacture ofH2SO 4 .
form the products.

8. A gas undergoes physical adsorption on a needs 1 hour to reach the wound. Once it
surface and follows the given Freundlich reaches there, the bacterial population goes
dN
x
adsorption isotherm equation = Kp 0. 5 down as = − 5N 2. What will be the plot of
m dt
N0
Adsorption of the gas increases with vst after 1 hour ?

N
(a) increase in p and increase in T
(b) increase in p and decrease in T
N0 N0
(c) decrease in p and decrease in T (a) (b)
N N
(d) decrease in p and increase in T
t(h) t(h)
Exp. (b)
For physisorption or physical adsorption,
N0 N0
Adsorption isotherm (Temperature, T = constant) (c) (d)
N N
is shown below:
t(h) t(h)
x
—
m
x
Moderate pressure zone, — ∝ p1/n Exp. (a)
m
The expression for bacterial growth is
N = N0et
p
N0
= e −t
where, x = amount of adsorbate, m = amount of N
adsorbent, From 0 to 1 hour N′(t ) = N0et
x
= degree of adsorption From 1 hour onwards,
dN
= −5N2
m dt
1 1
= order of the reaction, where, 0 < < 1 and On differentiating the above equation from N′ to
n n N we get.
so, 1< n < ∞ N t
−2
∫N dN = −5∫ dt [Q At 1 hour, N′ = eN0 ]
1
x
Here, = Kp2 , eN0 1
m
1 1 1 
i.e.
x
∝ p2  −  = 5(t − 1)
m  N eN0
Adsorption isobar (Pressure, p = constant) Multiply both sides by N0 , we get

N0 1 N 1
− = 5N0 (t − 1) or, 0 = 5N0 (t − 1) +
N e N e
= 5N0t +  − 5N0 
x N0 1
—
m N  e 
T
So, the rate of physical adsorption of the gas, N0
increases with p (when, T is constant) and —
N
decreases with T (when p is constant).
t(h)
9. A bacterial infection in an internal wound
grows as N ′ (t ) = N 0 exp (t ), where the timet On comparing the above equation with equation
is in hours. A dose of antibiotic, taken orally, of straight line, y = mx + c

1 Exp. (d)
We get m = 5N0 , c = − 5N0
e
N0 The explanation of the given statements are as
∴ Plot of vs t is shown aside. follows :
N
(a) Colloidal medicines are more effective
because they (dispersed phase) have larger
10. For the reaction of H2 with I2, the rate surface area.
constant is 2.5 × 10− 4 dm3 mol− 1s− 1 at 327ºC Thus, option (a) is incorrect.
and 1.0 dm 3 mol− 1 s− 1 at 527ºC. The (b) Brownian motion of dispersed phase particles
activation energy for the reaction, in in colloidal solution is faster if the viscosity of
the solution is very low. Thus, option (b) is
kJ mol− 1 is (R = 8.314 JK − 1 mol− 1) incorrect.
[JEE Main 2019, 10 April Shift-II] (c) Addition of alum (K 2SO 4 ⋅ Al 2 (SO 4 )3 ⋅ 24H2O),
(a) 59 (b) 72 (c) 150 (d) 166 an electrolyte to water makes it fit for drinking
Exp. (d) purposes because alum coagulates mud
particles from water.
Key Idea The Arrhenius equation for rate Thus, option (c) is incorrect.
constants at two different temperatures is (d) Precipitation of lyophobic solution particles by
k Ea  T2 − T1  electrophoresis is called cottrell precipitation.
log 2 =   [where, T2 > T1]
k1 2 .303R  TT 1 2 
Thus, option (d) is correct.
where, k1 and k2 are rate constants at
temperatures T1 and T2 , respectively.
12. In the following reaction; xA → yB
R = Gas constant, Ea = Activation energy  d[ A ] d[B ]
log 10 −  = log 10  + 0.3010
For the reaction, H2 + I2 → 2HI  dt   dt 
Given k1 = 2.5 × 10−4 dm3mol −1s −1 A and B respectively can be
T1 = (273 + 327 ) K = 600 K [JEE Main 2019, 12 April Shift-I]
k2 = 1 dm 3 mol −1 s −1 at T2 = (273 + 527 ) K = 800 K (a) n-butane and iso-butane
k2 Ea  T2 − T1  (b) C2H2 and C6 H6
Now, log =  
k1 2.303R  TT
1 2 
(c) C2H4 and C4 H8
1 Ea (d) N2O4 and NO2
⇒ log =
2.5 × 10 −4 2.303 × 8.314 × 10 −3
 800 − 600 
Exp. (c)
  In the given reaction; x A → y B
 600 × 800 
−d [ A]
log10  = log10 
d [B]
(10 × 10 ) 3
Ea 200 + 0.3010
⇒log = ×  dt   dt 
2.5 0.019 48 × 104
Value of log 2 = 0.3010
⇒log 4 + 3log 10 ~
− Ea × 0.022
Substituting 0.3010 by log2
2 × log 2 + 3 3.6 ~
⇒ Ea = = – 163.6 kJ mol −1
log10  −
d [ A ]
= log10 
d [B]
0.022 0.022 + log 2
 dt   dt 
11. The correct option among the following is Using logarithm rules,
 −d [ A] = 2 ×  d [B] ⇒ − 1  d [ A] =  d [B] …(i)
(a) colloidal medicines are more effective,  dt   dt  2  dt   dt 
because they have small surface area.
(b) brownian motion in colloidal solution is faster Using the rate equation (i) to determine the
if the viscosity of the solution is very high. reaction involved is
(c) addition of alum to water makes it unfit for 2 A → B
drinking. Option that fits correct in the above reaction is (c).
(d) colloidal particles in lyophobic sols can be 2C 2H4 → C 4H8 .
precipitated by electrophoresis.

Given, [N2O 5 ]initial = 3.00 mol L− 1

13. Peptisation is a [JEE Main 2019, 12 April Shift-I]
After 30 min, [N2O 5 ] = 2 .75 mol L− 1
(a) process of bringing colloidal molecule into
solution 2N2O 5 (g ) → 4NO 2 (g ) + O 2 (g )
(b) process of converting precipitate into colloidal t= 0 3.0 M
t = 30
2.75 M
solution
From the equation, it can be concluded that
(c) process of converting a colloidal solution into
1 − ∆[N2O 5 ] 1 ∆[NO 2 ]
precipitate × = ×
2 ∆t 4 ∆t
(d) process of converting soluble particles to form
− ∆[N2O 5 ] − (2.75 − 3.00) mol L− 1 0.25
colloidal solution = = ⇒
∆t 30 30
Exp. (b) ∆[NO 2 ] ∆(N2O 5 )
and = −2
Peptisation is a process of converting precipitate ∆t ∆t
∆[NO 2 ] 0.25
into colloidal solution. This process involves the ⇒ =−2 ×
shaking of precipitate with the dispersion medium in ∆t 30
the presence of small amount of electrolyte. The = − 1.667 × 10− 2 mol L− 1 min− 1
electrolyte added is called peptising agent.
During peptisation, the precipitate adsorbs one of 15 Among the following, the incorrect
the ions of the electrolyte on its surface. This causes statement about colloids is
the development of positive or negative charge on [JEE Main 2019, 12 April Shift-II]
precipitates, which ultimately breakup into smaller (a) They can scatter light
particles of the size of a colloid. (b) They are larger than small molecules and
have high molar mass
14. NO2 required for a reaction is produced by the (c) The osmotic pressure of a colloidal
decomposition of N 2O5 in CCl 4 as per the solution is of higher order than the true
equation, solution at the same concentration
(d) The range of diameters of colloidal
2N 2O5( g ) → 4NO2( g ) + O2( g ) particles is between 1 and 1000 nm
The initial concentration of N 2O5 is Exp. (c)
3.00 mol L−1 and it is 2.75 mol L −1 after Statement (c) is incorrect about colloids.
30 minutes. The rate of formation of NO2 is Colligative properties such as relative lowering
[JEE Main 2019, 12 April Shift-II] of vapour pressure, elevation in boiling point,
(a) 4167
. × 10−3 mol L −1 min −1 depression in freezing point and osmotic
pressure of a colloidal solution is of low order
(b)1667
. × 10−2 mol L −1 min −1 than the true solution at the same concentration.
(c) 8.333 × 10−3 mol L −1 min −1
16. Adsorption of a gas follows Freundlich
(d) 2.083 × 10−3 mol L −1 min −1
adsorption isotherm. In the given plot,x is
Exp. (b) the mass of the gas adsorbed on mass m
of the adsorbent at pressure p ⋅( x /m ) is
Key Idea The rate of a chemical reaction means proportional to
the speed with which the reaction takes place.
For R → P 2 unit
Rate of disappearance of R x
log m
Decrease in conc.of R ∆[ R ] 4 unit
= =−
Time taken ∆t
Rate of appearance of P
Increase in conc. of P ∆[ P] log p
= =+
Time taken ∆t (a) p 2
(b) p 1/ 4
(c) p1/ 2 (d) p

Exp. (c) Order of the reaction (n) = 1

According to Freundlich adsorption isotherm, ⇒ Now, let for the 1st experiment,
x
1
x r1 = k ⋅ [ A]
∝ pn ⇒ = Kp1/ n r1 6.93 × 10− 3
m m ⇒ k= = = 6.93 × 10− 2 s − 1
[ A] 0.1
On taking log on both sides, we get

0.693 0.693
log   = log K + log p ⇒ t 50 = = = 10 s
x 1
 m n k 6.93 × 10− 2
On comparing with equation of straight line,
x 18. Which of the salt-solution is most effective
y = mx + c, plot of log vs log p gives, for coagulation of arsenious sulphide?
m
( y − y1 ) 1 2 1 (a) BaCl 2 (b) AlCl 3 (c) Na 3 PO4 (d) NaCl
Slope 2 = ⇒ =
( x2 − x1 ) n 4 2 [JEE Main 2019, 9 Jan Shift-II]
x
∴ ∝ p1/ 2 Exp. (b)
m
Arsenious sulphide sol is a negative colloid,
17. The following results were obtained during As 2S3 .(S2− ). So, it will be coagulated by the cation
kinetic studies of the reaction; of an electrolyte.
2A + B → Products According to the Hardy-Schulze rule, the higher
the charge of the ion, the more effective it is in
Experiment Initial rate of
[A] [B]
reaction
bringing about coagulation. Here, the cations
(in mol L−1) (in mol L−1) available are Al 3+ (from AlCl 3 ), Ba 2+ (from BaCl 2 )
(in mol L−1 min −1)
and Na + (from Na 3PO 4 and NaCl). So, their power
I. 0.10 0.20 6.93 × 10 −3
to coagulate As 2S3 . (S2− ) will follow the order as
II. 0.10 0.25 6.93 × 10 −3
Al 3+ > Ba 2+ > Na +
−2
III. 0.20 0.30 .
1386 × 10
19. The correct match between item-I and
The time (in minutes) required to consume Item-II is
half of A is A. Benzaldehyde P. Dynamic phase
(a) 5 (b) 10 (c) 100 (d) 1 B. Alumina Q. Adsorbent
[JEE Main 2019, 9 Jan Shift-I] C. Acetonitrile R. Adsorbate
(a) (A) → (R) ; (B) → (Q); (C) → (P)
Exp. (b)
(b) (A) → (P); (B) → (R); (C) → (Q)
Let, the rate expression is r ∝ [ A]a [B] b .
(c) (A) → (Q); (B) → (P); (C) → (R)
From experiment I, (d) (A) → (Q); (B) → (R); (C) → (P)
a b
r2  0.1  0.25  [JEE Main 2019, 9 Jan Shift-II]
=  × 
r1  0.1  0.20 
Exp. (a)
6.93 × 10− 3
b
= 1 ×  
5
⇒ Using the principle of adsorption chromatography,
6.93 × 10− 3  4 qualitative and quantitative analysis of
b 0 b benzaldehyde can be done from its mixture with
1 =   ⇒   =  
5 5 5
⇒ ⇒ b =0 acetonitrile. Here, a mobile phase moves over a
 4  4  4 stationary phase (adsorbent). Adsorbents used
a b are alumina (Al 2O 3 ) and silica gel. The sample
r3  0.2   0.30 
From experiment II, =  ×  solution of benzaldehyde and acetonitrile when
r1  0.1   0.20 
comes in contact with the adsorbent,
1.386 × 10− 2 benzaldehyde gets adsorbed on the surface of the
⇒ = (2 )a × (1.5)0
0.693 × 10− 2 adsorbent. So, benzaldehyde acts as absorbate
whereas acetonitrile starts moving as mobile
⇒ 2 = 2 a × 1 ⇒ 21 = 2 a ⇒ a =1
phase over the stationary phase of the adsorbate.
⇒ So, r ∝ [ A]1[B]0 ⇒ r ∝ [ A] Hence, act as dynamic phase.

● In Haber’s process
20. For the reaction, 2 A + B → products Fe( s), Mo( s)
When concentration of both (A and B) N2 (g ) + 3H2 (g ) → 2NH3 (g )
becomes double, then rate of reaction ● Hydrogenation of vegetable oils,
increases from 0.3 mol L −1 s −1 to [(Ph P) Rh] Cl
2.4 mol L −1 s −1. Vegetable oil(l) 
3 3
→ Vanaspati( s )
(Unsaturated) or Ni ( s )
When concentration of only A is doubled, ● Ostwald’s process,
the rate of reaction increases from Pt( s)
0.3 mol L −1 s −1 to 0.6 mol L −1 s −1. 4NH3 (g ) + 5O 2 (g ) → 4NO(g ) + 6H2O(g )
V2O 5( s)
Which of the following is true? ● No catalyst is used in combustion of coal. The
(a) The whole reaction is of 4th order reaction is highly spontaneous in nature.
(b) The order of reaction w.r.t. B is one
C + O 2 → CO 2
(c) The order of reaction w.r.t. B is 2 (Coal)
(d) The order of reaction w.r.t. A is 2 22. Consider the given plots for a reaction
[JEE Main 2019, 9 Jan Shift-II] obeying Arrhenius equation
Exp. (c) (0°C < T < 300°C) : ( k and Ea are rate constant
For the reaction, 2 A + B → products. and activation energy, respectively)
Let, the rate expression is r ∝ [ A]a [B]b
a b
r2  2 A   2 B 
Expt 1 =   
r1  A   B  k k
2.4
⇒ = 2 a × 2 b ⇒ 2 3 = 2 a + `b
0.3
Ea T(°C)
⇒ 3 = a + b … (i)
a b
I II
r2  2 A   B  Choose the correct option.
Expt 2 =   
r1  A   B  [JEE Main 2019, 10 Jan Shift-I]
0.6 (a) Both I and II are wrong
⇒ = 2 a × 1 ⇒ 21 = 2 a ⇒ a = 1…(ii)
0.3 (b) Both I and II are correct
∴ From Eq. (i), 1 + b = 3 ⇒ b = 2 (c) I is wrong but II is right
⇒ Order of the reaction (n) = a + b = 1 + 2 = 3 (d) I is right but II is wrong
⇒ Order of the reaction wrt. A = 1
Exp. (b)
⇒ Order of the reaction wrt. B = 2
The Arrhenius equation is, k = A.e − Ea / RT
21. Which of the following is not an example of where, k = rate constant,
heterogeneous catalytic reaction? A = Arrhenius constant, Ea = activation energy,
(a) Haber’s process and T = temperature in K
(b) Combustion of coal From the equation, it is clear that k decreases
(c) Hydrogenation of vegetable oils exponentially with Ea . So, the plot-I is correct.
(d) Ostwald’s process In the plot-II, k is plotted with temperature (in °C but
[JEE Main 2019, 10 Jan Shift-I] not in K). So, at 0°C, k ≠ 0 and k will increase
exponentially with temperature upto 300°C.
Exp. (b) Therefore, the plot-II is also correct.
In heterogeneous catalytic reactions, physical
state of reactants and that of catalyst(s) used are 23. For an elementary chemical reaction,
k1
different.
Haber’s process, hydrogenation of vegetable oils
A2 =2 A , the expression for ddt[A ] is
k −1
and Ostwald’s process all are heterogeneous (a) 2k1 [A 2 ] − k −1 [A ]2 (b) k1 [A 2 ] − k −1 [A ]2
process. Combustion of coal is not a
(c) 2k1 [A 2 ] − 2k −1 [A ] 2
(d) k1 [A 2 ] + k −1 [A ]2
heterogeneous catalytic reaction.

Exp. (c) (ii) Very strong bonds which are formed.

k1 Both properties arise from, small size of
The elementary reaction, A2 c k −1
2A fluorine. I2 is being the least reactive halogen,
it requires a catalyst for the reaction.
follows opposing or reversible kinetics,
H2 + I2 → 2HI
(i) Rate of the reaction,

r = rforward − rbackward 26. An example of solid sol is
= k1[ A2 ] − k− 1[ A]2 … (i) (a) gem stones (b) hair cream
(c) butter (d) paint
(ii) Again, rate of the reaction can be expressed
d [ A2 ] 1 d[ A] [JEE Main 2019, 11 Jan Shift-I]
as, r = − =+
dt 2 dt Exp. (a)
So, the rate of appearance of A,
d[ A] Solid sol consists of solid as both dispersed phase
i.e. = 2 r = 2 k1[ A2 ] − 2 k− 1 [ A]2 and dispersion medium. In gemstones, metal
dt crystals (salt and oxides of metals) are dispersed
[From Eq. (i)] in solid (stone) medium. Hair cream is an emulsion
(liquid in liquid). Butter is a colloidal solution of
24 Haemoglobin and gold sol are examples of liquid in solid. Paint is also sol (solid in liquid).
(a) negatively and positively charged sols,
respectively 27. If a reaction follows the Arrhenius equation,
(b) negatively charged sols the plot lnk vs 1/(RT) gives straight line with
(c) positively charged sols a gradient (−y) unit.
(d) positively and negatively charged sols, The energy required to activate the reactant
respectively [JEE Main 2019, 10 Jan Shift-II] is [JEE Main 2019, 11 Jan Shift-I]
y
(a) unit (b) −y unit (c) yR unit (d) y unit
Exp. (d) R
Haemoglobin and gold sol both are colloids and
always carry an electric charge. Haemoglobin is a Exp. (d)
positively charged sol, because in haemoglobin, The temperature dependence of rate of a chemical
Fe 2+ ion is the central metal ion of the octahedral reaction is expressed by Arrhenius equation as,
complex. k = Ae − Eα / RT …(i)
All metal sols like, Au-sol, Ag-sol etc; are
where, A = Arrhenius factor or frequency factor or
negatively charged sols.
pre-exponential factor
25 Among the following reactions of hydrogen R = Gas constant, Ea = Activation energy
with halogens, the one that requires a Taking log on both sides of the Eq. (i), the
E
catalyst is equation becomes ln k = ln A − a
(a) H2 + Cl 2 → 2HCl (b) H2 + I2 → 2HI RT
(c) H2 + F2 → 2HF (d) H2 + Br2 → 2HBr
ln/k
Exp. (b)
Chemical reactivity of halogens decreases down
the group. 1/RT
The chemical reactivity follows the order.
On comparing with equation of straight line
∴ F2 > Cl 2 > Br2 > I2 . 1
(y = mx + c), the nature of the plot of lnk vs will
The highest reactivity of fluorine is attributed to two RT
factors: be:
(i) The low dissociation energy of F—F bond (i) Intercept = C = ln A
(which results in low attraction energy for the (ii) Slope/gradient = m = − Ea = − y ⇒ Ea = y
reaction). So, the energy required to activate the reactant,
(activation energy of the reaction, Ea is = y )

28. The reaction, 2 X → B is a zeroth order Exp. (a)

reaction. If the initial concentration of X is Dispersed Dispersion Type of Examples
0.2 M, the half-life is 6 h. When the initial phase medium colloid
concentration of X is 0.5 M, the time Liquid Solid Gel Cheese (C),
required to reach its final concentration of butter, jellies

0.2 M will be Liquid Liquid Emulsion Milk (M), hair
(a) 7.2 h cream
(b) 18.0 h Solid Gas Aerosol Smoke (S),
(c) 12.0 h dust
(d) 9.0 h [JEE Main 2019, 11 Jan Shift-II]
Thus, C : liquid in solid, M : liquid in liquid and S :
Exp. (b) solid in gas.
For zero order reaction,
30. Given, Gas : H 2 , CH 4 , CO2 , SO2
[ A0 ] − [ At ] = kt ...(i)
where, [ A0 ] = initial concentration
Critical temperature/K 33 190 304 630
On the basis of data given above, predict
[ At ] = final concentration at time ‘t’
which of the following gases shows least
k = rate constant
adsorption on a definite amount of
[A ]
Also, for zero order reaction, t 1/ 2 = 0 charcoal?
2k (a) CH4 (b) SO2
Given, t 1/ 2 = 6 h (c) CO2 (d) H2
and [ A0 ] = 0.2 M [JEE Main 2019, 12 Jan Shift-I]
0.2
∴ 6= Exp. (d)
2k
Same adsorbant (charcoal in this case) at same
02. 1
or, k= = temperature will adsorb different gases to different
2 × 6 60 extent. The extent to which gases are adsorbed is
Now, from Eq. (i) proportional to the critical temperature of gas.
8a
[ A0 ] − [ At ] = kt Q Tc =
27 Rb
Given, [ A0 ] = 0.5 M, [ At ] = 02
. M
where, a is the magnitude of intermolecular forces
∴ 0.5 − 02 . =
1
×t Qk = 1  between gaseous molecules.
60  60 
Thus, higher the cirtical temperature more is the
1 gas adsorbed. Among the given gases, H2 has the
0.3 = ×t
60 minimum critical temperature, i.e. 33K thus, it
t = 0.3 × 60 = 18 h shows least adsorption on a definite amount of
charcoal.
29. Among the colloids cheese (C ), milk ( M ) and
smoke (S), the correct combination of the
31. Among the following, the false statement is
(a) Tyndall effect can be used to distinguish
dispersed phase and dispersion medium, between a colloidal solution and a true
respectively is solution
(a) C : liquid in solid; M : liquid in liquid; (b) It is possible to cause artificial rain by
S : solid in gas throwing electrified sand carrying charge
(b) C : solid in liquid; M : liquid in liquid; opposite to the one on clouds from an
S : gas in solid aeroplane
(c) Lyophilic sol can be coagulated by adding an
(c) C : liquid in solid; M : liquid in solid;
electrolyte
S : solid in gas
(d) Latex is a colloidal solution of rubber particles
(d) C : solid in liquid; M : solid in liquid; which are positively charged
S : solid in gas [JEE Main 2019, 11 Jan Shift-II] [JEE Main 2019, 12 Jan Shift-II]

Exp. (d) k2
ln = 2.303
10− 5
Statement given as statement (d) is incorrect.
k2
Latex is a stable dispersion, i.e. emulsion of = 10 ⇒ k2 = 10− 4 s −1
polymer microparticles in an aqueous medium. 10−5
These microparticles belong to rubber and are Therefore, rate constant for the reaction at
negatively charged in nature. Natural latex 500 K is 10− 4s − 1.

contains some amount of sugar, resin, protein and
ash as well. 33. At 518°C, the rate of decomposition of a
The closest synthetic latex that can be associated sample of gaseous acetaldehyde, initially at
with the properties of natural latex is SBR, i.e. a pressure of 363 Torr, was 1.00 Torr s −1
Styro Butane Rubber. when 5% had reacted and 0.5 Torr s −1 when
Rest of all the statements are correct. 33% had reacted. The order of the reaction is :
[JEE Main 2018]
32. For a reaction, (a) 2 (b) 3 (c) 1 (d) 0
consider the plot
Slope = –4606 Exp. (a)
of lnk versus1 /T ln k
given in the For the reaction,
figure. If the rate Decomposes
CH3CHO( g ) → CH4 + CO
constant of this 1/ T
reaction at 400 K Let order of reaction with respect toCH3CHO is m.
is10− 5 s − 1, then the rate constant at 500 K is Its given, r1 = 1 torr/sec. when CH3CHO is 5%
reacted i.e. 95% unreacted. Similarly, r2 = 0.5
(a) 4 × 10− 4 s− 1 (b) 10− 6 s− 1
−4 −1
torr/sec when CH3CHO is 33% reacted i.e., 67%
(c) 10 s (d) 2 × 10− 4 s− 1 unreacted.
[JEE Main 2019, 12 Jan Shift-II] Use the formula,
Exp. (c) r ∝ (a − x)m
The temperature dependence of a chemical where (a − x) = amount unreacted
m
reaction is expressed by Arrhenius equation, r1 (a − x1 )m r1  a − x1 
− E / RT so, = or = 
k = Ae a$ …(i) r2 (a − x2 )m r2  a − x2 
Taking natural logarithm on both sides, the Now putting the given values
Arrhenius equation becomes, m
= 
1 0.95 
ln k = ln A − a
E 
0.5  0.67 
RT
E ⇒ 2 = (141
. )m or m = 2
where, − a is the slope of the plot and ln A gives
R
the intercept. 34. Two reactions R1 and R 2 have identical
Eq. (i) at two different temperatures for a reaction preexponential factors. Activation energy of
becomes, R1 exceeds that of R 2 by 10 kJ mol− 1. If k1 and
k E 1 1 k 2 are rate constants for reactionsR1 andR 2,
ln 2 = a  −  …(ii)
k1 R  T1 T2  k 
respectively at 300 K, then ln  2  is equal to
⇒ In the given problem,  k1 
T1 = 400 K, T2 = 500 K, k1 = 10− 5 s − 1, k2 = ? (R = 8.314 J mol − 1K − 1 ) [JEE Main 2017 (Offline)]
E
− a (Slope) = − 4606 (a) 8 (b) 12 (c) 6 (d) 4
R
On substituting all the given values in Eq. (ii), we get Exp. (d)
ln −2 5 = 4606 
k 1 1  According to Arrhenius equation
− 
10  400 500  k = Ae − Ea / RT

where, A = collision number or pre-exponential factor.

36. For a linear plot of log ( x /m ) versus log p in a
R = gas constant, T = absolute temperature
Freundlich adsorption isotherm, which of
Ea = energy of activation
the following statements is correct? (k and n
− Ea1 / RT are constants) [JEE Main 2016 (Offline)]
For reaction R1, k1 = Ae …(i)
− Ea2 / RT (a) 1/n appears as the intercept

For reaction R 2 , k2 = Ae …(ii)
(b) Only 1/n appears as the slope
On dividing Eq. (ii) by Eq. (i), we get
(c) log   appears as the intercept
1
( Ea − Ea )
k2 − 2 1
n
=e RT …(iii)
k1 (d) Both k and 1/n appear in the slope term
[Q Pre-exponential factor ‘A’ is same for both
reactions] Exp. (b)
Taking ln on both the sides of Eq. (iii), we get According to Freundlich adsorption isotherm,
 k  E a1 − E a 2 x
ln 2  = = kp1/ n
 k1  RT m
On taking logarithm of both sides, we get
Given, E a 1 = E a 2 + 10 kJ mol − 1
x
= Ea 2 + 10,000 J mol − 1 log = log k + log p1/ n
m
k2 10,000 J mol − 1 x 1
= log k + log p
∴ ln = =4 or log
k1 8.314 J mol − 1K − 1 × 300 K m n
y = c + mx
35. The Tyndall effect is observed only when
following conditions are satisfied
Slope= 1
[JEE Main 2017 (Offline)] θ n
log x/m
I. The diameter of the dispersed particles is

much smaller than the wavelength of the
light used. log k
II. The diameter of the dispersed particle is
not much smaller than the wavelength of log p
the light used.
x
III. The refractive indices of the dispersed y = log , c = intercept = log k,
phase and dispersion medium are almost m
similar in magnitude. 1
m = slope =
IV. The refractive indices of the dispersed n
phase and dispersion medium differ and x = log p
greatly in magnitude.
(a) I and IV (b) II and IV 37. Decomposition of H 2O2 follows a first order
(c) I and III (d) II and III reaction. In 50 min, the concentration of
H 2O2 decreases from 0.5 to 0.125 M in one
Exp. (b) such decomposition. When the concentration
Colloidal solutions show Tyndall effect due to ofH 2O2 reaches 0.05 M, the rate of formation
scattering of light by colloidal particles in all
directions in space. It is observed only under the of O2 will be [JEE Main 2016 (Offline)]
following conditions. −4 −1
(a) 6.93 × 10 mol min
(i) The diameter of the colloids should not be
(b) 2.66 L min −1 at STP
much smaller than the wavelength of light used.
(c)1.34 × 10−2 mol min −1
(ii) The refractive indices of the dispersed phase
and dispersion medium should differ greatly (d) 6.93 × 10−2 mol min −1
in magnitude.

Exp. (a) 39. Match the catalysts to the correct processes.

2.303 a
For first order reaction, k = log [JEE Main 2015]
t a− x
Catalyst Process
Given, t = 50 min, a = 0.5 M, a − x = 0125
. M
2.303 0. 5 (A) TiCl 3 (i) Wacker process
∴ k= = 0.0277 min−1
log
50 0125
. (B) PdCl 2 (ii) Ziegler- Natta
polymerisation
Now, as per reaction
(C) CuCl 2 (iii) Contact process
2H2O 2 → 2H2O + O 2
1 d [H2O 2 ] 1 d [H2O] d [O 2 ] (D) V2O 5 (iv) Deacon's process
− = =
2 dt 2 dt dt (a) (A)- (iii), (B) - (ii), (C) - (iv), (D) - (i)
d [H2O 2 ] (b) (A)- (ii), (B) - (i), (C) - (iv), (D) - (iii)
Rate of reaction, − = k [H2O 2 ]
dt (c) (A)- (ii), (B) - (iii), (C) - (iv), (D) - (i)
d [O 2 ] 1 d [H2O 2 ] 1 (d) (A)- (iii), (B) - (i), (C) - (ii), (D) - (iv)
∴ =− = k[H2O 2 ] …(i)
dt 2 dt 2
Exp. (b)
When the concentration of[H2O 2 ] reaches 0.05 M,
d [O2 ] 1 (a) TiCl 3 is used as Ziegler-Natta catalyst for the
= × 0.0277 × 0.05[from Eq. (i)] polymerisation of ethene.
dt 2
d [O2 ] (b) PdCl 2 is used in Wacker process, in which
or = 6.93 × 10−4 mol min −1 alkene changed into aldehyde via catalytic
dt
cyclic process initiated by PdCl 2 .
Alternative Method
(c) CuCl 2 is used in Deacon's process. (for Cl 2 )
In fifty minutes, the concentration of H2O 2 decreases
(d) V2O 5 is used in contact process of
from 0.5 to 0.125 M or in one half-life, concentration
manufacturing sulphuric acid.
of H2O 2 decreases from 0.5 to 0.25 M. In two
half-lives, concentration of H2O 2 decreases from Time Saving Technique This type of questions
0.5 to 0.125 M or 2 t 1/ 2 = 50 min can also be solved through elimination technique.
There is no need to know all the four matches to
t 1/ 2 = 25 min
select the correct response. Even if you know (b)
k = 
0.693  −1
∴  min matches then also you can solve the problem. e.g.
 25 
suppose you know the usage of V2O 5 in contact
d [O 2 ] 1 d [H2O 2 ] k[H2O 2 ] process (i.e. D matches with (iii) and TiCl 3 is
or =− =
dt 2 dt 2 connected to Ziegler-Natta catalyst (i.e. A matches
= 6.93 × 10−4 mol min−1 with ii).
These two combinations are present only in option
38. Higher order (>3) reactions are rare due to number (b). Likewise, for this question particularly
[JEE Main 2015] if you know that V2O 5 is used in contact process
(a) low probability of simultaneous collision of all then this combination is present in option (b) only
the reacting species out of all the four option given. In this way you can
(b) increase in entropy and activation energy as eliminate wrong options to get the correct response.
more molecules are involved
(c) shifting of equilibrium towards reactants due 40. For the non-stoichiometric reaction,
to elastic collisions 2 A + B → C + D, the following kinetic
(d) loss of active species on collision data were obtained in three separate
experiments, all at 298 K. [JEE Main 2014]
Exp. (a)
Initial Initial Initial rate of
The main conditions for the occurrence of a reaction concentration concentration formation of C
is proper orientation and effective collision of the (A) (B) (mol L −1 s −1)
reactants.
0.1 M 0.1 M 1.2 × 10 −3
Since the chances of simultaneous collision with
proper orientation between more than 3 species is 0.1 M 0.2 M 1.2 × 10 −3
very rare, so reaction with order greater than 3 are
0.2 M 0.1 M 2. 4 × 10 −3
rare.

The rate law for the formation of C is k2

Given, = 2 ; T2 = 310 K
dc dc k1
(a) = k [A ][B ] (b) = k [A ]2 [B ]
dt dt T1 = 300 K
dc dc
(c) = k [A ][B ]2 (d) = k [A ] On putting values,
dt dt
− Ea
⇒ log 2 =  1 − 1 
 
Exp. (d) 2.303 × 8.314  310 300 
Rate law equation is given by ⇒ Ea = 53603.93 J/mol = 53.6 kJ/mol
dc
= k [ A] x [B] y
dt 42. The coagulating power of electrolytes having
dc ions Na + , Al 3+ andBa 2+ for arsenic sulphide
∴ for C at various concentrations are
dt sol increases in the order [JEE Main 2013]
1.2 × 10−3 = k(0.1) x (0.1) y …(i) (a) Al 3 + < Ba 2 + < Na + (b) Na + < Ba 2 + < Al 3 +
−3
1.2 × 10 = k(0.1) (0.2 )
x y
…(ii) (c) Ba 2 + < Na 2 + < Al 3 + (d) Al 3 + < Na + < Ba 2 +
2 . 4 × 10−3 = k(0.2 ) x (0.1) y …(iii)
Exp. (b)
Solving for x [divide Eq. (iii) by Eq. (i)] According to Hardy Schulze rule, greater the
2 . 4 × 10−3 k (0.2 ) x (0.1) y charge on oppositely charged ion, greater is its
= coagulating power. Since arsenic sulphide is a
1.2 × 10−3 k (0.1) x (0.1) y
negatively charged sol, thus, the order of
2 = (2 ) x ⇒ x = 1 coagulating power is Na + < Ba 2 + < Al 3 + .
Solving for y [divide Eq. (iii) by Eq. (i)]
2 . 4 × 10−3 k (0.2 ) x (0.1) y
43. According to Freundlich adsorption isotherm
−3
= which of the following is correct?
1.2 × 10 k (0.1) x (0.2 ) y
[AIEEE 2012]
y
x
0.1  x
(a) ∝ p 0
x
(b) ∝ p1
x
(c) ∝ p1/n
2 = (2 )  
 0.2  m m m
(d) All of the above are correct for different range of
Put x = 1in above Eq., we get
y
pressure
 0.1 
2 = (2 )′   Exp. (d)
 0.2 
By Freundlich adsorption isotherm
1 = (0. 5) y
x
= kp1/ n
(1)0 = (0. 5) y ⇒ y=0 m
dc dc [In between low and high pressure range]
Thus, = k [ A]1 [B] 0 ⇒ = k [ A]1
dt dt x
When n = 1, ∝ p1 [In low pressure range]
m
41. The rate of a reaction double when its x
When n is large, = k [Independent of pressure]
temperature changes from 300 K to 310 K. m
Activation energy of such a reaction will be
(R = 8.314 JK −1 mol −1 and log 2 = 0.301)
( mx ∝ p)
−1
[JEE Main 2013]
−1
x ( mx ∝ p )
0
(a) 53.6 kJ mol (b) 48.6 kJ mol m

(c) 58.5 kJ mol −1 (d) 60.5 kJ mol −1
Exp. (a) ( mx ∝ p )
1/n
From Arrhenius equation, pressure (p)

k − Ea 1 1 x
log 2 =  −  Thus, ∝ p0 [At high pressure range when
k1 2.303 R  2
T T1 m saturation point is reached]

44. For a first order reaction, ( A ) → products Exp. (b)

the concentration of A changes from 0.1 M k1 k2
to 0.025 M in 40 min. The rate of reaction A → B, A  → C,
when the concentration of A is 0.01 M is By Arrhenius equation,
[AIEEE 2012] − Ea 1 / RT
k1 = A′e
(a) 1.73 × 10−5 M / min − Ea 2 / RT

(b) 3.47 × 10−4 M / min and k2 = A ′ e .[A' is Arrhenius constant]
(c) 3.47 × 10−5 M / min Q Ea 2 = 2 Ea1
(d) 1.73 × 10−4 M / min ∴ k2 = A ′ e
−2 Ea1 / RT
Exp. (b) − Ea / RT
k1 A ′e 1 E / RT
Rate constant for the first order reaction is given by = −2 Ea 1 / RT
= e a1
k2 A ′e
2.303  a 
k= log   ∴ k1 = k2 e
Ea / RT
1
t  a − x
a = 0.1 M 47. The time for half-life period of a certain
(a − x) = 0.025 M
reaction, A → products is 1 h. When the
t = 40 min
initial concentration of the reactant ‘A’ is
∴ k=
2.303
log
0.1
= 0.0347 min−1 2.0 mol L −1, how much time does it take for
40 0.025 M its concentration to come from 0.50 to
Rate =   = k[ A]1 = 0.0347 × 0.1
dx 0.25 mol L−1, if it is a zero order reaction?
 dt  (a) 4 h (b) 0.5 h [AIEEE 2010]
= 3.47 × 10–4 M min–1 (c) 0.25 h (d) 1 h
45. The rate of a chemical reaction doubles for Exp. (c)

every 10°C rise of temperature. If the Half- life for a zero order reaction is given by
temperature is raised by 50°C, the rate of the [A ]
t 1/ 2 = 0
reaction increases by about [AIEEE 2011] 2k
(a) 10 times (b) 24 times [where [ A0 ] = initial concentration of reactant]
(c) 32 times (d) 64 times [ A]0 2. 0 mol L−1
⇒ k0 = = = 1. 0 mol L−1 h−1
Exp. (c) 2 t 1/ 2 2 × 1h
For every 10°C rise of temperature, rate is Rate constant for a zero order reaction is given by
doubled. Thus, temperature coefficient of the 1 1
k = [( A0 ) − ( A)] ⇒ t = [( A0 ) − ( A)]
reaction = 2 t k
When temperature is increased by 50°, rate (0.50) − (0 .25) mol L−1
becomes t = ⇒ t = 0.25 h
1 mol L−1 h−1
=2 ( 50 10 )
= 2 times = 32 times
5
48. Consider the reaction,

46. A reactant (A) forms two products Cl 2(aq ) + H 2S(aq ) →
A
k1
→ B , Activation energy E a 1 S(s ) + 2H + (aq ) + 2Cl − (aq )
A
k2
→C , Activation energy E a 2 The rate equation for this reaction is,
If E a 2 = 2 E a 1 , then k1 and k 2 are related as rate = k[Cl 2] [H 2S]
[AIEEE 2011] Which of these mechanisms is/are consistent
E a 2 / RT E a 1 / RT with this rate equation? [AIEEE 2010]
(a) k1 = 2k 2 e (b) k1 = k 2 e
E a 2 / RT E a 1 / RT
(I) Cl 2 + H 2 S → H + + Cl – + Cl + + HS – (slow)
(c) k 2 = k1 e (d) k1 = Ak 2 e
Cl + + HS– → H + + Cl – + S (fast)

+
+ HS − 1
(II) H 2 S ºH (fast equilibrium) 51. For a reaction A → 2 B , rate of
Cl 2 + HS − −
→ 2 Cl + H + S +
(slow) 2
disappearance of ‘A’ is related to the rate of
(a) (II) only (b) Both (I) and (II) appearance of ‘B’ by the expression
(c) Neither (I) nor (II) (d) (I) only [AIEEE 2008]
d [A ] 1 d [B ] d [A ] 1 d [B ]
Exp. (d) (a) − = (b) − =
dt 2 dt dt 4 dt
Slowest step is the rate determining step. Thus, in
case (I), rate law is given as rate = k[Cl 2 ][H2S] d [A ] d [B ] d [A ] d [B ]
(c) − = (d) − =4
While for the reaction given in case (II), rate law is dt dt dt dt
given as rate = k[H2S][Cl 2 ][H+ ]–1.
Exp. (b)
Hence, only mechanism (I) is consistent with the 1
A → 2 B
given rate law. 2
49. Which of the following statements is Remember for a A → bB
incorrect regarding physisorptions? 1 d [ A] 1 d [B]
− = = Rate of reaction
(a) It occurs because of van der Waals’ forces a dt b dt
(b) More easily liquefiable gases are adsorbed For the given reaction
readily 2d [ A] 1 d [B]
(c) Under high pressure, it results into multi − = = Rate of reaction
dt 2 dt
molecular layer on adsorbent surface d [ A]
(d) Enthalpy of adsorption ( ∆H adsorption ) is slow Rate of disappearance of A = −
dt
and positive [AIEEE 2009] 1 d [B] 1 d [B]
= =
2 × 2 dt 4 dt
Exp. (d)
Adsorption is an exothermic process i .e., energy is 52. Gold numbers of protective colloids A, B, C
released against van der Waals’ force of attraction and D are 0.50, 0.01, 0.10 and 0.005,
(physisorptions). respectively. The correct order of their
Hence, ∆H is always negative. protective powers is [AIEEE 2008]
50. The half-life period of a first order chemical (a) D < A < C < B (b) C < B < D < A
reaction is 6.93 min. The time required for (c) A < C < B < D (d) B < D < A < C
the completion of 99% of the chemical
reaction will be (log 2 = 0.301) [AIEEE 2009] Exp. (c)
(a) 230.3 min (b) 23.03 min Higher the gold number, lesser will be the
(c) 46.06 min (d) 460.6 min protective power of colloid.
Exp. (c) 53. Consider the reaction, 2 A + B → product.
0.693
Half-life = 6 .93 min, k1 = = 0.1min −1 When concentration of B alone was
6.93 doubled, the half-life did not change. When
Rate constant for the first order reaction is given by the concentration of A alone was doubled,
2.303 [A ] the rate increased by two times. The unit of
k= log 0
t [ A] rate constant for this reaction is [AIEEE 2007]
where, [ A0 ] = initial concentration (a) L mol −1 s−1 (b) no unit
[ A] = final concentration (c) mol L−1 s−1 (d) s−1
2.303 100
0.1 = × log Exp. (a)
t 1
2.303 2 A + B → Products
0.1 = log 10 2
t [B] is doubled, half-life didn’t change.
2.303 × 2 Half-life is independent of change in
t = × 2 log 10 = 46.06 min concentration of reactant i.e., first order
0.1
First order wrt to B

When [ A] is doubled, rate increased by two times. 1

n= = 3.32
⇒ First order wrt A 0.301
Hence, net order of reaction = 1 + 1 = 2 Time = n × half-life
Unit for the rate constant = conc( 1− n ) t −1 = 3.32 × 30 = 99.6 days
= (mol L−1 )−1 ⋅ s −1 ≈ 100 days
Alternate method
= Lmol −1 s −1
Let the activity of safe working is A.
Given, A 0 = 10 [ A]
54. The energies of activation for forward and Radioactivity decay is the first order reaction.
reverse reactions for A 2 + B 2 2 AB are
r Let the activity of safe working is A.
180 kJ mol −1 and 200 kJ mol −1, respectively. It is given that,
The presence of a catalyst lowers the A 0 = 10 [ A]
activation energy of both (forward and
Half-life of a first order reaction is given by
reverse) reactions by 100 kJ mol −1. The
0. 693 0. 693 0. 693
enthalpy change of the reaction t 1/ 2 = ⇒ k= =
k t 1/ 2 30
( A 2 + B 2 → 2 AB ) in the presence of catalyst
will be (in kJ mol −1) [AIEEE 2007]
Rate constant for a first order reaction is given by,
2. 303 A
(a) 300 (b) 120 (c) 280 (d) 20 k= log 0
t A
Exp. (d) 2. 303 A0 2. 303 10 [ A]
t = log = log
A 2 + B2 r 2 AB k A (0. 693 / 30) [ A]
Ea (forward) = 180 kJ mol −1 =
2. 303
log 10 = 99. 69 days ≈ 100 days
Ea (backward) = 200 kJ mol −1 (0. 693 / 30)
In the presence of catalyst,

56. The following mechanism has been
Ea (forward) = 180 − 100 = 80 kJ mol −1
proposed for the reaction of NO with Br2 to
Ea (backward) = 200 − 100 = 100 kJ mol −1 form NOBr
∆ H = Ea (forward) − Ea (backward) NO( g ) + Br2( g ) r NOBr (g ) 2
= 80 − 100 = − 20 kJ mol −1
NOBr2( g ) + NO ( g ) → 2NOBr ( g )
For the value of enthalpy change of the reaction,
negative sign can be neglected. If the second step is the rate determining
step, the order of the reaction with respect to
55. A radioactive element gets spilled over the NO (g) is [AIEEE 2006]
floor of a room. Its half-life period is 30 days. (a) 1 (b) 0 (c) 3 (d) 2
If the initial activity is ten times the
permissible value, after how many days will Exp. (d)
it be safe to enter the room? [AIEEE 2007] Rat = k [NOBr2 ] [NO] ...(i)
(a) 1000 days (b) 300 days But NOBr2 is in equilibrium.
(c) 10 days (d) 100 days [NOBr2 ]
∴ Keq =
Exp. (d) [NO] [Br2 ]
Activity ∝ N [NOBr2 ] = Keq [NO] [Br2 ]

n
N  1 Putting the [NOBr2 ] in Eq. (i), we get
= 
N0  2  Rate = k ⋅ Keq [NO] [Br2 ] [NO]
n
1  1 Hence, Rate = k ⋅ Keq [NO]2 [Br2 ]
or =  or 10 = 2 n
10  2  Rate = k ′ [NO]2 [Br2 ]
Taking log on both sides
where k ′ = k ⋅ Keq
log 10 = n log 2

57. Rate of a reaction can be expressed by 60. A reaction involving two different reactants
Arrhenius equation as k = Ae − E / RT can never be [AIEEE 2005]
In this equation, E represents [AIEEE 2006] (a) bimolecular reaction
(b) second order reaction
(a) the energy above which all the colliding
(c) first order reaction

molecules will react
(d) unimolecular reaction
(b) the energy below which colliding molecules
will not react Exp. (d)
(c) the total energy of the reacting molecules at a There are two different reactants (say A and B).
temperature, T A + B → product
(d) the fraction of molecules with energy greater Thus, it is a bimolecular reaction.
dx
than the activation energy of the reaction If = k [ A] [B]
dt
Exp. (b) It is second order reaction.
 dx  = k [ A] = k [B]
According to Arrhenius equation If  
 dt 
k = Ae − E / RT
It is first order reaction.
where, E is the activation energy below which the
Molecularity is independent of rate but is the sum
colliding molecules will not react.
of the reacting substances. Thus, it cannot be
58. A reaction was found to be second order unimolecular reaction.
with respect to the concentration of carbon
monoxide. If the concentration of carbon
61. t1/4 can be taken as the time taken for the
monoxide is doubled, with everything else concentration of a reactant to drop to 3/4 of
its initial value. If the rate constant for a first
kept the same, the rate of reaction will
order reaction is k , the t1/4 can be written as
(a) remain unchanged [AIEEE 2006]
[AIEEE 2005]
(b) triple (a) 0.75 / k (b) 069
. /k
(c) increase by a factor of 4 (c) 0.29 / k (d) 010
. /k
(d) double
Exp. (c) Exp. (c)
r ∝ [CO] ; r ′ ∝ [2CO] ; r ′ ∝ 4 [CO]
2 2 2 A → Product
Initially a 0
r ′ 4 [CO]2
Hence, = or r ′ = 4 r After time t ( a − x) x
r [CO]2  a − a a
After t 1/ 4  
 4 4
59. In Langmuir’s model of adsorption of a gas
on a solid surface [AIEEE 2006] For first order kinetics,
2.303  a 
(a) the rate of dissociation of adsorbed molecules k= log  
from the surface does not depend on the t  a − x
surface covered 2.303 a
∴ k= log
(b) the adsorption at a single site on the surface t 1/ 4 3a
may involve multiple molecules at the same time 4
(c) the mass of gas striking a given area of surface 4
2.303 log
is proportional to the pressure of the gas t 1/ 4 = 3 = 0.29
(d) the mass of gas striking a given area of surface k k
is independent of the pressure of the gas
62. Consider an endothermic reaction X → Y
Exp. (c) with the activation energies E b and E f for
The adsorption of a gas is directly proportional to the backward and forward reactions
the pressure of the gas. respectively. In general [AIEEE 2005]

(a) there is no definite relation between E b and

Ef
64. The disperse phase in colloidal iron (III)
(b) E b = E f
hydroxide and colloidal gold is positively
(c) E b > E f
and negatively charged, respectively. Which
(d) E b < E f
of the following statement is not correct?
(a) Coagulation in both sols can be brought about

Exp. (d) by electrophoresis
(b) Mixing the sols has no effect
X → Y is an endothermic reaction, ∆H = + ve
(c) Sodium sulphate solution causes coagulation
in both sols
(d) Magnesium chloride solution coagulates the
Eb
Energy
u gold sol more readily than the iron (III)

Ef hydroxide sol [AIEEE 2005]
∆H Exp. (b)
Mixing the sols together can cause coagulation,
since the charges are neutralised.
Eb = energy of activation of backward reaction
Ef = energy of activation of forward reaction
65. The volume of a colloidal particle, VC as
∆H = heat of reaction compared to the volume of a solute particle
Thus, Ef = Eb + ∆H, Ef > Eb in a true solutionV S , could be [AIEEE 2005]
VC VC
63. A schematic plot of lnK eq versus inverse of (a) ≈103 (b) ≈ 10−3
VS VS
temperature for a reaction is shown below
VC VC
6.0 (c) ≈1023 (d) ≈1
VS VS
In Keq Exp. (a)

Size of colloidal particles = 1to 100 nm
2×10–3 (say 10 nm)
4 4
2.0 VC = πr 3 = π (10)3
1.5×10–3 3 3
1/T(K–1) Size of true solution particles ≈ 1nm
4
The reaction must be [AIEEE 2005] VS = π (1)3
3
(a) highly spontaneous at ordinary temperature VC
(b) one with negligible enthalpy change Thus, = 103
VS
(c) endothermic
(d) exothermic
66. The rate equation for the reaction
Exp. (d) 2 A + B → C is found to be rate = k [A] [B]
The correct statement in relation to this
Variation of Keq with temperature T is given by
van’t Hoff equation. reaction is that the [AIEEE 2004]
∆ H° ∆S ° (a) unit of k must be s−1
log Keq = − + (b) t 1/ 2 is a constant
2.303 RT R
A B (c) rate of formation of C is twice the rate of
Slope of the given line is positive indicating that disappearance of A
term A is positive, thus ∆H° is negative. (d) value of k is independent of the initial
concentrations of A and B
Thus, reaction is exothermic.

Exp. (d) Exp. (c)

2 A + B → C By Arrhenius equation,
Rate = k [ A] [B] k = Ae − Ea / RT ,
It represents second order reaction. k = Rate constant
Thus, unit of k is L mol −1 s −1. A = Pre-exponential, frequency factor
Hence, (a) is false. Ea = Activation energy, R = Gas constant

t 1/ 2 is dependent of concentration but not T = Temperature
constant. Hence, (b) is false.
1 d [ A] d [C ] 69. The rate law for a reaction between the
And − =
2 dt dt substances A and B is given by
Thus, (c) is also false. rate = k [ A ]n [B ]m . On doubling the
67. In a first order reaction, the concentration of concentration of A and halving the
the reactant, decreases from 0.8 M to 0.4 M in concentration of B, the ratio of the new rate
15 min. The time taken for the concentration to the earlier rate of the reaction will be as
to change from 0.1 M to 0.025 M is [AIEEE 2004] 1
(a) (b) (m + n )
(a) 30 min (b) 15 min (c) 7.5 min (d) 60 min 2m + n
(c) (n − m ) (d) 2 (n − m ) [AIEEE 2003]
Exp. (a)
Order = 1 Exp. (d)
Concentration changes from 0.8 M to 0.4 M in Rate, r = k [ A]n [B]m
(50%).
On doubling [ A] and halving[B], the rate becomes
15 min, thus half-life = 15 min = T50
r ′ = k [2 A]n [1 / 2 B]m
A change from 0.1 M to 0.025 is 75% and for first
order reaction r ′ k [2 A]n [1 / 2 B]m (2 )n
⇒ = = m = (2 )n ⋅ (2 )− m
T75 = 2 × T50 = 2 × 15 = 30 min r k [ A]n [B]m (2 )
Alternate method = (2 )n − m
T50 = 15 min 70. For the reaction system,
k=
2.303 log 2 2.303 log2
= 2NO( g ) + O2( g ) → 2NO2( g )
T50 15
volume is suddenly reduced to half its value
a = 0.1 M ⇒ (a − x) = 0.025 M
by increasing the pressure on it. If the
For first order
reaction is of first order with respect to O 2
2.303  a 
k= log   and second order with respect to NO; the
t  a − x rate of reaction will [AIEEE 2003]
2.303 log 2 2.303 0.1 2.303 (a) diminish to one-fourth of its initial value
= log = log 4 (b) diminish to one-eighth of its initial value
15 t 0.025 t
(c) increase to eight times of its initial value
2.303 log 2 2 × 2.303 log 2
∴ = (d) increase to four times of its initial value
15 t
∴ t = 30 min Exp. (c)
2
 dx  = k [NO]2 [O ] = k  nNO   nO 2 
68. In respect of the equation k = Ae − E a /RT in  
 dt  2  
 V   V 
chemical kinetics, which one of the
following statements is correct ? [AIEEE 2003]  dx  = k (n )2 (n )
 
(a) k is equilibrium constant  dt  V 3 NO O2
(b) A is adsorption factor 2

 dx  = k (nNO ) (nO 2 ) = 8  dx 
(c) E a is energy of activation    
 dt  (V /2 )3  dt 
(d) R is Rydberg constant

71. Which one of the following characteristics is 74. Rate constant, k of the first order reaction
not correct for physical adsorption? when initial concentration (C 0) and
(a) Adsorption on solids is reversible concentration (C t ) at time t , is given by
(b) Adsorption increases with increase in equation kt = log C 0 − log C t
temperature
Graph is a straight line if we plot [AIEEE 2002]

(c) Adsorption is spontaneous
(d) Both enthalpy and entropy of adsorption are (a) t vs log C 0 (b) t vs log C t
negative [AIEEE 2003] (c) t −1 vs log C t (d) log C 0 vs log C t
Exp. (b) Exp. (b)

As temperature increases desorption increases. kt = − loge Ct + loge C 0
Adsorbent + Adsorbate a Adsorbed state 1
t = − loge Ct + loge C 0
+ ∆E k
Adsorption is exothermic process (forward y = mx + c, straight line, negative slope.
direction), desorption is endothermic process
(backward direction). 75. Consider following two reactions,
According to Le-Chatelier’s principle, increase in
d[ A ]
temperature favours endothermic process. A → − = k1 [ A ]0
dt
72. For the reaction, H 2 + I 2 → 2HI, the
d [B ]
differential rate law is [AIEEE 2002] B → − = k 2 [B ]
d [H2 ] d [ I2 ] d [HI] dt
(a) − =− =2
dt dt dt k 1 and k 2 are expressed in terms of molarity
(b) − 2
d [H2 ]
=−2
d [I2 ] d [HI]
=
(mol L−1 ) and time ( s−1 ) as [AIEEE 2002]
dt dt dt (a) s−1 , M s −1 L−1 (b) M s−1 , M s−1
d [H2 ] d [I2 ] d [HI]
(c) − =− = (c) s−1 , M−1 s−1 (d) M s−1 , s−1
dt dt dt
(d) −
d [H2 ]
=−
d [I2 ] d [HI]
=
Exp. (d)
2dt 2dt dt 1 1
Unit of rate constant, k = .
Time (conc )n − 1
Exp. (b)
1 1
H2 + I2 → 2HI For k1, n = 0, k = .
t (conc )0 − 1
− d [H2 ] − d [I2 ] 1 d [HI]
Rate of reaction = = =
dt dt 2 dt Hence, conc t −1 ≡ M ⋅ s −1
− 2d [H2 ] − 2d [I2 ] d [HI] 1 1 1
or = = For k2 , n = 1, k= . = = s −1
dt dt dt t (conc. )1 − 1 t
73. For a reaction A + 2B → C, rate is given by 76. H 2 gas is adsorbed on the metal surface like
d [C] tungsten. This follows ..... order reaction.
+ = k [ A ] [B ], hence the order of the
dt [AIEEE 2002]
reaction is [AIEEE 2002] (a) third (b) second
(a) 3 (b) 2 (c) 1 (d) 0 (c) zero (d) first
Exp. (b) Exp. (c)

Rate of the reaction depend upon the Most of the reaction which takes place on the
concentration of A and Bboth, hence it is a second surface of heterogeneous catalyst proceeds
order reaction. being independent of concentration.

10
Periodicity of Elements
1. The size of the iso-electronic species Cl − , Ar Exp. (d)
and Ca 2+ is affected by The electronic configuration of given elements
[JEE Main 2019, 8 April Shift-I] are as follows :
(a) azimuthal quantum number of valence shell K(19) = 1s 2 2 s 2 2 p6 3s 2 3 p6 4s1
(b) electron-electron interaction in the outer Mg(12) = 1s 2 2 s 2 2 p6 3s 2
orbitals
Sr(38) = 1s 2 2 s 2 2 p6 3s 2 3 p6 4s 2 3d 10 4 p6 5s 2
(c) principal quantum number of valence shell
(d) nuclear charge Sc(21) = 1s 2 2 s 2 2 p6 3s 2 3 p6 4s 2 3d 1
First ionisation enthalpy (I.E.) of K is lowest among
Exp. (d) the given options. Here, the energy required to
The radius of isoelectronic species is inversely remove an electron from 4s1 is least as only one
proportional to their nuclear charge or atomic electron is present in the outermost shell. I.E. (I)
number (Z). Thus, greater the value of Z, lesser is comparatively high for Mg and Sr and two
electrons (fully-filled) are placed in s-orbital.
the radii of isoelectronic species.
Second ionisation enthalpy of K is highest
2. The IUPAC symbol for the element with among the given options.
atomic number 119 would be Now, removal of an electron occur from p6
[JEE Main 2019, 8 April Shift-II] (fully-filled). So, high energy is required to
remove the electron. From the above discussion,
(a) unh (b) uue
it can be concluded that (I.E 2 − I.E 1 ) value is
(c) uun (d) une maximum for K (potassium).
Exp. (b) 4. The element having greatest difference
Atomic number (119) = 1 1 9
un un en
between its first and second ionisation energy,
is [JEE Main 2019, 12 April Shift-I]
So, symbol of the element = uue
(a) Ca (b) Sc (c) Ba (d) K
Name of the element = ununennium
It is expected to be s-block element an alkali Exp. (d)
metal and the first element in eighth period. It is The electronic configuration of given elements
the lightest element that has not yet been are as follows :
synthesised.
K(19) = 1s 2 2 s 2 2 p6 3s 2 3 p6 4s1
3 The element having greatest difference Mg(12) =1s 2 2 s 2 2 p6 3s 2
between its first and second ionisation energy, Sr(38) = 1s 2 2 s 2 2 p6 3s 2 3 p6 4s 2 3d 10 4 p6 5s 2
is [JEE Main 2019, 9 April Shift-I]
Sc(21) = 1s 2 2 s 2 2 p6 3s 2 3 p6 4s 2 3d 1
(a) Ca (b) Sc (c) Ba (d) K

First ionisation enthalpy (I.E.) of K is lowest It possess completely filled s-orbitals. Hence,
among the given options. Here, the energy high amount of energy is required to pull the
required to remove an electron from 4s1 is least electron from the gaseous atom. Beryllium (4)
as only one electron is present in the outermost lies left to the boron (5) and on moving from left
shell. I.E. (I) is comparatively high for Mg and Sr to right an electron is added due to which
and two electrons (fully-filled) are placed in nuclear charge increases from Be to B.
s-orbital.
Second ionisation enthalpy of K is highest 7. In general, the properties that decrease and
among the given options. increase down a group in the periodic table,
Now, removal of an electron occur from p6 respectively are [JEE Main 2019, 9 Jan Shift-I]
(fully-filled). So, high energy is required to (a) electronegativity and atomic radius
remove the electron. From the above discussion, (b) electronegativity and electron gain enthalpy
it can be concluded that (I.E2 − I.E1 ) value is (c) electron gain enthalpy and electronegativity
maximum for K (potassium). (d) atomic radius and electronegativity
5. The group number, number of valence Exp. (a)
electrons and valency of an element with The summary of variation of periodic properties is
atomic number 15, respectively, are given in table below:
[JEE Main 2019, 12 April Shift I]
(a) 16, 5 and 2 (b) 15, 5 and 3 Variation
S. Periodic
(c) 16, 6 and 3 (d) 15, 6 and 2 No. property Along a Along a
period group
Exp. (b) 1. Atomic radius Decreases Increases
The group number, number of valence electrons 2. Electron gain Increases Decreases
and valency of an element with atomic number enthalpy
15 are 15, 5 and 3 respectively. Modern periodic
3. Electronegativity Increases Decreases
table is based on the atomic number. Number of
valence electrons present in an atom decides the Thus, electronegativity decreases and atomic
group number. radius increases down a group in the periodic
Electronic configuration of element having table.
atomic number 15 = 1s 2 2 s 2 2 p6 3s 2 3 p3
8. The correct option with respect to the Pauling
Valence electrons
electronegativity values of the elements is
As five electrons are present in valence shell, its
(a) P > S (b) Si < Al (c) Te > Se (d) Ga < Ge
group number is 15. Valency of element having
atomic number 15 is +3 (8 − 5 = 3).
Exp. (d)
6. In comparison to boron, beryllium has The electronegativity values of given elements on
[JEE Main 2019, 12 April Shift-II] the Pauling scale can be shown as follows:
(a) lesser nuclear charge and lesser first ionisation
enthalpy Period Group Group Group Group
(b) greater nuclear charge and lesser first ionisation No. 13 14 15 16
enthalpy 3 Al (1.5) Si (1.8) P (2.1) S (2.5)
(c) greater nuclear charge and greater first
ionisation enthalpy 4 Ga (1.6) Ge (1.8) Se (2.4)
(d) lesser nuclear charge and greater first ionisation 5 Te (2.01)
enthalpy
On moving from left to right across a period, i.e.
Exp. (d) from Ga to Se, the effective nuclear charge
In comparison to boron, beryllium has lesser increases and size decreases.
nuclear charge and greater first ionisation As a result, the value of electronegativity increases
enthalpy. due to increase in the attraction between the outer
electrons and the nucleus. Whereas on moving
Electronic configuration of Be(4) = 1s 2 , 2 s 2 .
down the group, (i.e. from Se to Te), the atomic
size increases.

Periodicity of Elements 131
As a result, the force of attraction between the the option in which the above trend is followed.
outer electron and the nucleus decreases. Hence, Option (c) is the only one in which this trend is
the electronegativity decreases. followed. Hence, it is the correct answer.
9. The element with Z = 120 (not yet discovered) 12. Which of the following represents the correct
will be an/a order of increasing first ionization enthalpy for
(a) transition metal (b) inner-transition metal Ca, Ba, S, Se and Ar ? [JEE Main 2013]
(c) alkaline earth metal (d) alkali metal (a) Ca < S < Ba < Se < Ar (b) S < Se < Ca < Ba < Ar
[JEE Main 2019, 12 Jan Shift-I] (c) Ba < Ca < Se < S < Ar (d) Ca < Ba < S < Se < Ar
Exp. (c) Exp. (c)

The element with Z = 120 will be an alkaline earth Ionisation energy increases along a period from
metal. Recently, oganesson (Og) with atomic left to right and decreases down a group. The
number 118 is named by IUPAC is a noble gas and position of given elements in the periodic table is as
placed just two place before 120. So, the general 2 16 18
electronic configuration is represented as [noble Ca S Ar
gas] ns 2 and element with Z = 120 exist as an Ba Se
alkaline earth metal. Thus, the order of increasing ∆HIE1 is
Ba <Ca <Se <S < Ar
10. Which of the following atoms has the highest
first ionisation energy? [JEE Main 2016 (Offline)] 13. The first ionisation potential of Na is 5.1 eV.
(a) Na (b) K (c) Sc (d) Rb The value of electron gain enthalpy of Na+ will
be [JEE Main 2013]
Exp. (c) (a) – 2.55 eV (b) – 5.1 eV
Order of first ionisation energy is Sc > Na > K > Rb. (c) –10.2 eV (d) + 2.55 eV
Due to poor shielding effect, removal of one
electron from 4s orbital is difficult as compared to
Exp. (b)
3s-orbital. Na → Na + + e − First IE
Na + e − → Na
+
11. The ionic radii (in Å) of N 3 − , O2– and F−
Electron gain enthalpy of Na +
respectively are [JEE Main 2015]
Because reaction is reverse so
(a) 1.36, 1.40 and 1.71 (b) 1.36, 1.71 and 1.40
(c) 1.71, 1.40 and 1.36 (d) 1.71, 1.36 and 1.40
∆Heg = − 5.1eV
Exp. (c) 14. The increasing order of the ionic radii of the
given isoelectronic species is [AIEEE 2012]
Number of electrons in N = 7 + 3 = 10
3–
(a) Cl − , Ca 2+ , K + , S 2 (b) S 2− , Cl − , Ca 2 + , K +
Number of electrons in O2 – = 8 + 2 = 10
(c) Ca 2 + , K + , Cl − , S 2− (d) K + , S 2− , Ca 2 + , Cl −
Number of electrons in F − = 9 + 1 = 10
Since, all the three species have each 10 electrons Exp. (c)
hence they are isoelectronic species. 1
It is considered that, in case of isoelectronic species For isoelectronic species, rn ∝
Z
as the negative charge increases, ionic radii
increases and therefore the value of ionic radii are Here, Z is atomic number
N3 − = 1.71 (highest among the three) Species Z Electrons
O2 − = 1.40 −
Cl 17 18
F − = 1.36 (lowest among the three)
Time Saving Technique There is no need to mug Ca 2 + 20 18
up the radius values for different ions. This K +
19 18
particular question can be solved through
2−
following time saving. S 16 18
Trick The charges on the ions indicate the size Thus, ionic size is in order
as N3 − > O 2 − > F − . Thus, you have to look for Ca 2 + < K + < Cl − < S2 −

15. Which one of the following orders presents the Exp. (d)
correct sequence of the increasing basic O 2− ,F − ,Na + ,Mg 2+ and Al 3+ are isoelectronic
nature of the given oxides? [AIEEE 2011] species.
(a) Al 2O 3 < MgO < Na 2O < K 2O For isoelectronic species, r ∝ 1/ z
Thus, larger the atomic number (effective nuclear
(b) MgO < K 2O < Al 2O 3 < Na 2O

charge) smaller is the ionic radii.
(c) Na 2O < K 2O < MgO < Al 2O 3
(d) K 2O < Na 2O < Al 2O 3 < MgO 18. The set representing the correct order of ionic
radius is [AIEEE 2009]
Exp. (a)
(a) Li + > Be 2+ > Na + > Mg 2+
In a period, the nature of oxides varies from basic
(b) Na + > Li + > Mg 2+ > Be 2+
to acidic while in a group, basic nature of oxides
increases. (c) Li 2+ > Na + > Mg 2+ > Be 2+
Thus (d) Mg 2+ > Be 2+ > Li + > Na +
Decreases In a period, basic nature
Oxides changes to acidic nature Exp. (b)
Basic nature The ionic radius in general increases moving top
Increases in a group to bottom and further decreases moving left to
Group 1 2 13 right. So the correct order is
Period 3 → Na 2O MgO Al 2O 3 Na + > Li+ >Mg 2+ > Be 2+
(Amphoteric oxide) 0.98 Å 0.68 Å 0.65 Å
Period 4 → K 2O (Strongly basic) 19. The charge/size ratio of a cation determines its
Hence, basic nature of oxides are as follows
polarising power. Which one of the following
Al 2O 3 <MgO <Na 2O <K 2O sequences represents the increasing order of
the polarising power of the cationic species,
16. The correct order of electron gain enthalpy K + , Ca 2+ , Mg 2+ , Be 2+ ? [AIEEE 2007]
with negative sign of F, Cl, Br and I, having (a) Mg 2 + < Be 2+ < K + < Ca 2+
atomic number 9, 17, 35 and 53 respectively, is
(b) Be 2+ < K + < Ca 2+ < Mg 2+
[AIEEE 2011]
(a) I > Br > Cl > F (b) F > Cl > Br > I (c) K + < Ca 2+ < Mg 2+ < Be 2+
(c) Cl > F > Br > I (d) Br > Cl > I > F (d) Ca 2+ < Mg 2+ < Be 2+ < K +
Exp. (c) Exp. (c)
As we go down the group in periodic table, atomic Higher the charge/size ratio, larger is the polarising
size increases, force of attraction for the added power.
electron decreases. Thus, the added electron ∴ K+ < Ca 2+ < Mg 2+ < Be 2+
becomes loosely bound. Hence, electron gain
enthalpy decreases down a group. 20. Which one of the following sets of ions
− − represents a collection of isoelectronic
X(g ) + e → X (g ) species ? [AIEEE 2006]
Actual order is Cl > F > Br > I (a) K + , Cl − , Ca 2+ , Sc 3+ (b) Ba 2+ , Sr 2+ , K + , S 2−
The fact that fluorine has a less electron gain enthalpy (c) N 3 – , O 2− , F − , S 2 – (d) Li + , Na + , Mg 2+ ,Ca 2+
than chlorine seems to be due to the relatively greater Exp. (a)
effectiveness of 2 p-electron in the small F-atom to Isoelectronic means having same number of
repel the additional electron entering the atom than electrons, K+, Cl − , Ca 2+, Sc 3+ (all are having
3p-electrons in the larger Cl-atom. 18 electrons).
17. The correct sequence which shows decreasing
order of the ionic radii of the elements is 21. The ionic mobility of alkali metal ions in
(a) Al 3+ > Mg 2+ > Na + > F – > O 2– [AIEEE 2010] aqueous soluton is maximum for [AIEEE 2006]
(b) Na + > Mg 2+ > Al 3+ > O 2– > F – (a) K + (b) Rb +
+ –
(c) Na > F > Mg 2+
>O 2–
> Al 3+ (c) Li + (d) Na +
(d) O 2– > F – > Na + > Mg 2+ > Al 3+

Periodicity of Elements 133
Exp. (b) 24. In which of the following arrangements the

Li+ is having largest hydrated ionic size while Rb+ order is not according to the property
is having smallest. indicated against it ? [AIEEE 2005]
Smaller the size, greater is the mobility. (a) Li < Na < K < Rb Increasing metallic radius
22. The increasing order of the first ionisation (b) I < Br < F < Cl Increasing electron gain enthalpy
enthalpies of the elements B, P, S and F (with negative sign)
(lowest first) is [AIEEE 2006] (c) B < C < N < O Increasing first ionisation enthalpy
(a) F < S < P < B (b) P < S < B < F (d) Al 3+ < Mg 2+ < Na + < F − Increasing ionic size
(c) B < P < S < F (d) B < S < P < F
Exp. (d) Exp. (c)
Examine the positions in periodic table. (a) Metallic radii increase in a group from top to
Group 13 14 15 16 17 bottom.
B C N O F Thus, Li < Na < K < Rb —True
P S (b) Electron gain enthalpy of Cl > F and
Ionisation enthalpy increases along a period due decreases along a group.
to increased nuclear charge and decreased Thus, I < Br < F < Cl is true.
atomic radii. While in a group, it decreases from (c) Ionisation enthalpy increases along a period
top to bottom. Along with this trend ionisation
from left to right but due to presence of half
enthalpy is highest for the elements possessing
filled orbitals in N, ionisation enthalpy of N > O.
half filled and sable electronic configuration.
Thus, B < C < N < O is incorrect.
Since, phosphorus is having stable half-filled
configuration. Hence, order is B < S < P < F. (d) Higher the negative charges, larger is their
ionic radii Al +3 < Mg 2 + < Na + < F − is also true.
23. Following statements regarding the periodic
trends of chemical reactivity of the alkali metals 25. Based on lattice energy and other
and the halogens are given. Which of these considerations which one of the following
statements give the correct picture? [AIEEE 2006] alkali metal chlorides is expected to have the
(a) The reactivity decreases in the alkali metals but highest melting point ? [AIEEE 2005]
increases in the halogens with increase in atomic (a) RbCl (b) KCl
number down the group
(c) NaCl (d) LiCl
(b) In both the alkali metals and the halogens the
chemical reactivity decreases with increase in Exp. (c)
atomic number down the group
(c) Chemical reactivity increases with increase in As we go down in the group, ionic character
atomic number down the group in both the alkali increases, hence melting point of halides should
metals and halogens increase but NaCl has the highest melting point
(d) In alkali metals, the reactivity increases but in the (800°C) due to its high lattice energy.
halogens it decreases with increase in atomic
number down the group 26. Which one of the following ions has the
Exp. (d) highest value of ionic radius ? [AIEEE 2004]
(a) Li + (b) B3 +
The chemical reactivity of alkali metals is due to
(c) O 2− (d) F −
their ability to loose electron more readily than other
elements. Since, the tendency to loose electron by Exp. (c)
alkali metals increases down the group, therefore,
their chemical reactivity increases down the group. All the ions belong to same period, thus for them
On the other hand, chemical reactivity of halogens cations will be smaller than anions. Now, O 2− and
1
is due to their ability to gain extra electron more F − are isoelectronic and rn ∝
readily than other elements. Since the tendency to Z
gain electron by halogens decreases down the Thus, ionic radius of O 2 − (Z = 8) > F − (Z = 9)
group, hence their chemical reactivity decreases
down the group.

27. The formation of the oxide ion O2− ( g ) requires 30. According to the periodic law of elements, the
first an exothermic and then an endothermic variation in properties of elements is related to
step as shown below their [AIEEE 2003]
O ( g ) + e − = O − ( g ); ∆H ° = − 142 kJ mol −1 (a) atomic masses
(b) nuclear masses

− − 2− −1
O ( g ) + e = O ( g ); ∆H ° = 844 kJ mol (c) atomic numbers
This is because [AIEEE 2004] (d) nuclear neutron-proton number ratios
(a) oxygen is more electronegative
Exp. (c)
(b) oxygen has high electron affinity
(c) O − ion will tend to resist the addition of another All physical and chemical properties of elements
electron are periodic function of their atomic number—
(d) O − ion has comparatively larger size than oxygen Modern Periodic Law.
atom
31. The radius of La 3+ (atomic number : La = 57) is
Exp. (c) 1.06 Å. Which one of the following given values
O − (g ) + e − → O 2 − ( g ); ∆H° = 844 kJ mol −1 will be closest to the radius of Lu 3+ (atomic
This process is unfavourable in the gas phase number : Lu = 71) ? [AIEEE 2003]
because the resulting increase in electron-electron (a) 160
. Å (b) 1.40 Å (c) 1.06 Å (d) 0.85 Å
repulsion overweighs the stability gained by
achieving the noble gas configuration. Exp. (d)
Due to lanthanide contraction, there occurs net
28. Which among the following factors is the most decrease in size. Only, 0.85 Å is smaller one.
important in making fluorine the strongest
oxidising agent ? [AIEEE 2004] 32. The atomic numbers of vanadium (V),
(a) Electron affinity chromium (Cr), manganese (Mn) and iron (Fe)
(b) Ionisation enthalpy are, respectively 23, 24, 25 and 26. Which one
(c) Hydration enthalpy of these may be expected to have the highest
(d) Bond dissociation energy second ionisation enthalpy ? [AIEEE 2003]
(a) V (b) Cr (c) Mn (d) Fe
Exp. (c)
F2 has the most negative ∆G° value which is Exp. (b)
dependent on hydration enthalpy. Fe + (26) = [Ar] 3d 6 ,4s1
Mn+ (25) = [Ar] 3 d 5 ,4s1
29. Among Al2O3 , SiO2 , P2O3 and SO2 the correct
V + (23) = [Ar]3d 2 , 4s 2
order of acid strength is [AIEEE 2004]
Cr + (24) = [Ar]3d 5 , 4s 0 [By first IP]
(a) SO 2 < P2O 3 < SiO 2 < Al 2O 3
(b) SiO 2 < SO 2 < Al 2O 3 < P2O 3 The electronic configuration of Cr + is most stable,
(c) Al 2O 3 < SiO 2 < SO 2 < P2O 3 hence formation of Cr 2+ by second IP requires
maximum enthalpy.
(d) Al 2O 3 < SiO 2 < P2O 3 < SO 2
Exp. (d) 33. Ce 3+ , La 3+ , Pm 3+

and Yb3+ have ionic radii in
the increasing order as [AIEEE 2002]
While moving along a group from top to bottom,
(a) La 3+ < Ce 3+ < Pm 3+ < Yb 3+
acidic nature of oxides decreases and along a
period from left to right, acidic nature increases. (b) Yb 3+ < Pm 3+ < Ce 3+ < La 3+
Al Si P S (c) La 3+ < Ce 3+ < Pm 3+ < Yb 3+
Z 13 14 15 16 (d) Yb 3+ < Pm 3+ < La 3+ < Ce 3+
Al 2O 3 SiO 2 P2O 3 SO 2 Exp. (b)
→ 1
amphoteric acidic max. acidic
rn (radius) ∝
Z
Thus, Al 2O 3 < SiO 2 < P2O 3 < SO 2 Thus, Yb 3 + < Pm3 + < Ce 3 + < La 3 + .

11
Principles and
Processes of Metallurgy
1. With respect to an ore, Ellingham diagram Generally, the diagram consists of plots of ∆G°
versus T for the formation of oxides of elements
helps to predict the feasibility of its
[JEE Main 2019, 8 April Shift-I] 2 xM(s ) + O 2 (g ) → 2 M xO(s )
Thermal reduction
(a) electrolysis product
(b) zone refining In this reaction, amount of gas decreases thus,
(c) vapour phase refining randomness decreases. Hence, ∆S becomes
(d) thermal reduction negative. Therefore, the value of free energy
increases with increase in temperature. There is a
Exp. (d) point in a curve below which ∆G is negative. So,
M xO is stable. Above this point, M xO will
With respect to an ore, Ellingham diagram helps to
decompose on its own.
predict the feasibility of its thermal reduction. It is a
graph representation of Gibbs energy change
versus absolute temperature. 2. The Mond process is used for the
0
–100
(a) purification of Ni (b) extraction of Mo
2Cu 2O
–200 4Cu+O 2 (c) purification of Zr & Ti (d) extraction of Zn
2FeO
O
2Fe+ 2
–300 C+O2 CO2 Exp. (a)
–400 2C+O
2CO 2 2
Mond process is used in the purification of Ni. It is
∆Gº/kJ mol–1 of O2
–500 +O 2 O 2CO a vapour phase refining process.

2CO 2Zn
–600 +O 2
2Zn It is based on the principle that Ni is heated in the
–700 presence of carbon monoxide to form nickel
–800 tetracarbonyl, which is a volatile complex. This
l +O 3
2 /3 A 2
–900 O2 complex is then decomposed by subjecting it to a
Al+ O
–1000 4/3 2Mg higher temperature (450-470 K) to obtain pure
+O 2
–1100 2Mg nickel metal.
–1200 Crude nickel (s) + 4 CO (g)
(Impure) Recycled
0°C 400°C 800°C 1200°C 1600°C 2000°C
273 K 673 K 1073 K 1473 K 1873 K 2273 K 330-350 K
Temperature
Gibbs energy (∆Gº) versus T plots (schematic) Ni (s)
[Ni (CO)4] (g) 450-470 K Pure + 4 CO (g)
for the formation of some oxides (Ellingham diagram)
(Volatile compound)

(a) I- (C) ; II-(D); III-(B) ; IV-(A)

3. The ore that contains the metal in the form of (b) I- (B) ; II-(C); III-(D) ; IV-(A)
fluoride is [JEE Main 2019, 9 April Shift-I]
(c) I- (C) ; II-(A); III-(B) ; IV-(D)
(a) magnetite (b) sphalerite (d) I- (B) ; II-(D); III-(A) ; IV-(C)
(c) malachite (d) cryolite [JEE Main 2019, 10 April Shift-I]
Exp. (d) Exp. (a)

Cryolite ore (Na 3 AlF6 , sodium hexafluoroaluminate) Refining of crude metals results pure metals
contain fluorine while other given options such as and its impurities get separated out.
malachite (Cu2 (CO)3 (OH)2 ), sphalerite ((Zn,Fe)S) I. Liquation In this method low melting
and bauxite (Al 2O 3 ) does not contain fluorine. metals like Sn, Pb, Bi and Hg can be made
to flow down through a sloping surface
4. Assertion For the extraction of iron, haematite leaving behind the higher melting impurities
ore is used. [JEE Main 2019, 9 April Shift-II] on the hearth.
Reason Heamatite is a carbonate ore of iron. II. Zone refining The basic principle of the
(a) Only the reason is correct. method is, impurities are more soluble in
(b) Both the assertion and reason are correct the molten metal than in the solid state of
explanation for the assertion. the metal. This method is useful to produce
(c) Both the assertion and reason are correct and the semiconductors and ultra-pure metals like
reason is the correct explanation for the assertion. B, Ga, In, Si and Ge.
(d) Only the assertion is correct. III. Mond process
330-350 K 450-470 K
Crude nickel (s) + 4CO(g) Ni(CO)4(g)
Exp. (d) (Impure) (Volatile compound)
Only assertion is correct and reason is incorrect. Recycled Ni(s)

4CO(g) +
Haematite is not a carbonate ore. It is an oxide ore, (Pure)
i.e. Fe 2O 3 . Cast iron is extracted chiefly from its
IV. van Arkel method
oxide ore (haematite) by heating in the presence of
500-600 K 1700-1800 K
coke and limestone in a blast furnace. M (s) + 2I2 (g) MI4(g)
(Crude (Volatile
metal) compound)
5. The one that is not a carbonate ore is Recycled M(s)
[JEE Main 2019, 9 April Shift-II] 2I2(g) +
(Ultra-pure)
(a) siderite (b) calamine
(c) malachite (d) bauxite Here, M = Zr, Hf, Ti
Hence, the correct matching is
Exp. (d) I→ (C), II→ (D), III → (B), IV → (A).
Bauxite is not a carbonate ore. Its chemical formula
is Al 2O 3 or AlO x(OH)3 − 2 x , where 0 < x < I. Chemical
7. The alloy used in the construction of
formula of other ores given in options are as follows:
aircrafts is [JEE Main 2019, 10 April Shift-II]
Siderite-FeCO 3 (a) Mg-Zn (b) Mg-Mn

(c) Mg-Sn (d) Mg-Al
Calamine-ZnCO 3
Malachite-CuCO 3 ⋅ Cu(OH)2 Exp. (d)
Names of magnesium alloys are given by two
6. Match the refining methods Column I with letters followed by two numbers. The common
metals Column II. alloying elements are A (Aluminium), Z (zinc), T
(tin), M (manganese) etc. Numbers indicate
Column I Column II
respective nominal compositions of main
(Refining Methods) (Metals)
alloying elements, e.g.
I. Liquation (A) Zr ‘AZ 91’ implies the composition of the alloy as :
II. Zone refining (B) Ni Al = 9%, Zn = 1% and Mg = 100 – (9 + 1) = 90%
III. Mond process (C) Sn Among the alloys given, Mg – Al (Magnalium ;
Mg = 5%, Al =95%) is being light, tough and
IV. van Arkel method (D) Ga strong, hence it is used in aircrafts.

Principles and Processes of Metallurgy 137
8. The correct statement is 10. The correct statement is

(a) zone refining process is used for the refining of (a) leaching of bauxite using concentrated NaOH
titanium. solution gives sodium aluminate and sodium
(b) zincite is a carbonate ore. silicate.
(c) sodium cyanide cannot be used in the (b) the hall-heroult process is used for the
metallurgy of silver. production of aluminium and iron.

(d) aniline is a froth stabiliser. (c) pig iron is obtained from cast iron.
[JEE Main 2019, 10 April Shift-II] (d) the blistered appearance of copper during
the metallurgical process is due to the
Exp. (d) evolution of CO 2 .
The explanation of given statements are as
follows: Exp. (a)
(a) Zone refining process is used for the refining The correct statement is ‘‘leaching of bauxite
of B, Ga, In, Si and Ge. using concentrated NaOH solution gives sodium
Ti is refined by van Arkel method. aluminate and sodium silicate’’. Bauxite usually
Thus, statement (a) is incorrect. contains SiO 2 , iron oxides and titanium oxide
(TiO 2 ) as impurities.
(b) Zincite (ZnO) is an oxide ore of Zn.
Concentration is carried out by digesting the
Thus, statement (b) is incorrect.
powdered ore with a concentrated solution of
(c) NaCN is used in the hydrometallurgy of silver. NaOH at 473-523 K and 35-36 bar pressure.
It is known as Mc. Arthur Forrest process.
Al 2O 3 is leached out as sodium aluminate (and
The reactions occuring during the process are SiO 2 too as sodium silicate) leaving the impurities
as follows: behind.
Ag 2S + 4NaCN → 2Na[Ag(CN)2 ] + Na 2S Al 2O 3 (s ) + 2NaOH(aq ) + 3H2O(l ) →
4Na 2S + 2H2O + 5O 2 → 2Na 2SO 4 2Na[Al(OH)4 ](aq )
+ 4NaOH + 2S The aluminate in solution is neutralised by passing
2Na[Ag(CN)2 ] + Zn → Na 2[Zn(CN)4 ] + 2Ag CO 2 gas and hydrated Al 2O 3 is precipitated. Here,
Thus, statement (c) is incorrect. the solution is seeded with freshly prepared
(d) Aniline and cresol help in stabilising the froth samples of hydrated Al 2O 3 which induces
in froth floatation process. precipitation.
Thus, statement (d) is correct. 2Na[Al(OH)4 ](aq ) + CO 2 (g ) →
Al 2O 3 ⋅ xH2O(s ) + 2NaHCO 3 (aq )
9. The idea of froth floatation method came
The sodium silicate remains in the solution and
from a person X and this method is related to
hydrated alumina is filtered, dried and heated to
the process Y of ores. X and Y , respectively, give back pure Al 2O 3 .
are [JEE Main 2019, 12 April Shift-I]
Al 2O 3 ⋅ xH2O(s ) 1470
 K
→ Al 2O 3 (s) + xH2O(g )
(a) fisher woman and concentration
(b) washer woman and concentration
(c) fisher man and reduction
11. The ore that contains both iron and copper is
(a) malachite (b) azurite
(d) washer man and reduction
(c) dolomite (d) copper pyrites
Exp. (b) [ JEE Main 2019, 9 Jan Shift-I]
The idea of froth floatation method came from a Exp. (d)

person ‘washer woman’ ( X ) and this method is The formulae of the given ores are as follows:
related to the process concentration (Y ) of ores.
Malachite : CuCO 3 ⋅ Cu(OH)2
This method is based upon the preferential
Copper pyrites : CuFeS2
wetting properties with the frothing agent
(collector) and water. Dolomite : CaMg(CO 3 )2
Azurite : Cu3 (CO)3 (OH)2

12. The correct statement regarding the given 14. The electrolytes usually used in the
Ellingham diagram is electroplating of gold and silver,
O respectively, are
→ 2Cu 2
+O 2 (a) [Au(OH)4 ]− and [Ag(OH)2 ]−
4Cu
(b) [Au(NH3 )2 ]+ and [Ag(CN)2 ]−
–300 (c) [Au(CN)2 ]− and [Ag(CN)2 ]−

(d) [Au(CN)2 ]− and [AgCl 2 ]−
∆Gº (kJ/mol)
2C
+O
nO 2 →2 [ JEE Main 2019, 10 Jan Shift-II]
–600 O2 → 2Z CO
2Zn+
Exp. (c)
O3
3 Al 2 Electroplating is a process of coating one metal or
→ 2/
l+O 2
4 /3 A metal object with a very thin layer of another metal
–1050 typically applying a direct electric current.
500ºC 800ºC 2000ºC
Electrolytes used in the electroplating of gold and
Temperature (ºC)
silver are given in the table below:
Pure metal block
(a) At 800°C, Cu can be used for the extraction of Article to
acts an anode Electrolyte
Zn from ZnO be plated
Process by which (aqueous
(b) At 1400°C, Al can be used for the extraction of out acts as
electroplating will solution)
cathode
Zn from ZnO be done
(c) At 500°C, coke can be used for the extraction of (a) Gold Article Ai(S) I
Zn from ZnO Na[A u(CN)2 ]
plating
(d) Coke cannot be used for the extraction of Cu (Sodium
from Cu 2O auro-cyanide)
I
(b) Silver Article Ag(S) Na[A g(CN)2 ]
Exp. (b) plating
(Sodium
From the Ellingham diagram, we can say that any argento
oxide with lower value of ∆G° is more stable than a cyanide)
oxide with higher value of ∆G°. We can also
predict that the oxide placed higher in the diagram
can be reduced by the element involved in the 15. Match the ores ( Column A ) with the metals
formation of its oxide placed lower at that (Column B).
temperature in the diagram. It is happening in case Column A Column B
of ZnO for its reduction by Al at 1400°C.
Ores Metals
13. Hall-Heroult’s process is given by A. Siderite P. Zinc
Coke, 1673 K
(a) ZnO + C → Zn + CO B. Kaolinite Q. Copper
(b) Cr2O3 + 2Al → Al 2O3 + 2Cr C. Malachite R. Iron
(c) 2 Al 2O3 + 3C → 4Al + 3CO2 D. Calamine S. Aluminium
(d) Cu 2 + (aq ) + H2 ( g ) → Cu( s ) + 2 H+ (aq ) (a) A - P; B- Q; C - R; D- S
[ JEE Main 2019, 10 Jan (Shift-I)] (b) A - R; B- S; C - P; D- Q
Exp. (c) (c) A - Q; B- R; C - S; D- P
(d) A - R; B- S; C - Q; D- P
Hall-Heroult’s process is an electro-reduction
process by which pure alumina (Al 2O 3 ) is reduced
to crude Al. In this process, electrolysis of a fused Exp. (d)
mixture of Al 2O 3 , Na 3 [AlF6 ] (cryolite) and CaF2
The correct match is: A → R; B→ S; C→ Q; D→ P.
(fluorspar) is carried out at carbon cathode and
graphite anode. The overall reaction is (A) Siderite is an ore of iron with molecular
represented as: formula FeCO 3 (R).
2Al 2O 3 + 3C → 4Al + 3CO 2 (B) Kaolinite is an ore of aluminium with molecular
formula Al 2Si 2 (OH)2 O 5 (S).

Principles and Processes of Metallurgy 139
(C) Malachite is an ore of copper with molecular

formula CuCO 3 ⋅ Cu(OH)2 (Q).
18. The pair that does not require calcination is
(a) ZnO and MgO
(D) Calamine is an ore of zinc with molecular
formula ZnCO 3 (P). (b) ZnO and Fe2O3 ⋅ xH2O
(c) ZnCO3 and CaO
16. The reaction that does not define
(d) Fe2O3 and CaCO3 ⋅ MgCO3

calcination is
∆ [JEE Main 2019, 12 Jan Shift-II]
(a) Fe2O3 ⋅ XH2 O → Fe2 O3 + XH2 O
Exp.(a)
∆
(b) ZnCO3 → ZnO + CO2 The hydroxide, hydrated oxides and carbonate
∆ ores, after concentration, are subjected to
(c) CaCO3 ⋅ MgCO3 → CaO + MgO + 2 CO2
calcination. In the process, the ore is heated
∆ below its melting point in the limited supply or
(d) 2Cu 2S + 3O2 → 2Cu 2 O + 2 SO2
absence of air. As the result, these are converted
[JEE Main 2019, 11 Jan (Shift-II) into their oxides.
Exp. (d) So, among the given options, the options having
Calcination is one of the pyrometallurgical either carbonates (e.g. ZnCO 3 and
process, like roasting by which a concentrated ore CaCO 3 ⋅ MgCO 3 ) or hydrated oxide (e.g.
gets converted into its oxide. Fe 2O 3 ⋅ xH2O), require calcination while pair of
In calcination, a hydrated carbonate or option (a), i.e. ZnO and MgO does not require
bicarbonate ore or a hydrated ore is heated at calcination.
lower temperature (compared to roasting) in
absence of air to give its oxide as in options (a), (b) 19. Which series of reactions correctly represent
and (c). Here, volatile non-metallic oxides like H2O, chemical relations related to iron and its
CO 2 , are also produced. compound? [JEE Main 2014]
Dil . H 2 SO 4 H 2 SO 4 , O 2
Roasting is valid mainly for sulphide ores like Heat
(a) Fe → FeSO 4 → Fe 2( SO 4 )3 → Fe
option (d), where SO 2 gets liberated. In this
reaction, calcination cannot be used. O 2 , heat dil . H 2 SO 4 Heat
(b) Fe → FeO → FeSO 4 → Fe
17. In the Hall-Heroult process, aluminium is Cl , heat Heat, air Zn
formed at the cathode. The cathode is made (c) Fe →
2
FeCl 3 → FeCl 2 → Fe
out of O , heat CO, 600 ° C CO, 700 ° C
(d) Fe →
2
Fe3O 4 → FeO → Fe
(a) platinum (b) carbon
(c) pure aluminium (d) copper Exp. (d)
[JEE Main 2019, 12 Jan (Shift-I) This problem involves the concept of Ellingham
diagram as this diagram predicts the basis of
Exp. (b) oxidation state and stability of iron compounds.
In the Hall-Heroult’s process, aluminium in formed dil . H 2SO 4 H 2SO 4 , O 2
at the cathode. The cathode is made out of (a) Fe → FeSO 4 → Fe 2 (SO 4 )3
carbon. In this method, Al 2O 3 is melted with
cryolite, Na 3 [AlF6 ] and electrolysed in a graphite →
Heat
Fe
lined steel tank, which serves as the cathode. The The above given reaction series is incorrect.
anode is also made of graphite. The correct reactions series is as follows
The cell runs continuously and at intervals molten Fe + H2SO 4 → FeSO 4 + H2
aluminium is drained from the bottom of the cell
1
and more bauxite is added. The electrolytic H2SO 4 + 2FeSO 4 + O 2 → Fe 2 (SO 4 )3 + H2O
reactions are as follows: 2
∆
At cathode Al 3+ + 3 e − → Al Fe 2 (SO 4 )3 → Fe 2O 3 (s ) + 3 SO 3 ↑
At anode O 2 , heat dil . H 2SO 4
C(s) + O 2 − (melt) → CO(g ) + 2e −
Heat
(b) Fe → FeO → FeSO 4 → Fe
2− −
C(s) + 2O (melt) → CO 2 (g ) + 4e This reaction series is also incorrect.

The correct reaction series is than CS2 . Also, metal sulphides are
O2 thermodynamically more stable than CS2 .
F → FeO [It could also beFe 2O 3 or Fe 3O 4 ]
∆ Metal sulphides are more stable than the
FeO + H2SO 4 → FeSO 4 + H2O corresponding oxides, so they are roasted to
∆ convert into less stable oxides.
2FeSO 4 → Fe 2O 3 + SO 2 + SO 3
Cl 2 , heat
Heat , air Zn 22. During the process of electrolytic refining of
(c) Fe → FeCl 3 → FeCl 2 → Fe
copper, some metals present as impurity
The reaction of FeCl 3 is not possible. Thus, the settle as ‘anode mud’. These are [AIEEE 2005]
above reaction series is incorrect. (a) Fe and Ni (b) Ag and Au
∆ CO, 600 °C CO, 700 °C (c) Pb and Zn (d) Se and Ag
(d) Fe → Fe 3O 4 → FeO → Fe
O2
Exp. (b)
This reaction series is correct.
During electrolysis, noble metals (inert metals) like
20. Which method of purification is represented Ag, Au and Pt are not affected and separate as
anode mud from the impure anode.
by the following equation? [AIEEE 2012]
523 K 1700 K 23. Which one of the following ores is best
Ti (s ) + 2 I 2( g ) → TiI 4 ( g ) → Ti ( g ) concentrated by froth-floatation method ?
+ 2 I 2( g ) (a) Magnetite (b) Cassiterite
(a) Zone refining (b) Cupellation (c) Galena (d) Malachite
(c) Polling (d) van-Arkel [AIEEE 2004]
Exp. (c)
Exp. (d) Froth-floatation is used to concentrate sulphide
van-Arkel method is used for refining Titanium and ores [Galena (PbS)].
Zirconium. This method is useful for removing
volatile impurities like O 2 , N2 , I2 present in the 24. Aluminium is extracted by the electrolysis
metals of Zr and Ti. of [AIEEE 2002]
In this method, metal iodide is formed by direct (a) alumina
combination of metal and iodine. (b) bauxite
The metal iodide undergo decomposition on a (c) molten cryolite
tungsten filament and thus, pure metal is (d) alumina mixed with molten cryolite
deposited on the filament.
Exp. (d)
21. Which of the following factors is of no Aluminium is extracted by electrolysis of a fused
significance for roasting sulphide ores to the mixture of alumina (2-8%), synthetic cryolite
oxides and not subjecting the sulphide ores Na 3 AlF6 (80-85%), AlF3 and fluorspar.
to carbon reduction directly? [AIEEE 2008] This makes alumina good conductor and lowers
(a) Metal sulphides are thermodynamically more the fusion temperature also.
stable than CS 2
25. Cyanide process is used for the extraction of
(b)CO 2 is thermodynamically more stable than
(a) barium (b) silver [AIEEE 2002]
CS 2
(c) Metal sulphides are less stable than the (c) boron (d) zinc
corresponding oxides Exp. (b)
(d)CO 2 is more volatile than CS 2
Cyanide process or Mac Arthur-Forest cyanide process
Exp. (c) 2Ag 2S + 8NaCN + O 2 + 2H2O →
2 MS + C → 2 M + CS2 ; ∆G1 = +ve 4Na [Ag(CN)2 ] + 4NaOH + 2S
2 MO + C → 2 M + CO 2 ; ∆G2 = –ve Soluble silver complex is filtered and treated with
The value of ∆G for the formation of CO 2 is zinc dust and silver gets precipitated.
negative, i,e., it is thermodynamically more stable 2Na [Ag(CN)2 ]+ Zn → Na 2 [Zn(CN)4 ] + 2Ag ↓

12
Hydrogen,
s-and p-Block Elements
The correct order of hydration enthalpies of alkali
1. Diborane (B2H6 ) reacts independently with O2 metal ions is
and H2O to produce, respectively. Li + > Na + > K + > Rb + > Cs +
[JEE Main 2019, 8 April Shift-I] Li + possesses the maximum degree of hydration due
(a) B2O 3 and H3 BO 3 (b) B2O 3 and [BH4 ]− to its small size. As a consequence of hydration
(c) H3 BO 3 and B2O 3 (d) HBO 2 and H3 BO 3 enthalpy, their mobility also get affected. Cs+ has
highest and Li + has lowest mobility in aqueous
Exp. (a) solution.
Diborane (B 2H 6 ) reacts independently with O 2 and
H 2O to produce B 2O 3 and H 3BO 3 respectively.
3. The statement that is incorrect about the
Diborane is a colourless, highly toxic gas, having interstitial compounds is
boiling point 180 K. Because of its inflammable [JEE Main 2019, 8 April Shift-II]
nature, it catches fire spontaneously when exposed to (a) they are very hard
air and burns in oxygen releasing an enormous
(b) they have metallic conductivity
amount of energy as:
B 2H 6 + 3O 2 → B 2O 3 + 3H 2O + 1976 kJ/mol (c) they have high melting points
It gets hydrolysed readily to give boric acid. (d) they are chemically reactive
B 2H 6 + 6H 2O → 2H 3BO 3 + 6H 2 ↑
Borane Orthoboric acid Dihydrogen
Exp. (d)
Interstitial compounds are formed when a neutral
2. The correct order of hydration enthalpies of atom with a small radius occupies in an interstitial hole
(tetrahedral or octahedral voids) in a transition metal’s
alkali metal ions is
hcp or ccp lattices (host lattice). Examples of small
[JEE Main 2019, 8 April, (Shift-I)] atoms (guest atom) are H, B, C and N.
(a) Li + > Na + > K + > Cs+ > Rb+ Interstitial compounds are non-stoichiometric
(b) Na + > Li + > K + > Rb+ > Cs+ (Birtholide) in composition. They are very hard with
(c) Na + > Li + > K + > Cs+ > Rb+ very high melting points. The electrical conductivity of
interstitial compounds are comparable to that of the
(d) Li + > Na + > K + > Rb+ > Cs+ pure metal. These are chemically unreactive in nature.
Exp. (d) 4. The covalent alkaline earth metal halide
Key Idea The amount of energy released when (X = Cl, Br, I) is [JEE Main 2019, 8 April Shift II]
one mole of gaseous ions combine with water to (a) SrX 2 (b) CaX 2
form hydrated ions is called hydration enthalpy. (c) MgX 2 (d) BeX 2

Exp. (d) Exp. (b)

••
Key Idea According to Fajan’s rule, degree of For I Cl 5
covalency (ionic potential), φ ∝-polarisation 1
H=
(7 + 5 − 0 + 0)
power of the cation ∝ charge on the cation 2
1 = 6 ( sp3d 2 )
∝ .
size of the cation [refer the solution of Q. No. 4]
Cl
Alkaline earth metals contains bipositive (H 2 + ) ions in 3 2
their compounds. Cl Cl sp d -hybridised
Geometry : Octahedral
So, here I Shape / Structure : Square pyramidal
(i) Charge on cation, i.e. + 2 is constant.
Cl Cl
(ii) Halide present ( X − ) is also constant.
So, the covalent character depends on the size of For &&I Cl −4
alkaline earth metal. As we move down the group, size 1
H= (7 + 4 − 0 + 1)
of metal ion increases. 2
Be 2+ < Mg 2+ < Ca 2+ < Sr 2+ < Ba 2+ = 6 ( sp3d 2 )
2+
So, Be readily forms covalent compounds like BeX 2, Cl
3 2
Cl sp d -hybridised
because of very high positive charge density over its s Geometry : Octahedral
small size, so that it readily polarises anionic spherical I Shape/Structure : Square planar
electron cloud.
Cl Cl
5. The strength of 11.2 volume solution of H2O2 is
[Given that molar mass of So, ICl 5 and ICl −4 are isolobal but not isostructural.
H =1 g mol −1 and O =16 g mol −1 ] 7. C 60 an allotrope of carbon contains
[JEE Main 2019, 8 April Shift-II] [JEE Main 2019, 9 April Shift I]
(a) 1.7% (b) 34% (c) 13.6% (d) 3.4% (a) 16 hexagons and 16 pentagons
(b) 20 hexagons and 12 pentagons
Exp. (d) (c) 12 hexagons and 20 pentagons
11.2 volume of H 2O 2 means that 1 mL of this H 2O 2 will (d) 18 hexagons and 14 pentagons
give 11.2 mL of oxygen at STP.
2H 2O 2 ( l ) → O 2( g ) + 2H 2O( l )
Exp. (b)
2 × 34 g 22.4 L at STP C 60 is aromatic allotrope of carbon containing
12 pentagons and 20 hexagons. It is a fullerene
22.4 L of O 2 at STP is produced from H2O 2 = 68 g having a shape like soccer ball and called
∴11.2 L of O 2 at STP is produced from Buckminster fullerene.
68
H 2O 2 = × 11.2 = 34 g
22.4 8. Magnesium powder burns in air to give
∴34 g of H2O 2 is present in 1000 g of solution [JEE Main 2019, 9 April Shift I]
34
∴ % w/w = × 100 = 3.4%. (a) MgO and Mg 3 N 2
1000
(b) Mg(NO 3 )2 and Mg 3 N 2
(c) MgO only
6. The correct statement about ICl 5 and ICl −4 is
(d) MgO and Mg(NO 3 )2
(a) ICl 5 is square pyramidal and ICl −4 is Exp. (a)
tetrahedral Magnesium powder burns in air to give MgO and
(b) ICl 5 is square pyramidal and ICl −4 is square Mg 3N 2. MgO does not combine with excess oxygen to
planar give any superoxide. Mg reacts with nitrogen to form
(c) Both are isostructural magnesium nitride (Mg 3N 2 ).
(d) ICl 5 is trigonal bipyramidal and ICl −4 is Mg + O 2 → MgO
tetrahedral 3Mg + N 2 → Mg 3 N 2

Hydrogen, s- and p-Block Elements 143
molecule and fluorine atom of another molecule as

9. The correct order of the oxidation states of shown below.
nitrogen in NO, NO2 , NO2 and N 2O3 is δ+ δ− δ+ δ− δ+ δ−
…H  F …H  F …H  F
In this molecule, hydrogen bond behaves like a bridge
(a) NO 2 < NO < N 2O 3 < N 2O between two atoms that holds one atom by covalent
(b) N 2O < NO < N 2O 3 < NO 2 bond and the other by hydrogen bond.
(c) O 2 < N 2O 3 < NO < N 2O
(d) N 2O < N 2O 3 < NO < NO 2
12. The structures of beryllium chloride in
the solid state and vapour phase, respectively
Exp. (b) are [JEE Main 2019, 9 April Shift-II]
The correct increasing order of oxidation state of (a) dimeric and dimeric (b) chain and chain
nitrogen for nitrogen oxides is (c) dimeric and chain (d) chain and dimeric
+1 +2 +3 +4
N 2O < N O < N 2 O 3 < N O 2 Exp. (d)
● Oxidation state of N in N 2O is
The structures of beryllium chloride in the solid state
2( x ) − 2 = 0 and vapour phase, respectively are dimeric and chain.
2
x = + = +1 In vapour phase at above 900°C, BeCl 2 is monomeric
2 having a linear structure ClBeCl. The bonding in
● Oxidation state of N in NO is BeCl 2 is covalent and Be atom accommodates
x−2 = 0 2 + 2 = 4 electrons in the two sp-hybrid orbitals.
x = +2 Below 900°C, beryllium chloride in vapour phase exists
● Oxidation state of N in N 2O 3 is as a mixture of monomer BeCl 2 and dimer Be 2Cl 4 .
2 x + 3( −2 ) = 0
6 13. The correct statements among I to III
x= =3 regarding group 13 element oxides are:
2
● Oxidation state of N in NO 2 is [JEE Main 2019, 9 April Shift-II]
x + 2( −2 ) = 0 I. Boron trioxide is acidic.
x−4 = 0 II. Oxides of aluminium and gallium are
x = +4 amphoteric.
III. Oxides of indium and thallium are basic.
10. The amorphous form of silica is
(a) I, II and III (b) I and III only
(c) I and II only (d) II and III only
(a) tridymite (b) kieselguhr
(c) cristobalite (d) quartz Exp. (a)
All the given statements are correct. For group 13
Exp. (b) elements, the acidic nature of oxides decreases and
Silica occurs in nature in several amorphous and the basic nature of oxides increases on moving from B
crystalline forms. Kieselguhr is the amorphous form of to Tl. This is because as we move down the group, the
silica. Quartz, tridymite and cristobalite are crystalline atomic size of elements goes on increasing, whereas
forms of silica. the ionisation energy decreases, due to which the
strength of metal oxide (MO) bond goes on
11. HF has highest boiling point among hydrogen decreasing.
halides, because it has Thus, boron trioxide or boron oxide is acidic and
reacts with basic oxides to give metal borates.
(a) lowest ionic character Aluminium and gallium oxides are amphoteric while
(b) strongest van der Waals’ interactions oxides of indium and thallium are basic in nature.
(c) strongest hydrogen bonding
(d) lowest dissociation enthalpy 14 The oxoacid of sulphur that does not contain
bond between sulphur atoms is
Exp. (c) [JEE Main 2019, 10 April Shift-I]
HF has highest boiling point among hydrogen halides (a) H2 S 2O 3 (b) H2 S 2O 4
because it has strongest hydrogen bonding. Here, the (c) H2 S 2O 7 (d) H2 S 4O 6
hydrogen bond exists between hydrogen of one

Exp. (c) 380-393 K 1

CaSO 4 ⋅2H 2O → CaSO 4 ⋅ H 2O
−1/ 2 H 2O 2
S  S bond is not present in H 2S 2O 7 (pyrosulphuric Gypsum
Plaster of Paris
acid or oleum). >393K
O O →
1
CaSO 4
− H 2O Dead burnt
2
plaster
H2S2O7 ⇒ HO—S—O—S—OH (anhydrous)

Therefore, the reaction takes place as follows :
O O
< 373K
While the other given oxoacids of sulphur, i.e. Na 2CO 3 ⋅ 10H 2O → Na 2CO 3 ⋅ H 2O
−9H 2O
Washing soda Monohydrate
H 2S 2O 3 (thiosulphuric acid), H 2S 2O 4 (hyposulphurous ( X) (Y )
or dithionous acid) and H 2S 4O 6 (tetrathionic acid)
contains SS bonds. →
>373K
Na 2CO 3
−H 2O
O Anhydrous white powder
(soda ash) ( Z)
H2S2O3 ⇒ HO—S—OH
17. The number of pentagons in C 60 and trigons
S (triangles) in white phosphorus, respectively,
O OH are [JEE Main 2019, 10 April Shift-II]
H2S2O4 ⇒ S——S
HO
(a) 20 and 3 (b) 12 and 4
O
O O (c) 20 and 4 (d) 12 and 3
H2S4O6 ⇒ HO—S—S—S—S—OH Exp. (b)

In C 60 (Buckminster fullerene) twenty hexagons and
O O twelve pentagons are present which are interlocked
resulting a shape of soccer ball. Every ring in this
15. The correct order of catenation is structure is aromatic.
(a) C > Sn > Si ≈ Ge (b) Si > Sn > C > Ge
(c) C > Si > Ge ≈ Sn (d) Ge > Sn > Si > C
Exp. (c)
Catenation property is an unique property of group 14
elements. Down the group 14, catenation power
decreases as:
C > Si > Ge ≈ Sn
Pb does not show catenation. Structure of C 60 Buckminster fullerene
Phosphorus has large atomic size and less
16. A hydrated solid X on heating initially gives a electronegativity, so it forms single bond instead of pπ-
monohydrated compoundY . pπ multiple bond. So, it consists of discrete tetrahedral
Y upon heating above 373 K leads to an P4 molecule as shown below :
anhydrous white powder Z . X and Z , P
respectively, are
P P
(a) baking soda and soda ash P
(b) washing soda and soda ash ∴ Number of trigons (triangles) = 4
(c) baking soda and dead burnt plaster
(d) washing soda and dead burnt plaster 18. The correct statements among (a) to (d) are:
Exp. (b) 1. Saline hydrides produce H 2 gas when
Baking soda (NaHCO 3 ) is not a hydrated solid. Thus, reacted with H 2O.
( X ) is not baking soda. Thus, option (a) and (c) are
incorrect. Dead burnt plaster (CaSO 4 ) is obtained from
2. Reaction of LiAlH 4 with BF3 leads to B2H 6 .
gypsum via the formation of plaster of Paris.

3. PH3 and CH 4 are electron rich and electron Exp. (c)

precise hydrides, respectively.
The basic structural unit of feldspar, zeolites, mica and
4. HF and CH 4 are called as molecular asbestos is (SiO 4 )4 − . These all are silicates. All
hydrides. silicates involve two types of Si  O bonds.
(a) (1), (2), (3) and (4) (b) (1), (2) and (3) only (i) Terminal Si O bonds in which oxygen is
(c) (3) and (4) only (d) (1), (3) and (4) only bonded to a silicon and not other atom.
(ii) Bridging Si O Si bonds in which oxygen is
Exp. (a) bonded to two silicon atoms.
The explanation of given statements are as follows : O– s
1. Saline or ionic hydrides produce H 2 with H 2O.
⊕ È Si O–
M H + H 2O → H 2 ↑ + MOH
Thus, statement (1) is correct. O– O– s s
Ether
Tetrahedral structure of SiO 2−
4 anion
2. 3LiAlH 4 + 4BF3 → 2B 2H 6 + 3LiF + 3AlF3
(Diborane) In SiO 44 − ion, each Si atom is bonded to four oxygen
Thus, statement (2) is correct. atoms tetrahedrally.
3. PH 3 andCH 4 are covalent hydrides and in both of
the hydrides, octet of P and C have been
21. The correct sequence of thermal stability of the
satisfied. But P in PH 3 has one lone pair of following carbonates is
electrons and C in CH 4 does not have so PH 3 [JEE Main 2019, 12 April Shift-I]
(group 15) and CH 4 (group 14) are electron rich (a) BaCO 3 < CaCO 3 < SrCO 3 < MgCO 3
and electron precise hydrides, respectively. (b) MgCO 3 < CaCO 3 < SrCO 3 < BaCO 3
Thus, statement (3) is correct. (c) MgCO 3 < SrCO 3 < CaCO 3 < BaCO 3
4. HF and CH 4 are called as molecular hydrides (d) BaCO 3 < SrCO 3 < CaCO 3 < MgCO 3
because of their discrete and sterically
Exp. (b)
symmetrical structure.
Thus, statement (4) is also correct. The correct sequence of thermal stability of
carbonates is
19. The metal that gives hydrogen gas upon MgCO 3 < CaCO 3 < SrCO 3 < BaCO 3
treatment with both acid as well as base is On moving down the group, i.e. from Mg to Ba, atomic
radius generally increases. It is due to the addition of
[JEE Main 2019, 12 April Shift-I] shell. As a result, the atomic size increases.CO 2−3 is a
(a) magnesium (b) mercury large anion. Hence, more stabilised by Ba 2 + (large
(c) zinc (d) iron cation) and less stabilised by Mg 2 + . Therefore, BaCO 3
Exp. (c) has highest thermal stability followed by SrCO 3,
CaCO 3 and MgCO 3.
Metal that gives hydrogen gas upon treatment with
both acid as well as base is zinc. 22. The correct statement among the following is
Hence, it is amphoteric in nature. [JEE Main 2019, 12 April Shift-I]
Reactions involved are as follows: (a) (SiH3 )3 N is planar and less basic than
Zn + Dil. NaOH → Na 2ZnO 2 + H 2 ↑ (CH3 )3 N.
Zn + 2HCl(dil. ) → ZnCl 2 + H 2 ↑ (b)(SiH3 )3 N is pyramidal and more basic than
(CH3 )3 N.
20. The basic structural unit of feldspar, zeolites, (c) (SiH3 )3 N is pyramidal and less basic than
mica and asbestos is (CH3 )3 N.
[JEE Main 2019, 12 April Shift-I] (d) (SiH3 )3 N is planar and more basic than(CH3 )3 N.
(a) ( SiO3 )2 − (b) SiO2 (c) ( SiO4 )4 −
R
Exp. (d)
 The correct statement is that (SiH 3 )3N is planar and
(d)  ( Si  O )
n ( R = Me) less basic than (CH 3 )3N. The compounds
 trimethylamine (CH 3 )3N and trisilylamine (SiH 3 )3N have
R similar formulae, but have totally different structures.

In trimethylamine the arrangement of electrons is as

follows : 25. The temporary hardness of a water sample is
1s 2s 2p due to compound X . Boiling this sample
Electronic structure of
nitrogen atom converts X to compound Y . X and Y ,
(ground state)
Three unpaired electrons
respectively, are
form bonds with CH3 groups [JEE Main 2019, 12 April, (Shift II)]
tetrahedral arrangements of
three bond pairs and one lone pair (a) Mg(HCO 3 )2 and Mg(OH)2
In trisilylamine, three sp2 orbitals are used for (b) Ca(HCO 3 )2 and Ca(OH)2
σ -bonding, giving a plane triangular structure. (c) Mg(HCO 3 )2 and MgCO 3
H3Si SiH3 (d) Ca(HCO 3 )2 and CaO
N N Exp. (a)
H3C CH3
SiH3 The temporary hardness of a water sample is due to
CH3
compound X [i.e. Mg(HCO 3 )2]. Boiling of this sample
N(CH3)3 N(SiH3)3 converts X[i.e. Mg(HCO 3 )2] to compound Y[i.e.
molecule molecule
Mg(OH)2]. Generally, temporary hardness is due to
presence of magnesium and calcium hydrogen
23. The incorrect statement is carbonates. It can be removed by boiling. During
[JEE Main 2019, 12 April, (Shift II)] boiling, the soluble Mg(HCO 3 )2 is converted into
insoluble Mg(OH)2 and Ca(HCO 3 )2 changed to
(a) lithium is the strongest reducing agent among insoluble CaCO 3. These precipitates can be removed
the alkali metals. by filteration.
(b) lithium is least reactive with water among the Mg(HCO 3 )2 Heating
→ Mg(OH)2 ↓ + 2CO 2 ↑
alkali metals. Heating
Ca(HCO 3 )2 → CaCO 3 ↓ + H 2O + CO 2 ↑
(c) LiNO 3 decomposes on heating to give LiNO 2
and O 2 .
(d) LiCl crystallise from aqueous solution as 26. Among the following, the energy of
LiCl ⋅ 2H2O. 2s-orbital is lowest in
[JEE Main 2019, 12 April, (Shift II)]
Exp. (c) (a) K (b) H
Statement (c) is incorrect. LiNO 3 (Lithium nitrate) on (c) Li (d) Na
heating gives a mixture of Li 2O, NO 2 and O 2.
∆
4LiNO 3 → 2Li 2O + 4NO 2 ↑ + O 2 ↑
Exp. (a)
The energy of 2 s-orbital is lowest in K(potassium). An
Among the alkali metals, lithium is the strongest
orbital gets larger as the principal quantum number n
reducing agent.
increases.
24. The C  C bond length is maximum in Correspondingly, the energy of the electron in such an
[JEE Main 2019, 12 April, (Shift II)] orbital becomes less negative, meaning that the
electron is less strongly bound and has less energy.
(a) graphite (b) C70
The graph of principal quantum number with atomic
(c) C60 (d) diamond number is
Exp. (d)
The C C bond length is maximum in diamond
Principal quantum
2
having value 154 pm. Here, each carbon atom
undergoes sp3-hybridisation and linked to four other
number
carbon atoms by using hybridised orbitals in

tetrahedral fashion. It has a rigid three-dimensional
network of carbon atoms. 1 2s
C  C bond length within the layers of graphite is
141.5 pm. In C 60, C  C distances between single and 1 25 50 75 100
double bonds are 143.5 pm and 138.3 pm Atomic number
respectively.

B 3 + does not exist in free states. All B(III) compounds

27. The alkaline earth metal nitrate that does not are covalent.
crystallise with water molecules, is + 1oxidation states
(a) Ca(NO 3 ) 2 (b) Sr(NO 3 ) 2 B + < Al + < Ga + < In + < Tl +
(c) Ba(NO 3 ) 2 (d) Mg(NO 3 ) 2
B + does not exist in ionic as well covalent
[ JEE Main 2019, 9 Jan Shift-I] compounds.
Exp. (c) 30. The isotopes of hydrogen are

I
(a) deuterium and tritium only
A saturated aqueous solution of M (NO 3 )2 on
(b) protium and deuterium only
crystallisation will produce hydrated crystal,
II (c) protium, deuterium and tritium
M (NO 3 )2 ⋅ nH 2O only when hydration enthalpy (∆H°hyd ) (d) tritium and protium only
of M 2 + ion will be appreciably more negative. [ JEE Main 2019, 9 Jan Shift-I]
Hydration of an ion depends on its size. Smaller the Exp. (c)
size of an ion, higher will be its charge density and as a
result it will remain more solvated (hydrated) through There are three known isotopes of hydrogen, each
ion dipole interaction. possessing an atomic number 1 and atomic masses
1, 2 and 3 respectively. These are named as protium
Size of group-2 metal ions increases on going down
the group. So, their ability to form hydrated crystals (1H ), deuterium
follows the order: ( 2H or D) and tritium ( 3H or T)
Be 2 + >> Mg 2 + >> Ca 2 + >> Sr 2 + >> Ba 2 + The most common isotope is the ordinary hydrogen
usually called protium. It consists of one proton in the
Thus, Ba(NO 3 )2 is slightly or almost insoluble in water.
nucleus and an electron revolving around it.
The second isotope of hydrogen is called heavy
28. The one that is extensively used as a
hydrogen or deuterium. It consists of one proton and
piezoelectric material is one neutron in the nucleus and an electron revolving
(a) quartz around it. The third isotope of hydrogen is called
(b) tridymite tritium. It consists of one proton and two neutrons in
(c) amorphous silica the nucleus and an electron revolving around it.
(d) mica [ JEE Main 2019, 9 Jan Shift-I]
31. Correct statements among (I) to (IV) regarding
Exp. (a) silicones are:
Piezoelectric materials are those materials that I. They are polymers with hydrophobic
produce an electric current when they are placed character.
under mechanical stress. Crystalline solids can be II. They are biocompatible.
used as piezoelectric material hence, quartz is a
III. In general, they have high thermal stability
correct answer.
and low dielectric strength.
29. Aluminium is usually found in +3 oxidation IV. Usually, they are resistant to oxidation and
used as greases.
state. In contrast, thallium exists in +1 and +3
(a) I and II only (b) I, II, III only
oxidation states. This is due to
(c) I, II, III and IV (d) I, II and IV only
(a) lattice effect
(b) lanthanoid contraction
(c) inert pair effect Exp. (d)
(d) diagonal relationship Silicones are polysiloxanes with general chemical
[ JEE Main 2019, 9 Jan Shift-I] formula, [R 2SiO]n, where R is an organic group such
as:  CH 3,  C 2H 5,  C 6H 5 etc.
Exp. (c) Silicones have many useful properties:
Due to inert pair effect, group-13 elements ( ns 2np1 ) (i) They repel water and form watertight seals.
show + 3 and + 1 oxidation states in their (ii) They are heat resistant because of constancy
compounds. Stability order of these oxidation states of properties over a wide range of temperature
will be as, (− 100° to 250° C).
+ 3 oxidation states (iii) Silicones are non-toxic.
B 3 + > Al 3 + > Ga 3 + > In3 + > Tl 3 +

(iv) Silicones are biocompatible because these Exp. (a)

do not support microbiological growth and
As given, the first electron gain enthalpy of oxygen can
these have high gas permeability at room
be shown as,
temperature.
O( g ) + e − → O − ( g ), ∆e g H1 = − 141 kJ/mol
(v) They are resistant to O 2 , O 3 and UV-radiation.
The expression of second electron gain enthalpy of

(vi) Silicones are formulated to be electrically
oxygen will be,
insulative.
O − ( g ) + e − → O 2− ( g ), ∆e g H2 = + ve
(vii) Silicone grease is typically used as a lubricant
for brake components in automobiles, since it ∆e g H2 of oxygen is positive, i.e. endothermic,
is stable at high temperature, is not water because a strong electrostatic repulsion will be
soluble and is a odourless viscous liquid. observed between highy negative O − and the
incoming electron (e − ). A very high amount of energy
32. What is reason of temporary hardness of water? will be consumed (endothermic) by the system to
(a) Na 2SO 4 (b) CaCl 2 overcome the electrostatic repulsion.
(c) NaCl (d) Ca(HCO 3) 2
[ JEE Main 2019, 9 Jan Shift-II] 35. The metal that forms nitride by reacting
Exp. (d) directly with N2 of air, is
(a) Rb (b) K (c) Cs (d) Li
Temporary hardness of water is due to presence of
soluble Ca(HCO 3 )2 or Mg(HCO 3 )2 [ JEE Main 2019, 9 Jan Shift-II]
Permanent hardness of water is due to the presence Exp. (d)
of CaCl 2 or CaSO 4 or MgCl 2 or MgSO 4 .
Among the group-1 metals, only Li is able to form its
Temporary hardness of water is also called
nitride, Li 3N. [All alkaline earth metals of group-2 form
carbonate hardness which can be easily removed by
their nitride, M 3N 2]
boiling or by treatment withCa(OH)2 (Clark’s method).
6Li + N 2 → 2Li 3N (Ruby red solid)
33. Good reducing nature of H3 PO2 is attributed (Air)
I II
to the presence of [3M + N 2 → M 3N 2 ]
(a) two P  H bonds (b) one P  H bond
Li ⊕ is the smallest metal ion of group-1. Smaller size of
(c) two P  OH bonds (d) one P  OH bond
Li ⊕ and larger size of nitride ion, N 3− , enable Li ⊕ to
[ JEE Main 2019, 9 Jan (Shift-II)] polarise the spherical electron cloud ofN 3− and it gives
higher stability to Li 3N.
Exp. (a)
The structure of H 3PO 2 (hypophosphorous) acid is 36. The chemical nature of hydrogen peroxide is
O (a) oxidising and reducing agent in both acidic
and basic medium
P (b) oxidising and reducing agent in acidic
H medium, but not in basic medium
HO H
(c) reducing agent in basic medium, but not in
Due to the presence of two P H bonds, H 3PO 2 acts acidic medium
a strong reducing agent. e.g., (d) oxidising agent in acidic medium, but not in
+1 +1
4 AgNO 3 + H 3PO 2 + 2H 2O → basic medium [ JEE Main 2019, 10 Jan Shift-I]
0 +5
4 Ag ↓ + H 3 PO 4 + 4HNO 3 Exp. (a)
H 2O 2 can act as both oxidising and reducing agents in
34. When the first electron gain enthalpy (∆e g H )
both acidic and basic medium.
of oxygen is −141 kJ /mol, its second electron H2O 2 as oxidising agent
gain enthalpy is
In acidic medium:
(a) a positive value
(b) a more negative value than the first H 2O 2 + 2H+ + 2e − → 2H 2O
(c) almost the same as that of the first In basic medium,
(d) negative, but less negative than the first −
H 2O 2 + 2 O H + 2e − → 2H 2O + 2O 2−

H2O 2 as reducing agent Only tritium (T) is radioactive, because of its very high
In acidic medium : H 2O 2 → O 2 + 2H + + 2e − n n 
value,  = 2  .
p p 
In basic medium :
H 2O 2 + 2OH − → O 2 + 2H 2O + 2e − 40. The electronegativity of aluminium is similar to
(a) lithium (b) carbon

37. The metal used for making X-ray tube window (c) beryllium (d) boron
is [ JEE Main 2019, 10 Jan Shift-I] [ JEE Main 2019, 10 Jan Shift-I]
(a) Na (b) Be (c) Mg (d) Ca Exp. (c)
Exp. (b) Let, us consider the electronegativity values of the
Among the four elements given, Na, Be, Mg and Ca, given elements,
Be has highest IE value because of its smallest size Group-1 Group-2 Group-13 Group-19
and 2 s 2 valence shell configuration. Period 2 ⇒ Li Be B C
So, X-ray cannot cause ionisation from the material ( 1. 0 ) ( 1. 5 ) ( 2 . 0) ( 2 . 5)
used, i.e. Be in the tube window, which may cause
Period 3 ⇒ Al
interference in the study. ( 1. 5)
Be and Al show diagonal relationship which is based

38. The type of hybridisation and number of lone Z∗
pair(s) of electrons of Xe in XeOF 4 , respectively, on their same value (Z * is effective nuclear charge,
r
are [ JEE Main 2019, 10 Jan Shift-I] r = atomic radius). So, they have similar electronegativity.
(a) sp 3d 2 and 1 (b) sp 3d and 2
(c) sp 3d and 1 (d) sp 3d 2 and 2 41. The pair that contains two PH bonds in each
of the oxoacids is
Exp. (a) (a) H4 P2O 5 and H4 P2O 6 (b) H3PO 3 and H3PO 2
In XeOF4 , Xe is sp3d 2-hybridised. Geometry of the (c) H4 P2O 5 and H3PO 3 (d) H3PO 2 and H4 P2O 5
molecule is octahedral, but shape of the molecule is [ JEE Main 2019, 10 Jan Shift-II]
square pyramidal.
According to VSEPR, theory it has one π bond. Exp. (d)
Remaining six electron pairs form an octahedron with Let us consider the structure of the phosphorus
one position occupied by a lone pair. oxyacids,
O
F F
P P
Number of bp = 5 H OH HO H
Xe H OH
Number of lp = 1 H3PO2 H3PO3
Hypophosphorus Orthophosphorus
F F acid acid
(P  H bonds=2) (P  H bond=1)
Here, Xe contains one lone pair of electrons.
39. The total number of isotopes of hydrogen and

P P P P
number of radioactive isotopes among them, H O H O OH
respectively, are [ JEE Main 2019, 10 Jan Shift-I] HO OH OH OH
H4P2O5 H4P2O6
(a) 2 and 1 (b) 3 and 2 (c) 2 and 0 (d) 3 and 1 Pyrophosphorus Hypophousphoric
acid acid
Exp. (d) (P  H bonds=2) (P  H bond=0)
Hydrogen has three isotopes:
1 2 3
42. Sodium metal on dissolution in liquid
1H 1H 1H ammonia gives a deep blue solution due to the
Protium (P) Deuterium (D) Tritium (T) formation of [ JEE Main 2019, 10 Jan Shift-II]
p 1 1 1 (a) sodium ammonia complex
(b) sodium ion-ammonia complex
n 0 1 2
(c) sodamide
n/ p 0 1 2 (d) ammoniated electrons

Exp. (d) Hydrides of p-block elements are covalent in nature,

viz, electron deficient hydrides (by group-13
Sodium metal on dissolution in liquid ammonia gives elements), electron-precise hydrides (by group-14
a deep blue solution due to the formation of elements), and electron-rich hydrides (by group 15-17
ammoniated electrons. The reaction is represented as elements). Hydrides of d , f -block metals are called
follows: interstitial or metallic hydrides.
Na ( s ) + ( x + y) NH 3( l ) →
[Na(NH)x ] + + [e (NH 3 )y ] 45. The correct statements among (a) to (d)
[Ammoniated Na + [Ammoniated regarding H2 as a fuel are :
or expanded Na] electrons]
I. It produces less pollutants than petrol.
Ammoniated (solvated) electrons show electronic
transition in visible region and the solution becomes II. A cylinder of compressed dihydrogen weights
deep blue coloured. ~ 30 times more than a petrol tank producing
This deep blue solution also shows the following the same amount of energy.
properties due to the presence of ammoniated III. Dihydrogen is stored in tanks of metal alloys
electrons. like NaNi 5 .
(i) It is strongly reducing in nature. IV. On combustion, values of energy released per
(ii) It is paramagnetic. gram of liquid dihydrogen and LPG are 50 and
142 kJ, respectively.
(iii) It is a good conductor of electricity.
(a) I, II and III only
43. The number of 2-centre-2-electron and (b) II, III and IV only
(c) II and IV only
3-centre-2-electron bonds in B2H6 ,
(d) I and III only [ JEE Main 2019, 11 Jan Shift-I]
respectively, are
(a) 4 and 2 (b) 2 and 4 Exp. (a)
(c) 2 and 2 (d) 2 and 1
(I) H2 is a 100% pollution free fuel. So, option (I) is
correct.
Exp. (a) 1
(II) Molecular weight of H2 (2u). = × molecular
29
The structure of B 2 H 6 can be shown as :
weight of butane, C 4H10 (LPG) [58u].
H H H
H So, compressed H2 weighs ~30 times more
H eH than a petrol tank and option (b) is correct.
–2
3c–3e 2c 3
B B Þ B B sp (III) NaNi 5 , Ti - TiH2 etc. are used for storage of H2
H H in small quantities. Thus, option (c) is correct.
H H H
H (IV) On combustion values of energy released per
In B 2H 6, four 2-centre-2-electron (2c − 2e ) bonds are gram of liquid dihydrogen (H2 ) : 142 kJ g −1,
present in the same plane and two 3-centre-2-electron and for LPG : 50 kJ g −1. So, option (d) is incorrect.
( 3c − 2e ) bonds are present in another plane.
46. The correct order of the atomic radii of
44. NaH is an example of C, Cs, Al and S is
(a) metallic hydride (a) C < S < Al < Cs (b) C < S < Cs < Al
(b) electron-rich hydride (c) S < C < Cs < Al (d) S < C < Al < Cs
(c) saline hydride [ JEE Main 2019, 11 Jan Shift-I]
(d) molecular hydride
[ JEE Main 2019, 11 Jan Shift-I] Exp. (a)
Element Period No. Group No.
Exp. (c)
r s C 2nd 14
Na H is an example of ionic or saline hydride. These
 Al 3rd 13  Along the period
hydrides are formed when hydrogen combines with 
 atomic radius
metals having less electronegativity and more S 3rd 16 
electropositive character with respect to hydrogen. decreases, so, radii :
Except Be and Mg, all s-block metals form saline Al > S.
hydrides. Cs 6th 1

With the addition of a new shell, period number as well Here, M can be Si, Sn and Pb because they have
as atomic radius increases. It is because of the vacant nd-orbital. But, carbon is a member of second
successive addition of one extra shell of electrons. So, period (n = 2, l = 0, 1), it does not have d-orbital
the order of the atomic radii of the given elements will ( l = 2 ). So, CCl 4 will not be hydrolysed and correct
be: C < S < Al < Cs option is (b).
47. The amphoteric hydroxide is 49. The relative stability of + 1 oxidation state of
(a) Be(OH) 2 (b) Ca(OH) 2 group 13 elements follows the order
(c) Sr(OH) 2 (d) Mg(OH) 2 (a) Al < Ga < Tl < In (b) Al < Ga < In < Tl
[ JEE Main 2019, 11 Jan Shift-I] (c) Tl < In < Ga < Al (d) Ga < Al < In < Tl
Exp. (a)
For group-2 metal hydroxides, basicity increases Exp. (b)
down the group, as: The stability order of + 3 and + 1 oxidation states of
Be(OH)2 < Mg(OH)2 < Ca(OH)2 group 13 elements will be:
3+
< Sr(OH)2 < Ba(OH)2 B > Al 3 + > Ga 3 + > In3 + >>Tl 3 +
This is because as the size of metal atom increases, (order of + 3 oxidation state)
M—OH bond length increases or M—OH bond B + <<Al + < Ga + < In + < Tl +
become weaker thus readily breaks to release OH − (order of + 1 oxidation state)
ions which are responsible for the basicity of these The presence of two oxidation states in p-block
solutions. elements is due to the inert pair effect.
But Be(OH)2 shows amphoteric (basic as well as Because of the presence of poor shielding d and
acidic) character as it reacts with acid and alkali both f-orbitals, as we move from Ga to Tl, effective nuclear
which is shown in the following reactions. Be(OH)2 as charge of these elements increases so as to hold the
a base : valence ns 2 electrons tightly. It causes difficulty to the
Be(OH)2 + 2HCl → BeCl 2 + 2H 2O ionisation of ns 2-electrons and it remains inert, only
Be(OH)2 as an acid : np1-electron ionises to give + 1 oxidation state.
Be(OH)2 + 2NaOH → Na 2[Be(OH)4 ]
50. The hydride that is not electron deficient is
48. The chloride that cannot get hydrolysed is (a) AlH 3 (b) B2H 6
(a) SnCl 4 (b) CCl 4 (c) PbCl 4 (d) SiCl 4 (c) SiH 4 (d) GaH 3
[ JEE Main 2019, 11 Jan Shift-I] [ JEE Main 2019, 11 Jan Shift-II]
Exp. (b) Exp. (c)

The compounds given are the tetrahalides GaH 3, AlH 3 and B 2H 6 are the hydrides of group-13
(MCl 4 ) of group 14 elements. For the hydrolysis, ( ns 2np1 ), whereas SiH 4 is an hydride of group 14.
(nucleophilic substitution) of MCl 4 the nature of the H H
M—Cl bond should be as:
sp2 sp2
Ga Al
δ+ δ– H H H H
M——Cl
6e – around 6e – around
It must expand its covalency beyond 4 by the use Ga 3+ <8e – (octet) Al 3+ <8e – (octet)
of its vacant d-orbital which will accommodate the (GaH3) (AlH3)
lone pair of electrons of H2O (the–nucleophile). 3c–2e – bridge bond
H
sp3d H sp3 H
sp3 B B
Cl3 M——Cl Cl3 M——Cl H H
d + d – OH2 H
B is sp3, but cannot satisfy octet due
d0
O
H H to the attachment of two 3c-2e –
–HCl bridge bonds (B–H–B)
Transition state
3H2O sp3 So, B 2H 6, AlH 3 and GaH 3 are electron deficient

M(OH)4 Cl3 M—(OH) hydrides.
–3HCl
But, SiH 4 is an electron precise hydride of group-14
( ns 2np2 ), i.e. these hydrides can have the required

number of electrons to write their conventional Lewis (iv) Portland cement constitutes, tricalcium
structures. aluminosilicate, 3CaO ⋅Al 2O 3 . SiO 2 ,
H i.e. Ca 3 Al 2O 6 ⋅ SiO 2 .
8e– around Si (Octet gets satisfied)
Si 52. A metal on combustion in excess air forms X . X
H
H H upon hydrolysis with water yields H2O2 and O2

along with another product. The metal is
51. Match the following items in Column I with the (a) Li (b) Mg (c) Rb (d) Na
corresponding items in Column II. [ JEE Main 2019, 12 Jan Shift-I]
Column I Column II Exp. (c)

(i) Na 2CO 3 ⋅ 10H 2O A. Portland cement Metal (A) is rubidium (Rb). In excess of air, it forms
ingredient RbO 2( X ). X is a superoxide that have
O −2 ion. It is due to the stabilisation of large anion by
(ii) Mg(HCO 3 )2 B. Castner-Kellner large cations through lattice energy effects. RbO 2(X)
process gets easily hydrolysed by water to form the hydroxide,
(iii) NaOH C. Solvay process H 2O 2 and O 2.
The reaction involved are as follows:
(iv) Ca 3Al 2O 6 D. Temporary hardness
Rb + O 2 → RbO 2 (superoxide)
(X )
(a) (i) - (D); (ii) - (A); (iii) - (B); (iv) - (C)
(b) (i) - (B); (ii) - (C); (iii) - (A); (iv) - (D) 2RbO 2 + 2H 2O → 2RbOH + H 2O 2 + O 2
(X )
(c) (i) - (C); (ii) - (B); (iii) - (D); (iv) - (A)
(d) (i) - (C); (ii) - (D); (iii) - (B); (iv) - (A) 53. Iodine reacts with concentrated HNO3 to yield
[ JEE Main 2019, 11 Jan Shift-II] Y along with other products. The oxidation
state of iodine inY , is
Exp. (d)
(a) 1 (b) 3 (c) 7 (d) 5
(i) Washing soda (Na 2CO 3 ⋅ 10H2O) is
manufactured in Solvay process. In this
method, CO 2 gas is passed through a Exp. (d)
conc. solution of NaCl saturated with NH3 . It Iodine reacts with concentrated HNO 3to yield HIO 3
gives ammonium carbonate followed by along with NO 2 and H 2O. The reaction involved in as
ammonium hydrogen carbonate. follows :
The obtained NH4HCO 3 is treated with I 2 + 10HNO 3 → 2HIO 3 + 10NO 2 + 4H 2O
solution of NaCl which result in the formation The oxidation state of ‘I’ in HIO 3 is + 5 as calculated
of NaHCO 3 . The crystal obtained are heated below :
to obtain Na 2CO 3 . 1 + x + 3( −2 ) = 0
NaCl + NH3 + CO 2 + H2O → x − 5 = 0, x = + 5
NaHCO 3 + NH4Cl
54. The volume strength of 1 M H2O2 is
∆
2NaHCO 3 → Na 2CO 3 (Molar mass of H2O2 = 34 g mol− 1 )
−H 2O, CO 2
(a) 16.8 (b) 22.4 (c) 11.35 (d) 5.6
Crystallisation
→ Na 2CO 3 ⋅ 10H2O [ JEE Main 2019, 12 Jan Shift-II]
(ii) Mg(HCO 3 )2 and Ca(HCO 3 )2 cause temporary Exp. (c)
hardness to water that can be easily removed Concentration of H 2O 2 is expressed in terms of
by boiling. volume strength, i.e. “volume of O 2 liberated by H 2O 2
(iii) NaOH is manufactured by Castner-Kellner at NTP”. Molarity is connected to volume strength as:
process. x
Molarity (M) = or x = Molarity × 11.2
In this reaction, Na amalgam flows out and 112 .
treated with water to give NaOH and H2 gas. where, x = volume strength
During electrolysis, hydrogen is evolved at So, for 1 M H 2O 2
cathode and chlorine is evolved at anode, x = 1 × 112
. = 112.
which are the by product of this process. Among the given options, 11.35 is nearest to 11.2.

II. They participate in the oxidation of glucose to

55. The element that shows greater ability to form produce ATP.
pπ-pπ multiple bonds, is III. Along with sodium ions, they are responsible
(a) Ge (b) Si (c) Sn (d) C for the transmission of nerve signals.
[ JEE Main 2019, 12 Jan Shift-II] (a) I, and III only (b) I, II and III
Exp. (d) (c) I and II only (d) III only

Carbon (C) has greatest ability to form stable pπ-pπ [ JEE Main 2019, 12 Jan Shift-II]
multiple bonds. 2 p-orbitals of this element participate
in the process. The stability of multiple bonds of C is Exp. (b)
attributed to their closeness with C-nucleus. Thus, the All the statements are correct. K + being metallic
smaller size of C plays a significant role in the process. unipositive ions work as enzyme activators.
These also participate in many reactions of glycolysis
56. Chlorine on reaction with hot and oncentrated and Kreb’s cycle to produce ATP from glucose.
sodium hydroxide gives Being unipositive these are also equally responsible
(a) Cl − and ClO − (b) Cl − and ClO −3 for nerve signal transmission along with Na + . (Na +
(c) ClO −3 and ClO −2 (d) Cl − and ClO −2 ion-pump theory)
59. The recommended concentration of fluoride
Exp. (b) ion in drinking water is up to 1 ppm as fluoride
Halogens form halates and halides with hot and ion is required to make teeth enamel harder by
concentrated solution of NaOH as : converting [3Ca 3 (PO4 )2 ⋅ Ca(OH)2 ] to :
3 X 2 + 6NaOH → 5NaX + NaXO 3 + 3H 2O [JEE Main 2018]
So, Cl 2 will also give Cl − (as NaCl) and ClO −3 (a) [CaF2 ] (b) [3(CaF2 ) ⋅ Ca(OH)2 ]
(as NaClO 3 ) in the above reaction. (c) [3Ca 3(PO 4 )2 ⋅ CaF2 ] (d) [3{Ca 3(PO 4 )2 } ⋅ CaF2 ]
Thus, option (b) is correct.
Exp. (c)
Note When halogens react with cold and dilute
solution of NaOH, hypohalites and halides are Fluoride ions help in making teeth enamel harder by
produced as: converting [3Ca 3(PO 4 )2 ⋅ Ca(OH)2 ] i.e. Hydroxy
apatite to [3Ca 3(PO 4 )2 ⋅ CaF2 ] i.e., Fluorapatite
X 2 + 2NaOH → NaX + NaXO + H 2O
(Harder teeth enamel) via following reaction:
57. The element that does not show catenation is [3Ca 3(PO 4 )2 ⋅ Ca(OH)2 ] + 2F −
From
(a) Ge (b) Sn (c) Si (d) Pb drinking water
[ JEE Main 2019, 12 Jan Shift-II] → [3Ca 3(PO 4 )2 ⋅ CaF2 ] + 2OH −

Exp. (d)
The property of self-linking of atoms of an element 60. Total number of lone pair of electron in
through covalent bonds to form straight or branched I−3 ion is [JEE Main 2018]
chains and rings of different sizes is called catenation.
Down the group, catenation tendency decreases due
(a) 3 (b) 6
to decrease in element bond strength. Carbon (C), (c) 9 (d) 12
silicon (Si), germanium (Ge), tin (Sn), lead (Pb) are
group-14 elements. Exp. (c)
Catenation tendency is highest in carbon while silicon The structure of I −3 ion is
has second highest tendency of catenation among all –
elements of family due to higher bond energy. The
decreasing tendency of catenation among group 14 I
elements is as follows:
C >> Si > Ge ≈ Sn
However, Pb does not show catenation. I
58. The correct statement(s) among I to III with

respect to potassium ions that are abundant I
within the cell fluids is/are
I. They activate many enzymes. Hence, 9 is the correct answer.

61. Hydrogen peroxide oxidises [Fe(CN)6 ]4 − to 63. When metal ‘M ’ is treated with NaOH, a
[Fe(CN)6 ]3− in acidic medium but reduces white gelatinous precipitate ‘X ’ is obtained,
which is soluble in excess of NaOH.
[Fe(CN)6 ]3− to [Fe(CN)6 ]4 − in alkaline
Compound ‘X ’ when heated strongly gives
medium. The other products formed are, an oxide which is used in chromatography
respectively. [JEE Main 2018] as an adsorbent. The metal ‘M ’ is

(a) (H2O + O 2 ) and H2O [JEE Main 2018]
(b) (H2O + O 2 ) and (H2O + OH− ) (a) Zn (b) Ca (c) Al (d) Fe
(c) H2O and (H2O + O 2 )
Exp. (c)
(d) H2O and (H2O + OH− )
Among the given metals Al forms white gelatinous
Exp. (c) ppt. with NaOH. Hence, the probable metal can be
Al.
Both reactions in their complete format are written
below This ppt. is dissolved in excess of NaOH due to the
formation of sodium metal Aluminate. Both the
(i) In acidic medium, reactions are shown below.
−1
[Fe 2+(CN)6 ]4 − + H2 O 2 + 2H+ Al 3 + NaOH
→ Al(OH)3 ↓
White gelatinous
−2
→ [Fe 3+(CN)6 ]3 − + 2H2 O
ppt. ( X) of
aluminium
hydroxide
(ii) In alkaline medium,

−1  Excess of NaOH
[Fe 3+(CN)6 ]3 − + H2 O 2 + 2OH− → ↓
[Fe 2 + (CN)6 ]4 − + O 2 + 2H2O NaAlO 2
(Sodium
metaaluminate)
Hence, H2O (for reaction (i)) and O 2 + H2O soluble
(for reaction (ii)) are produced as by product.
Aluminium hydroxide on strong heating gives
alumina (Al 2O 3 ) which is used as an adsorbent in
62. The compound that does not produce chromatography. This reaction can be seen as :
nitrogen gas by the thermal decomposition
∆
is [JEE Main 2018] 2Al(OH)3 → Al 2O 3 + 3H2O
(a) Ba(N 3 )2
Thus, metal M is Al.
(b) (NH4 )2 Cr2O 7
Ca, being below sodium in electrochemical
(c) NH4 NO 2
reactivity series, cannot displaces Na from its
(d) (NH4 )2 SO 4 aqueous solution.
Exp. (d) Zn reacts with NaOH to form sodium zincate which
is a soluble compound.
The thermal decomposition of given compounds Fe reacts with sodium hydroxide to form
is shown below tetrahydroferrate (II) sodium which is again a
∆
(NH4 )2 Cr2O 7 → N2 + 4H2O + Cr2O 3 soluble complex.
∆
NH4NO 2 → N2 + 2H2O 64. Both lithium and magnesium display
several similar properties due to the
∆
(NH4 )2 SO 4 → 2NH3 +H2SO 4 diagonal relationship; however, the one
which is incorrect is [JEE Main 2017 (Offline)]
Ba(N3 )2 → Ba + 3N2
(a) Both form basic carbonates
Thus, only (NH4 )2 SO 4 does not gives N2 on (b) Both form soluble bicarbonates
heating (It give NH3 ). While rest of the given (c) Both form nitrides
compounds gives N2 on their thermal
(d) nitrates of both Li and Mg yieldNO 2 andO 2 on
decomposition. heating
Exp. (a)

Mg can form basic carbonate while Li can not. Species Hybridisation

5 Mg 2 + + 6 CO 2–
3 + 7H2O →
4MgCO 3 ⋅ Mg(OH)2 ⋅ 5H2O + 2 HCO −3 N sp2

–
65. The products obtained when chlorine gas O
reacts with cold and dilute aqueous NaOH

N sp2
are [JEE Main 2017 (Offline)] –
(a) ClO − and ClO −3
(b) ClO −2 and ClO −3
(c) Cl − and ClO − N sp2
(d) Cl − and ClO −2 +
N sp
Exp. (c)
Cl 2 , Br2 and I2 form a mixture of halide and 68. The pair in which phosphorus atoms have a
hypohalites when react with cold dilute alkalies formal oxidation state of +3 is
while a mixture of halides and haloate when react [JEE Main 2016 (Offline)]
with concentrated cold alkalies. (a) pyrophosphorous and hypophosphoric acids
Cl 2 + 2NaOH → NaCl + NaClO + H2O (b) orthophosphorous and hypophosphoric acids
Cold and dilute (c) pyrophosphorous and pyrophosphoric acids
∴ Cl − and ClO − are obtained as products when (d) orthophosphorous and pyrophosphorous
chlorine gas reacts with cold and dilute aqueous acids
NaOH.
Exp. (d) O
66. The hottest region of Bunsen flame shown 
in the figure given below is Orthophosphorous acid, H3PO 3 : HO  P  OH

x
H
Region 4 H3 PO3 = 3 + x + 3(−2 ) = 0 or x = + 3
Region 3
Pyrophosphorous acid,
Region 2
Region 1 O O
 
H4P2O 5 : HO  P O  P OH
 
H H
x
(a) region 2 (b) region 3 H4 P2 O 5 = 4 + 2 x + 5 ( − 2) = 0
(c) region 4 (d) region 1
4 + 2 x − 10 = 0 ⇒ x = + 3
Exp. (a)
69. Which one of the following statements about
Region 1 (Pre-heating zone) water is false? [JEE Main 2016 (Offline)]
Region 2 (Primary combustion zone, hottest (a) Water can act both as an acid and as a base
zone) (b) There is extensive intramolecular hydrogen
Region 3 (Internal zone) bonding in the condensed phase
Region 4 (Secondary reaction zone) (c) Ice formed by heavy water sinks in normal
water
67. The species in which the N-atom is in a state (d) Water is oxidised to oxygen during
of sp hybridisation is photosynthesis
Exp. (b)
(a) NO −2 (b) NO −3
There is extensive intermolecular H-bonding in
(c) NO 2 (d) NO +2 the condensed phase.
Exp. (d)

On the other hand, rest metals i.e. Ca, Ba, Sr have

70. The main oxides formed on combustion of
bigger size and that's why lattice energy is greater
Li, Na and K in excess of air respectively
than hydration energy.
are [JEE Main 2016 (Offline)]
(a) LiO 2 , Na 2O 2 and K 2O Time Saving Technique In the question of finding
hydration energy only check the size of atom. Smaller
(b) Li 2O 2 , Na 2O 2 and KO 2
(c) Li 2O, Na 2O 2 and KO 2 sized atom has more hydration energy.
(d) Li 2O , Na 2O and KO 2 Thus, in this question Be is placed upper most in the
group has lesser size and not comparable with the
Exp. (c) size of sulphates. Hence, BeSO 4 is the right
1
2Li + O 2 (g ) → Li 2O response.
2
(Excess)
73. Which among the following is the most
2Na + O 2 (g ) → Na 2O 2 reactive? [JEE Main 2015]
( Excess)
(a) Cl 2 (b) Br2
K + O 2 (g ) → KO 2 (c) I 2 (d) ICl
(Excess)
71. From the following statements regarding Exp. (d)

H 2O2, choose the incorrect statement. Cl2 , Br2 and I2 are homonuclear diatomic molecule in
[JEE Main 2015] which electronegativity of the combining atoms is
(a) It can act only as an oxidising agent same, so they are more stable and less reactive,
(b) It decomposed on exposure to light whereas, I and Cl have different electronegativities
(c) It has to be stored in plastic or wax lined and bond between them are polarised and hence,
glass bottles in dark reactive. Therefore, interhalogen compounds are
(d) It has to be kept away from dust more reactive.
Time Saving Technique In this type of question of
Exp. (a) halogen, only go through the polarity of the molecule.
H2O 2 acts as an oxidising as well as reducing As we know, diatomic molecule does not have
agent, because oxidation number of oxygen in polarity but molecules with dissimilar sizes have
H2O 2 is –1. So, it can be oxidised to oxidation polarity resulting in more reactivity.
state 0 or reduced to oxidation state −2.
H2O 2 decomposes on exposure to light. So, it 74. Which one has the highest boiling point?
has to be stored in plastic or wax lined glass [JEE Main 2015]
bottles in dark for the prevention of exposure. It (a) He (b) Ne
also has to be kept away from dust. (c) Kr (d) Xe
72. Which one of the following alkaline earth Exp. (d)

metal sulphates has its hydration enthalpy As we move down the group of noble gases,
greater than its lattice enthalpy? molecular mass increases by which dipole produced
[JEE Main 2015] for a moment and hence London forces increases
from He to Xe. Therefore more amount of energy is
(a) CaSO 4 (b) BeSO 4
required to break these forces, thus boiling point also
(c) BaSO 4 (d) SrSO 4 increases from He to Xe.
Exp. (b) 75. Among the following oxoacids, the correct
As we move down the group, size of metal decreasing order of acid strength is
increases. Be has lower size while SO 2−
4 has (a) HOCl > HClO 2 > HClO 3 > HClO 4
bigger size, that's why BeSO 4 breaks easily and (b) HClO 4 > HOCl > HClO 2 > HClO 3
lattice energy becomes smaller but due to lower (c) HClO 4> HClO 3 > HClO 2 > HOCl
size of Be, water molecules are gathered around
(d) HClO 2 > HClO 4> HClO 3 > HOCl [JEE Main 2014]
and hence hydration energy increases.

Exp. (c) Exp. (a)

Acidic strength of oxoacids depends upon the The electronic configuration of NO[15 e − ] is given
stability of conjugate base. More stable the by σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 , σ2 pz2 , π2 p2x
conjugate base of an acid, stronger is the acid.
= π2 py2 , π* 2 p1z
ClO −4 + H+
HClO 4 S
Thus, NO possess one unpaired electron, hence,
HClO 3 S ClO −3 + H+
it is paramagnetic in nature. However, it dimerises
HClO 2 S ClO −2 + H+ at low temperature to become diamagnetic.
HOCl S ClO − + H+ 2NO s N2O 2
Conjugate bases stabilizes by resonance. 1
- Bond order of NO = [10 − 5] = 2.5
O O 2
Thus, bond order of NO is 2.5 and it combines with
O 2 to give NO 2 .
ClO4– Cl Cl
Hence, the correct option is (a).
–
O O O O
O O 77. Which of the following is wrong statement?
(a) ONCl and ONO − are not isoelectronic
O (b)O 3 molecule is bent
O (c) Ozone is violet-black in solid sate
(d) Ozone is diamagnetic gas [JEE Main 2013]
Cl
Cl
–
O O Exp. (a), (b), (c) and (d)
O O O
O
- (a) Number of electrons in
ONCl = 3.2 e −
ClO3–
ONO − = 24 e −
O Thus, ONCl and ONO − are not isoelectronic.
–
O O
(b) O 3 has bent shape structure.
Cl Cl Cl Central atom O is sp2 hybridised with 1 lone
– pair of electrons.
O O –
O
O O O O
– O O
O O
(c) Ozone is violet-black in solid state.
ClO2– Cl Cl (d) O 3 has no unpaired electrons, thus it is
O
–
O diamagnetic.
Hence, all the given statements are correct.
ClO − does not show resonance. Thus, the stability 78. Which of the following exists as covalent
order of conjugate base due to resonance is
crystals in the solid state? [JEE Main 2013]
ClO −4 > ClO −3 > ClO −2 > ClO −
(a) Iodine
Hence, the acidic strength of given oxoacids is as
follows (b) Silicon
HClO 4 > HClO 3 > HClO 2 > HClO (c) Sulphur
(d) Phosphorus
76. Which one of the following properties is not
shown by NO? [JEE Main 2014] Exp. (b)
(a) It is diamagnetic in gaseous state Silicon exists as covalent crystal in solid state. It
(b) It is a neutral oxide exhibits a network structure like diamond.
(c) It combines with oxygen to form nitrogen
dioxide
(d) Its bond order is 2.5

(d) N 2 O 4 can form two resonance structures

79. Which of the following on thermal
decomposition yields a basic as well as r r - r r
O N N O O N N O
acidic oxide? [AIEEE 2012]
(a) NaNO 3 (b) KCIO 3
sO sO O O
(c) CaCO 3 (d) NH4 NO 3 s

Thus it is correct.
Exp. (c)
∆ 82. Which of
(a) 2NaNO 3 → 2NaNO 2 + O 2 the following statements
regarding sulphur is incorrect? [AIEEE 2011]
∆
(b) 2KClO 3 → 2KCl + 3O 2 (a) S2 molecule is paramagnetic
∆ (b) The vapour at 200°C consists mostly of S8 rings
(c) CaCO 3 → CaO + CO 2
(c) At 600°C, the gas mainly consists of S2
Basic Acidic
molecules
∆
(d) NH4NO 3 → N2O + H2O (d) The oxidation state of sulphur is never less
than +4 in its compounds
80. Very pure hydrogen (99.9) can be made by
which of the following processes? Exp. (d)
(a) Reaction of methane with steam [AIEEE 2012] (a) S2 molecule is paramagnetic due to unpaired
electrons in MO and is blue coloured
(b) Mixing natural hydrocarbons of high
compound, thus true.
molecular weight
(b) The vapour at 200°C consists mostly of S8
(c) Electrolysis of water
rings, thus correct.
(d) Reaction of salts like hydrides with water
(c) At 600°C, the gas mainly consists of S2
Exp. (d) molecules, thus correct.
(d) Oxidation states of sulphur are
Hydrides are instant source of hydrogen of higher
purity. They react with H2O forming H2 gas. −2 in H2S
CaH2 + 2H2O → Ca(OH)2 + 2H2 0 in S8
+2 in S2O 2−
3
81. Which of the following statements is wrong? + 4 in SO 2
(a) The stability of hydrides increases from NH3
to BiH3 in group 15 of the periodic table + 6 in SO 3
(b) Nitrogen can’t form dπ-pπ bond Thus, incorrect. (Valency can be less than 4)
(c) Single N—N bond is weaker than the single Hence, correct option is (d).
P—P bond
(d) N 2O 4 has two resonance structure 83. Boron can’t form which one of the following
[AIEEE 2011] anions? [AIEEE 2011]
Exp. (a) (a) BF63 − (b) BH−4 (c) B(OH)−4 (d) BO −2
(a) Thermal stability of the hydrides decrease as Exp. (a)

we go down the group in periodic table for
B5
group 15 (N-family) 1s 2 2s 2 2p 1
BiH 3 < SbH 3 < AsH 3 < PH 3 < NH 3
Ground state
Least stable Most stable
2s 1 2p 2
M-H — 255 247 322 391
Bond-energy Excited state
kJ mol −1
Fourth lone pair is accommodated
(b) Due to absence of d-orbital, nitrogen can’t in this empty orbital
form dπ − pπ bond, thus it is correct.
Maximum covalency = 4
(c) The N–N bond (BE 160 kJ mol −1) is weaker
than P–P bond (BE 209 kJ mol −1). Thus, it is
correct.

Due to absence of 2d-orbital, maximum covalency As metallic character of the element attached to
is four. Thus, BF63− is not formed. oxygen atom increases, the basic character of
oxides increases.
Therefore, (a) is not formed while
BH−4 (BH3 + H− ), B(OH)–4 , (B[OH)3 + OH– ] and Hence, the increasing correct order of basic
BO –2 are formed. nature is Al 2O 3 < MgO < Na 2O < K 2O.
87. Among the following, the maximum

84. The products obtained on heating LiNO3 covalent character is shown by the
will be [AIEEE 2011] compound. [AIEEE 2011]
(a) LiNO 2 + O 2 (b) Li 2O + NO 2 + O 2 (a) SnCl 2 (b) AlCl 3 (c) MgCl 2 (d) FeCl 2
(c) Li 3 N + O 2 (d) Li 2O + OH + O 2
Exp. (b)
Exp. (b) Greater the charge and smaller the size of the
LiNO 3 behave differently from other alkali metal cation, larger the charge density. Thus, greater is
nitrates. the polarization of M − Cl bond and hence,
Lithium nitrates decompose on heating producing maximum covalent character is possessed by the
NO 2 . Whereas other alkali nitrates like NaNO 3 compound.
produces nitrite and oxygen on decomposition. Among the given species, only AlCl 3 possesses
∆ Li O +2NO + 1 O maximum covalent charge due to the presence of
2Li NO 3 → 2 2 2 large charge density on Al 3+ ion.
2
NaNO 3 → ∆ NaNO + 1 O
2
2
2 88. In which of the following arrangements, the
sequence is not strictly according to the
85. What is the best description of the change property written against it? [AIEEE 2009]
that occurs when Na 2O(s) is dissolved in (a) CO 2 < SiO 2 < SnO 2 < PbO 2
water? [AIEEE 2011] increasing oxidising power
(a) Oxidation number of sodium decreases (b) HF < HCl < HBr < HI
(b) Oxide ion accepts a shared pair of electrons increasing acid strength
(c) Oxide ion donates a pair of electrons (c) NH3 > PH3 < AsH3 < SbH3
(d) Oxidation number of oxygen increases increasing basic strength
Exp. (c) (d) B < C < O < N
Na 2O +H2O → 2NaOH increasing first ionisation enthalpy
Oxidation number +1 −2 −2 +1 +2 Exp. (c)

of Na and Oxygen The correct increasing basic strength
No change in oxidation number, so (a) and (d) SbH3 < AsH3 < PH3 < NH3
are not true. NH3 is most basic because of its small size, the
(b) is also not true. electron density of electron pair is concentrated
Oxide ion donates a pair of electrons, thus over small region.
changes to OH− . As the size increases, the electron density gets
86. Which one of the following order represents diffused over a large surface area and hence the
the correct sequence of the increasing basic ability to donate the electron pair (basicity)
nature of the given oxides? [AIEEE 2011] decreases. Hence, basic strength decreases
(a) MgO < K 2O < Al 2O 3 < Na 2O down the group.
(b) Na 2O < K 2O < MgO < Al 2O 3
89. Which one of the following reaction of
(c) K 2O < Na 2O < Al 2O 3 < MgO
xenon compounds is not feasible?
(d) Al 2O 3 < MgO < Na 2O < K 2O
(a) XeO 3 + 6HF → XeF6 + 3H2O
Exp. (d) (b) 3XeF4 + 6H2O → 2Xe + XeO 3 + 12HF + 1.5O 2
Metallic character decreases on moving along a (c) 2XeF2 + 2H2O → 2Xe + 4HF + O 2
period in the sequence as Na > Mg > Al and
increases down the group. (d) XeF6 + RbF → Rb[XeF7 ] [AIEEE 2009]

Exp. (a) 92. Among the following substituted silanes the

XeF6 has much tendency to hydrolyse. The one which will give rise to cross linked
reverse reaction is more spontaneous. silicone polymer on hydrolysis is
XeF6 + 3H2O → XeO 3 + 6HF [AIEEE 2007]
(a) R4 Si (b) R SiCl 3

90. The bond dissociation energy of B—F in BF3 (c) R2 SiCl 2 (d) R3 SiCl
is 646 kJ mol −1 whereas that of C—F in CF4 is
515 kJ mol −1. The correct reason for higher Exp. (b)
B—F bond dissociation energy as compared RSiCl 3 give cross linked silicone polymer on
to that of C—F is [AIEEE 2009] hydrolysis.
(a) smaller size of B-atom as compared to that of 93. Which one of the following is the correct
C-atom
statement ? [AIEEE 2007]
(b) stronger σ-bond between B and F in BF3 as
compared to that between C and F in CF4 (a) Boric acid is a protonic acid
(c) significant pπ - pπ interaction between B and F (b) Beryllium exhibits coordination number of six
in BF3 whereas there is no possibility of such (c) Chlorides of both beryllium and aluminium
interaction between C and F in CF4 have bridged chloride structures in solid
(d) lower degree of pπ - pπ interaction between phase
B and F in BF3 than that between C and F in CF4 (d) B2 H6 ⋅ 2NH3 is known as ‘inorganic benzene’
Exp. (c) Exp. (c)

Due to identical sizes of 2 p −orbitals on B and F, Chlorides of both beryllium and aluminium have
back donation of a lone pair of electrons from the bridged structures in solid phase.
filled 2 p − orbital of F to the empty 2 p -orbital of B
occurs to a considerable extent. 94. Identify the incorrect statement among the
As a result, B  F bond has some double bond following [AIEEE 2007]
character and hence, bond dissociation energy of (a) Ozone reacts with SO 2 to give SO 3
B  F bond in BF3 is much higher that of C  F (b) Silicon reacts with NaOH (aq ) in the presence
bond in CF4 . This is due to the absence of empty of air to give Na 2 SiO 3 and H2O
2 p − orbital and hence, back donation does not (c) Cl 2 reacts with excess of NH3 to give N 2 and
occur. HCl
(d) Br2 reacts with hot and strong NaOH solution
91. In context with the industrial preparation of to give NaBr, NaBrO 4 and H2O
hydrogen from water gas (CO + H 2 ) , which
of the following is the correct statement ? Exp. (d)
(a) CO and H2 are fractionally separated using Br2 reacts with hot and strong NaOH to give NaBr,
differences in their densities [AIEEE 2008] NaBrO 3 and H2O.
(b) CO is removed by absorption in aqueous
Cu 2Cl 2 solution 95. The stability of dihalides of Si, Ge, Sn and Pb
(c) H2 is removed through occlusion with Pd increases steadily in the sequence
(d) CO is oxidised to CO 2 with steam in the [AIEEE 2007]
presence of a catalyst followed by absorption (a) GeX 2 < SiX 2 < SnX 2 < PbX 2
of CO 2 in alkali. (b) SiX 2 < GeX 2 < PbX 2 < SnX 2
Exp. (d) (c) SiX 2 < GeX 2 < SnX 2 < PbX 2
(d) PbX 2 < SnX 2 < GeX 2 < SiX 2
CO is oxidised to CO 2 with steam in the presence
of a catalyst followed by the absorption of CO 2 in Exp. (c)
alkali
Inert pair effect becomes predominant due to
Steam
CO + H2 → CO 2 + 2H2 which +2 oxidation state becomes more stable
catalyst down the group and hence, the stability of
 KOH dihalides increases down the group.
↓
SiX 2 < GeX 2 < SnX 2 < PbX 2
K 2CO 3

96. Regular use of which of the following Exp. (c)

fertilizers increases the acidity of soil ? In MCl 2 , oxidation state of M = + 2
(a) Potassium nitrate [AIEEE 2007] In MCl 4 , oxidation state of M = + 4
(b) Urea Higher the oxidation state, smaller is the size.
(c) Superphosphate of lime Greater the polarising power, greater is the

(d) Ammonium sulphate covalent characteristic.
Exp. (d) Hence, MCl 4 is more covalent and MCl 2 is more
ionic.
(NH4 )2 SO 4 → 2NH 4+ + SO 24 −
Acidic 100. The structure of diborane (B 2H 6 ) contains
97. The type of hybridisation of boron in (a) four 2c − 2e − bonds and four 3 c − 2e − bonds
diborane is [AIEEE 2007] (b) two 2c − 2e − bonds and two 3 c − 3e − bonds
(a) sp hybridisation (c) two 2c − 2e − bonds and four 3 c − 2e − bonds
(b) sp 2 hybridisation (d) four 2 c − 2e − bonds and two 3c − 2e − bonds
[AIEEE 2005]
(c) sp 3 hybridisation
3 2 Exp. (d)
(d) sp d hybridisation
Structure of B 2H6
Exp. (c) Electrons of H Electrons of B
Boron atom in B 2H6 (diborane) is sp3 hybridised. 3c-2e– bonds
98. Which of the following statements is true ?

[AIEEE 2006]
2c-2e– bonds B B
(a) H3 PO 3 is a stronger acid than H2 SO 3 2c-2e– bonds
(b) In aqueous medium, HF is a stronger acid
than HCl
(c) HClO 4 is weaker acid than HClO 3 3c-2e– bonds
(d) HNO 3 is a stronger acid than HNO 2
Exp. (d) 101. Heating of an aqueous solution of
aluminium chloride to dryness will give
Conjugate base of HNO 3 is resonance stablised (a) Al(OH)Cl 2 (b) Al 2O 3 [AIEEE 2005]
than that of HNO 2 . Hence, HNO 3 is stronger acid
(c) Al 2Cl 6 (d) AlCl 3
than HNO 2 .
O
- Exp. (b)
O
Aqueous solution of AlCl 3 is acidic, as it gives HCl
HON HN
on hydrolysis.
O
- O AlCl 3 + 3H2O r Al(OH)3 + 3HCl
On strongly heating, Al(OH)3 is converted into
O Al 2O 3 .
HON No resonance ∆
2Al(OH)3 → Al 2O 3 + 3H2O
99. A metal, M forms chlorides in its +2 and
102. The number of hydrogen atom(s) attached
+4 oxidation states. Which of the
to phosphorus atom in hypophosphorous
following statements about these chlorides acid is
is correct? [AIEEE 2006] (a) three (b) one [AIEEE 2005]
(a) MCl 2 is more volatile than MCl 4 (c) two (d) zero
(b) MCl 2 is more soluble in anhydrous ethanol
than MCl 4 Exp. (c)
(c) MCl 2 is more ionic than MCl 4
Hypophosphorous acid (H3PO 2 ) is a monobasic
(d) MCl 2 is more easily hydrolysed than MCl 4
acid and has only one ionisable H because two

H-atoms are directly attached to phosphorus. Exp. (c)

Thus, the correct statement is (c).
In a group, ∆G °f (HX) changes from negative to
The structure of H3PO 2 is positive downwards.
H HF(g ), ∆G = − 273.20 kJ mol −1
|
HI(g ), ∆G = + 1.72 kJ mol −1
H P  O  H Ionisable as directly attached to O.

|| Thus, HF is thermally stable and HI not.
O
Thus, HF > HCl > HBr > HI
103. Which of the following oxides is amphoteric
in character? [AIEEE 2005] 106. One mole of magnesium nitride on reaction
(a) SnO 2 (b) SiO 2 with an excess of water gives [AIEEE 2004]
(c) CO 2 (d) CaO (a) one mole of ammonia
(b) one mole of nitric acid
Exp. (a) (c) two moles of ammonia
A species is amphoteric, if it is soluble in acid (d) two moles of nitric acid
(behave as a base) as well as in base (behave as
an acid). Exp. (c)
SnO 2 + 4HCl → SnCl 4 + 2H2O Mg 3N2 (s ) + 6H2O(l ) → 3Mg(OH)2 +2NH3 (g )
Base Acid 1 mol 2 mol
SnO 2 +2NaOH → Na 2SnO 3 + H2O 107. Excess of KI reacts with CuSO4 solution and
Acid Base then Na 2S2O3 solution is added to it. Which
104. In silicon dioxide [AIEEE 2005] of the following statements is incorrect for
this reaction? [AIEEE 2004]
(a) there are double bonds between silicon and
oxygen atoms (a) Cu 2 I2 is formed
(b) silicon atom is bonded to two oxygen atoms (b) CuI2 is formed
(c) each silicon atom is surrounded by two (c) Na 2 S 2O 3 is oxidised
oxygen atoms and each oxygen atom is (d) Evolved l 2 is reduced
bonded to two silicon atoms
(d) each silicon atom is surrounded by four Exp. (b)
oxygen atoms and each oxygen atom is CuSO 4 + 2KI → CuI2 + K 2SO 4
bonded to two silicon atoms
Unstable
Exp. (d) 2CuI2 → Cu2I2 + I 2
In SiO 2 , each silicon atom is bonded to four Thus, CuI2 is not formed.
oxygen atoms, that are arranged tetrahedrally
around it and each O − atom is attached to two 108. Beryllium and aluminium exhibit many
silicon atoms by covalent bonds. properties which are similar. But the two
elements differ in [AIEEE 2004]
O O (a) exhibiting maximum covalency in
Si Si compounds
O O (b) forming polymeric hydrides
O O O
(c) forming covalent halides
(d) exhibiting amphoteric nature in their oxides
105. The correct order of the thermal stability of
hydrogen halides ( H — X) is [AIEEE 2005] Exp. (a)
(a) HI > HCl > HF > HBr Be (Z = 4) has maximum covalency of 4 while Al
(b) HCl < HF > HBr < HI (Z = 13) has maximum covalency of 6.
(c) HF > HCl > HBr > HI
(d) HI > HBr > HCl > HF

109. Aluminium chloride exists as dimer, Al 2Cl 6 112. The solubilities of carbonates decrease
in solid state as well as in solution of down the magnesium group due to a
non-polar solvents such as benzene. When decrease in
dissolved in water, it gives [AIEEE 2004] (a) lattice energies of solids [AIEEE 2003]
(a) Al 3 + + 3Cl − (b) hydration energies of cations
(b) [Al[H2O)6 ]3 + + 3Cl − (c) inter ionic attraction

(c) [Al(OH)6 ]3 – + 3HCl (d) entropy of solution formation
(d) Al 2O 3 + 6HCl Exp. (b)

Exp. (b) The solubilities of carbonates of the alkaline earth
metals decrease down the group mainly due to
AlCl 3 is covalent but in water, it become ionic due decreasing hydration ethalpies of the cartions
to large hydration energy of Al 3+. from Be 2+ to Ba 2+ .
AlCl 3 + 6H2O r [Al(H O) ] 3+
+ 3Cl −
2 6 113. The substance not likely to contain CaCO3,
110. The soldiers of Napolean army while at is [AIEEE 2003]
Alps during freezing winter suffered a (a) a marble statue (b) calcined gypsum
serious problem as regards to the tin (c) sea shells (d) dolomite
buttons of their uniforms. White metallic tin
buttons got converted to grey powder. This Exp. (b)
transformation is related to Calcined gypsum does not contain CaCO 3 as
(a) a change in the crystalline structure of tin gypsum is CaSO 4 ⋅ 2H2O.
(b) an interaction with nitrogen of the air at very i.e., it is sulphate.
low temperature
(c) a change in the partial pressure of oxygen in 114. Which one of the following processes will
the air produce hard water ? [AIEEE 2003]
(d) an interaction with water vapour contained in (a) Saturation of water with CaCO 3
the humid air [AIEEE 2004] (b) Saturation of water with MgCO 3
(c) Saturation of water with CaSO 4
Exp. (a) (d) Addition of Na 2 SO4 to water
As temperature decreases, white tin (β -form
changes to grey tin (α-form). Exp. (c)
13.2 °C Alkaline earth metal salts causes hardness of
α - Sn r β - Sn water. Temporary hardness is caused by soluble
α -Sn has a much lower density. Ca and Mg hydrogen carbonates. Whereas
calcium and magnesium soluble sulphates and
111. Which one of the following statements chlorides cause permanent hardness of water.
regarding helium is incorrect? [AIEEE 2004]
(a) It is used to fill gas balloons instead of hydrogen 115. The substance used in Holmes signals of
because it is lighter and non-inflammable the ship is a mixture of [AIEEE 2003]
(b) It is used as a cryogenic agent for carrying out (a) CaC2 + Ca 3 P2
experiments at low temperatures (b) Ca 3 (PO 4 )2 + Pb3O 4
(c) It is used to produce and sustain powerful (c) H3 PO 4 + CaCl 2
superconducting magnets
(d) NH3 + HOCl
(d) It is used in gas-cooled nuclear reactors
Exp. (a)
Exp. (c)
In Holmes signals of the ship, mixture of CaC 2 and
Helium is not used to produce and sustain Ca 3P2 is used.
powerful superconducting magnets. All others are
the uses of helium.

116. In curing cement plasters, water is i.e., one layer can slide over other to cause
sprinkled from time to time. This helps in lubricacy. It cannot be melted easily as large
[AIEEE 2003] number of atoms being bonded strongly in the
layer to form big entity.
(a) keeping it cool
(b) developing interlocking needle-like crystals of
119. Which one of the following is an

hydrated silicates
amphoteric oxide? [AIEEE 2003]
(c) hydrating sand and gravel mixed with cement
(a) ZnO (b) Na 2O (c) SO 2 (d) B2O 3
(d) converting sand into silicic acid
Exp. (b) Exp. (a)
The calcium aluminates and silicates present in ZnO can react with both acid as well as base to
cement on hydration gives corresponding form salt and water.
hydrated colloidal gel. ZnO + 2HCl → ZnCl 2 + H2O
3CaO.Al 2O 3 + 6H2O → 3CaO ⋅ Al 2O 3 ⋅ 6H2O ZnO + 2NaOH → Na 2 ZnO 2 + H2O
Tricalcium Hydrated colloidal gel
aluminate of tricalcium aluminate 120. Concentrated hydrochloric acid when kept
2CaO ⋅ SiO 2 + xH2O → 2CaO ⋅ SiO 2 ⋅ xH2O in open air sometimes produces a cloud of
Hydrated colloidal gel white fumes. The explanation for it is that
of dicalcium silicate (a) concentrated hydrochloric acid emits strongly
The hydration of calcium aluminates and silicates smelling HCl gas all the time
involved in the setting of cement is an exothermic (b) oxygen in air reacts with the emitted HCl gas
process, hence cement structures have to be to form a cloud of chlorine gas
cooled during setting by sprinkling water. (c) strong affinity of HCl gas for moisture in air
117. Glass is a [AIEEE 2003] results in forming of droplets of liquid solution
which appears like a cloudy smoke
(a) microcrystalline solid
(d) due to strong affinity for water, concentrated
(b) super cooled liquid
hydrochloric acid pulls moisture of air towards
(c) gel itself. This moisture forms droplets of water
(d) polymeric mixture and hence, the cloud [AIEEE 2003]
Exp. (b) Exp. (b)

Glass is a supercooled liquid, which forms a 1
2HCl + O 2 → H2O + Cl 2
non-crystalline solid. The common lime-soda 2
glass used for bottles and jars is a supercooled
mixture of sodium and calcium silicates. 121. The metallic sodium dissolves in liquid
ammonia to form a deep blue coloured
118. Graphite is a soft solid lubricant extremely solution. The deep blue colour is due to the
difficult to melt. The reason for this
formation of [AIEEE 2002]
anomalous behaviour is that graphite
(a) solvated electron e− (NH3 ) x
(a) is a non-crystalline substance
(b) is an allotropic form of diamond (b) solvated atomic sodium, Na(NH3 ) y
(c) has molecules of variable molecular masses (c) (Na + + Na − )
like polymers (d) NaNH2 + H2
(d) has carbon atoms arranged in large plates of
rings of strongly bound carbon atoms with Exp. (a)
weak interplate bonds [AIEEE 2003] All alkali metals dissolve in liquid ammonia and
gives solvated ammoniated electrons.
Exp. (d) M + ( x + y) NH3 → M + (NH3 ) x + e − (NH3 )y
C-atoms of graphite form covalently bonded These electrons are excited to higher energy
plates (layers). These layers are held together by levels and the absorption of photons occurs in the
weak forces of attraction. red region of the spectrum. Thus, solution
appears blue.

122. KO2 is used in space and submarines 124. Alum is widely used to purify water since
because it (a) it forms complex with clay particles
(a) absorbs CO 2 and increases O 2 concentration (b) it coagulates the mud particles
(c) it exchanges Ca 2 + and Mg 2 + ions present in
(b) absorbs moisture
hard water
(c) absorbs CO 2 (d) its sulphate ion is water purifier [AIEEE 2002]
(d) produces ozone [AIEEE 2002]
Exp. (b)
Exp. (a) Mud is colloidal charged solution which on
4KO 2 + 2CO 2 → 2K 2CO 3 + 3O 2 treatment with alum (Al 3+ ) gets neutralised or
coagulated.
123. A metal M forms water soluble MSO4 and
inert MO. MO in aqueous solution forms 125. PCl 3 and PCl 5 both exist; NCl 3 exists but
insoluble M (OH)2, soluble in NaOH. Metal NCl 5 does not exist. It is due to [AIEEE 2002]
M is [AIEEE 2002] (a) lower electronegativity of P than N
(a) Be (b) Mg (b) lower tendency of N to form covalent bond
(c) Ca (d) Sr (c) availability of vacant d-orbital in P but not in N
(d) statement is itself incorrect
Exp. (a), (b)
Exp. (c)
Both Be(OH)2 and Mg(OH)2 being insoluble are
obtained from NaOH solution through Phosphorus (3rd period element) can raise
precipitation. covalency facilitating vacant d-orbitals
P (ground) [Ne] 3s 2 3 p3 3d 0
P (excited) [Ne] 3s1 3 p3 3d 1

13
d- & f-Block Elements

and Coordination Chemistry
1. The following ligand is 2. The correct order of the spin only magnetic
NEt2 moment of metal ions in the following low
N spin complexes, [V(CN)6 ]4 − , [Fe(CN)6 ]4 − ,
[Ru(NH 3 )6 ]3+ , and[Cr(NH 3 )6 ]2+ , is
O– –
O [JEE Main 2019, 8 April Shift-I]
2+ 3+
(a) Cr > Ru > Fe2 + > V 2 +
2+ 2+
(b) V > Cr > Ru 3 + > Fe2 +
(a) hexadentate (b) tetradentate (c) V 2 + > Ru 3 + > Cr 2 + > Fe2 +
(c) bidentate (d) tridentate (d) Cr 2 + > V 2 + > Ru 3 + > Fe2 +
Exp. (b) Exp. (b)

Key Idea Denticity of ligand is defined as donor Key Idea In presence of strong field ligands,
sites or number of ligating groups.
∆ 0 > p, for fourth electron it is more energetically
The given ligand is tetradentate. It contains four favourable to occupy t 2 g orbital with configuration
donor atoms. It can bind through two nitrogen t 24 g e g0 and form low spin complexes.
and two oxygen atom to the central metal ion.
Ligand bound to the central atom or ion through The correct order of the spin only magnetic
coordinate bond in the coordination entity. It act moment of metal ions in the given low-spin
as a Lewis base. The attacking site of the given complexes is V 2 + > Cr 2 + > Ru3 + > Fe 2 + .
ligand is given in bold.
All the given complexes possess strong field
NEt2 ligands (CN, NH3 ). Hence, readily form low spin
N complexes.
O- -O

d- & f-Block Elements and Coordination Chemistry 167
Complex Oxidation Configuration Orbital No. of used as an anti-tumor agent in the treatment of
state splitting unpaired cancer.
electrons
H 3N II Cl
eg
Pt
[V(CN)6]4– V
2+ 3
t2g eg
0
3 H 3N Cl
t2g
5. The calculated spin only magnetic moments
eg
4
(BM) of the anionic and cationic species of
[Cr(NH3)6]2+ Cr2+ t2g eg0 2
[Fe(H 2O)6 ]2 and [Fe(CN)6 ], respectively, are
t2g
eg (a) 0 and 4.9 (b) 2.84 and 5.92
[Ru(NH3)6]3+ Ru3+ t25g eg0 1 (c) 0 and 5.92 (d) 4.9 and 0
t2g Exp. (a)
eg [Fe(H2O)6 ]2 ⇒ It will form 2 cationic species, i.e.
II
[Fe(CN)6]4– Fe2+ t26g eg0 0 I. (i) As [Fe(H2O)6 ]2+ ⇒ High spin octahedral
t2g complex of Fe 2+ .
Fe 2+ : 3d 6 , x = 4 (unpaired electrons)
3. The lanthanide ion that would show colour µ = 4(4 + 2 ) BM = 4.9 BM
III
is [JEE Main 2019, 8 April Shift-I] or (ii) as [Fe(H2O)6 ]3+ = High spin octahedral
(a) Gd 3 + (b) Sm3 + (c) La 3 + (d) Lu 3 + complex of Fe 3+ .
Exp. (b) Fe 3+ : 3d 5 , x = 5, µ = 5(5 + 2 ) = 5.92 BM
The lanthanide ion that would show colour is [H2O is a neutral weak field ligand]
Sm3+ . Colour of a compound depends on the So, [Fe(H2O)6 ]2+ will be the cationic specie,
number of electrons in 4f-orbitals. µ = 4.9 BM.
Electronic configuration of given lanthanides are [Fe(CN)6 ] will have two anionic complexes
as follows: II
Gd 3+ = 4f 7 II. (i) [Fe(CN)6 ]4– ⇒ Low spin, octahedral complex
Sm3+ = 4f 5 of Fe 2+ .
As CN− is a strong ligand it will pair up the
La 3+ = 4f 0
electrons.
Lu3+ = 4f14 d2sp3
3+ Fe2+(3d6)
Gd have half-filled 4f-orbitals.
La 3+ have no electron in 4f-orbitals.
Lu3+ have fully-filled 4f-orbitals. n=0, µ=0
Only Sm3+ contain 4f 5 . The electrons can easily III
undergoes excitation. That result in a formation or, (ii) [Fe(CN)6 ] 3–
⇒ Low spin octahedral
of colour. complex of Fe 3+ .
d2sp3
Fe3+ ⇒ (3d5)
4. The compound that inhibits the growth of
tumors is [JEE Main 2019, 8 April Shift-II]
(a) trans-[Pt(Cl)2 (NH3 )2 ] n=1, µ=√1(1+2)
(b) cis-[Pd(Cl)2 (NH3 )2 ] =1.73 BM
(Not in options)
(c) cis-[Pt(Cl)2 (NH3 )2 ]
[CN− is an anionic strong field ligand]
(d) trans-[Pd(Cl)2 (NH3 )2 ]
So,the anionic species is [Fe(CN)6 ]4− , µ = 0
Exp. (c) Thus, the calculated spin only magnetic
cis-[Pt(Cl)2 (NH3 )2 ] is known as cis-platin. It is a moments (BM) of the anionic and cationic
σ-bonded organo-metallic compound and is species of [Fe(H2O)6 ]2 and [Fe(CN)6 ]
respectively are 4.9 and 0.

6. The degenerate orbitals of[Cr(H 2O)6 ]3+ are 8. The one that will show optical activity is (en
[JEE Main 2019, 9 April Shift-I] = ethane-1, 2-diamine)
(a) d and d xz [JEE Main 2019, 9 April Shift-I]
z2
(b) d xz and d yz A A
A B B B
(c) d and d xy
x 2 − y2 (a) M (b) M
(d) d yz and d
z2 B A B B
Exp. (b) B A
A A
The degenerate orbitals of [Cr(H2O)6 ]3+ are d xz
A
and d yz . Electronic configuration of Cr 3+ is
(c) M en (d) en M en
3d 5 4s1. The five d-orbitals in an isolated gaseous B
atom or ion have same energy, i.e. they are
degenerate. This degeneracy has been removed B A
due to the ligand electron–metal electron
repulsions in the octahedral complex to yield Exp. (c)
three orbitals of lower energy, t 2 g set and two Optical activity is the ability of a chiral molecule
orbitals of higher energy, e g set. to rotate the plane of polarised light, measured
(e g ) by a polarimeter. A chiral molecule does not
dx 2–y2 dz2 have any plane of symmetry. If a molecule
∆0 possess any plane of symmetry, then it is an
achiral molecule. Given options (a), (b) and (d)
Free metal ion (t2g)
possess plane of symmetry.
dxy dxz dyz
A A
7. The number of water molecule(s) not B
coordinated to copper ion directly in B
en M en
CuSO4 ⋅ 5H 2O, is [JEE Main 2019, 9 April Shift-I] M
(a) 2 (b) 3 B
B
(c) 1 (d) 4
A A
Exp. (c)
(b) (d)
In CuSO 4 ⋅ 5H2O, one molecule of water is
indirectly connected to Cu. In this molecule, four
B
water molecules form coordinate bond with A B
Cu2+ ion while one water molecule is associated
with H-bond with SO 2−
4 . M
Structure of CuSO 4 ⋅ 5H2O A
B
H H
δ– δ+
O O H A
H O– O
H S
(a)
Cu2+ O
H δ– δ+
H O– O Only molecule (c) does not possess any plane of
O O H
symmetry. Hence, it is a chiral molecule and
H H shows optical activity.
[Cu(H2O)4 ] SO 4 ⋅ H2O

9. The maximum number of possible

Exp. (b)
oxidation states of actinoides are shown by Key Idea The wavelength (λ ) of light absorbed
[JEE Main 2019, 9 April, Shift-II] by the complexes is inversely proportional to its
(a) berkelium, (Bk) and californium (Cf) ∆ 0 CFSE (magnitude). ∆ 0 (CFSE) ∝ 1 / λ
(b) nobelium (No) and lawrencium (Lr) The complexes can be written as:
(c) actinium (Ac) and thorium (Th) I. [CoCl(NH3 )5 ]2 + ≡ [Co(NH3 )5 (Cl)]2 + ]
(d) neptunium (Np) and plutonium (Pu) II. [Co[NH3 ]5 H2O]3 + ≡ [Co(NH3 )5 (H2O)]3 +
Exp. (d) III. [Co(NH3 )5 ]3 + ≡ [Co(NH3 )5 (NH3 )]3 +
The maximum number of possible oxidation So, the differentiating ligands in the octahedral
states of actinoids are shown by neptunium (Np) complexes of Co (III) in I, II and III are Cl s, H2O and
and plutonium (Pu). These actinoids exhibit NH3 respectively. In the spectrochemical series,
oxidation states of +3, +4, +5 and +6. the order of this power for crystal field splitting is
Cl − < H2O < NH3 .
10. The maximum possible denticities of a So, the crystal field splitting energy (magnitude)
order will be
ligand given below towards a common
∆CFSE (I) < ∆CFSE (II) < ∆CFSE (III)
transition and inner-transition metal ion, 0 0 0
respectively, are [JEE Main 2019, 9 April Shift-II] and the order of wavelength (λ ) of light absorbed
by the complexes will be
sooc coos
λ(I) > λ(II) > λ(III) Q Energy (∆CFSE ) ∝ 1 
 λ 
0
N N N
sooc
coo s coos
12. Consider the hydrated ions of Ti2+ , V 2+ , Ti3+
(a) 8 and 8 (b) 8 and 6
and Sc 3+ . The correct order of their
(c) 6 and 6 (d) 6 and 8
spin-only magnetic moment is
Exp. (d) [JEE Main 2019, 10 April Shift-I]
The maximum possible denticities of given (a) Sc 3 + < Ti 3 + < Ti 2 + < V 2 +
ligand towards a common transition and inner (b) Sc 3 + < Ti 3 + < V 2 + < Ti 2 +
transition metal ion, are 6 and 8 respectively. (c) Ti 3 + < Ti 2 + < Sc 3 + < V 2 +
(d) V 2 + < Ti 2 + < Ti 3 + < Sc 3 +
–OOC COO–
N N N
–OOC
COO–
Exp. (a)
COO– The spin only magnetic moment (µ ) of each ion
The given ligand act as hexadentate ligand in can be calculated as :
transition metal ion because the common µ = n (n + 2 ) BM
oxidation state shown by them is +3. Whereas, in [Q n = No. of unpaired electron(s)] ⇒µ ∝ n, i.e.
case of inner transition metal ion, its denticity is 8 higher the number of unpaired electron, higher
because their common oxidation state is +4. will be the value of µ.
11. Three complexes, Metal ion Z n (for metal M Nature

2+ 3+ ion) (BM)
[CoCl(NH 3 )5] (I), [Co(NH 3 )5 H 2O] (II)
Ti 2 + 22 2 (3d 2) 8 Paramagnetic
3+
and[Co(NH 3 )6 ] (III) V 2+
23 3 ( 3d 3 ) 15 Paramagnetic
absorb light in the visible region. The correct Ti 3 + 22 1 ( 3d 1 ) 3 Paramagnetic
order of the wavelength of light absorbed by 3+
Sc 21 0 ( 3d 0 ) 0 Diamagnetic
them is [JEE Main 2019, 10 April Shift-I]
(a) II > I > III (b) I > II > III Thus, the correct order of spin only magnetic
(c) III > I > II (d) III > II > I moments of given hydrated ions will be
Sc 3 + < Ti 3 + < Ti 2 + < V 2 +

(d) Ti < Mn < Ni < Zn

13. The species that can have a trans-isomer
is (en = ethane -1, 2-diamine, ox = oxalate) Exp. (d)
[JEE Main 2019, 10 April Shift-I] The 3d-transition series is
(a) [Pt(en)Cl 2 ] Sc Ti V Cr Mn Fe Co Ni Cu Zn
+ Atomic number 21 22 23 24 25 26 27 28 29 30
(b) [Cr(en)2 (ox)]
⇒
(c) [Pt(en)2 Cl 2 ]2 + Outermost 3d24s2 3d54s2 3d84s2 3d104s2
Electronic
(d) [Zn(en)Cl 2 ]
Configurection
Exp. (c) In 1st ionisation, one electron will be removed from
4s 2 subshell/orbital.
Key Idea Square planar complexes of With increase in atomic number (Z ), i.e. with
general formulae : [M(a − a)b2 ] and increase in number of protons in the nucleus,
[M(a − a) (b − b)] do not show geometrical effective nuclear charge (Z* ) also increases from Sc
isomerism. Whereas, an octahedral complex to Zn.
of general formula [M(a − a)2 b2 ] can show
IE ∝ Z*
geometrical (cis-trans) isomerism.
So, IE order of the given elements will be,
[Pt(en)2 (Cl 2 )]2+ with formula [M(a − a)2 b2 ] will
Ti < Mn < Ni < Zn
show geometrical isomerism as follows:
2+
2+ Cl 16. The incorrect statement is
en [JEE Main 2019, 10 April Shift-II]
Cl (a) the gemstone, ruby, hasCr 3 + ions occupying the
Pt en Pt en octahedral sites of beryl
Cl (b) the color of[CoCl(NH3 )5 ]2 + is violet as it absorbs
en the yellow light
cis-
Cl (c) the spin only magnetic moments of Fe(H2O)6 ]2 +
trans-
(optically active) (optically inactive) and [Cr(H2O)6 ]2 + are nearly similar
(I)
(d) the spin only magnetic moment of
[Ni(NH3 )4 (H2O)2 ]2 + is 2.83 BM
14. The highest possible oxidation states of
uranium and plutonium, respectively, are Exp. (a)
The explanation of given statements are as follows
(a) 7 and 6 (b) 6 and 7 :
(c) 6 and 4 (d) 4 and 6 (a) Ruby, a pink or blood-red coloured gemstone
belongs to corundum (Al 2O 3 , alumina) system
Exp. (b) which has trigonal crystalline lattice containing
Actinoids show a variety of oxidation states the repeating unit of Al 2O 3 – Cr 3+ . So, ruby does
due to comparable energies of 5f, 6d and 7s not belong to beryl lattice (Be 3 Al 2Si 6O18 ).
energy levels.
Thus, statement (a) is incorrect.
In the actinoids family (5f-block), uranium (U)
(b) [Co(Cl)(NH3 )5 ]2+ is a low spin octahedral
neptunium (Np), plutonium (Pu) and americium
(Am) have highest possible oxidation states of complex of Co 3+ . It absorbs low energy yellow
+6, + 7, + 7 and +6 respectively. light and high energy complementary violet light
will be shown off. Thus, statement (b) is correct.
15. The correct order of the first ionisation (c) [Fe(H2O)6 ]2+ and [Cr(H2O)6 ]2+ are the high-spin
enthalpies is [JEE Main 2019, 10 April Shift-II] octahedral complexes of Fe2+ (3d 6 , n = 4) and
(a) Mn < Ti < Zn < Ni Cr 2+ (3d 5 , n = 5) ions and weak field ligand, H2O
(b) Ti < Mn < Zn < Ni respectively. So, spin-only magnetic moment
(c) Zn < Ni < Mn < Ti = n(n + 2 ) of the complexes.

[Fe(H2O)6 ]2+, µ 1 = 4(4 + 2 )

18. The complex ion that will lose its crystal field
(n = 4), = 24 = 4.89 BM
stabilisation energy upon oxidation of its
[Cr(H2O)6 ]2+, µ 2 = 5(5 + 2 ) metal to +3 state is
(n = 5), = 35 = 5.92 BM [JEE Main 2019, 12 April Shift-I]
So, µ 1 ≈ µ 2 .Thus, statement (c) is correct.

(d) [Ni(NH3 )4 (H2O)2 ]2+ is also a high-spin
octahedral complex of Ni 2+ (3d 8 , n = 2) (Phen =
µ = 2(2 + 2 ) N N
= 8 = 2.83 BM Ignore pairing energy
Thus, statement (d) is correct.
(a) [Co(phen)3 ]2 + (b) [Ni(phen)3 ]2 +
17. The crystal field stabilisation energy (CFSE) (c) [Zn(phen)3 ]2 + (d) [Fe(phen)3 ]2 +
of[Fe(H 2O)6 ]Cl 2 and K 2[NiCl 4 ], respectively,
are [JEE Main 2019, 10 April Shift-II] Exp. (d)
(a) − 0.4 ∆o and −1.2 ∆t
Key Idea Crystal field splitting occurs due to
(b) − 0.4 ∆o and − 08
. ∆t
the presence of ligands in a definite geometry.
(c) − 2.4 ∆o and −1.2 ∆t In octahedral complexes the energy of two, e g
(d) . ∆o and − 08
− 06 . ∆t orbitals will increase by (0.6) ∆ o and that of
Exp. (b) three t 2 g will decrease by (0.4) ∆ o .
The complex ion that will lose its crystal field

Key Idea Crystal field stabilisation energy
stabilisation energy upon oxidation of its metal to
(CFSE) for octahedral complexes
+3 state is [Fe(phen)3 ]2+ .
= (−0.4 x + 0.6 y)∆ o
−e −
where, x = number of electrons occupying t 2 g [Fe(phen)3 ]2 + → [Fe(phen)3 ]3 +
orbital. In [Fe(phen)3 ]2+ , electronic configuration of Fe 2+
y = number of electrons occupying e g orbital. is 3d 6 4s 0 . Phenanthrene is a strong field
CFSE for tetrahedral complexes symmetrical bidentate ligand. The splitting of
= (−0.6 x + 0.4 y)∆ t orbital in Fe 2+ is as follows:
where, x = number of electrons occupying e
eg
orbital.
y = number of electrons occupying t orbital. +0.6 ∆o
Fe2+
In [Fe(H2O)6 ]Cl 2 , H2O is a weak field ligand, so it
is a high spin (outer orbital) octahedral complex –0.4 ∆o
of Fe 2+ . t2g
eg CFSE = 6 × −0.4∆o = −2 .4 ∆o .
Fe2+(3d6) = The splitting of orbital and arrangement of
t2g
electrons in Fe 3+ is as follows :
∴ CFSE = (−0.4 x + 0.6 y)∆o eg
= [−0.4 × 4 + 0.6 × 2 ]∆o = − 0.4∆o
In K 2 [NiCl 4 ], Cl − is a weak field ligand, so it is a +0.6 ∆o
high spin tetrahedral complex of Ni 2+ . Fe3+
–0.4 ∆o
t
Ni2+(3d6) = t2g
e CFSE = 5 × −0.4 ∆o = −2 . 0 ∆o
Fe 2+ upon oxidation of its metal to +3 state lose
∴ CFSE = (−0.6 × 4 + 0.4 × 4)∆t its CFSE from −2 .4 ∆o to −2 .0∆o .
= − 0.8∆t

19. Complete removal of both the axial ligands 20. Thermal decomposition of a Mn compound
(along the z-axis) from an octahedral (X ) at 513 K results in compound (Y ), MnO2
complex leads to which of the following and a gaseous product. MnO2 reacts with
splitting patterns? (relative orbital energies NaCl and concentrated H 2SO4 to give a
not on scale). [JEE Main 2019, 12 April Shift-I]

pungent gas Z . X ,Y and Z , respectively, are
dx2 – y2 dz2 [JEE Main 2019, 12 April Shift-II]
(a) K3 MnO4 , K2MnO4 and Cl 2
dxy dx2 – y2
(a) E (b) E (b) K2MnO4 , KMnO4 and SO2
dz2 dxz, dyz (c) KMnO4 , K2MnO4 and Cl 2
dxz, dyz dxy (d) K2MnO4 , KMnO4 and Cl 2
dx2 – y2 dx2 – y2 Exp. (c)

Thermal decomposition of Mn compound (X), i.e.
dz2 dz2
KMnO 4 at 513 K results in compound Y(i.e.
(c) E (d) E
dxy dyz, dxz K 2MnO 4 ), MnO 2 and a gaseous product. MnO 2
reacts with NaCl and concentrated H2SO 4 to give
dxz, dyz dxy a pungent gas Z(i.e. Cl 2 ). The reactions involved
are as follows :
Exp. (a) 2KMnO 4 513  K
→ K 2MnO 4 + MnO 2 + O 2 (g )
(X ) ∆ (Y)
Complete removal of both the axial ligands
(along the z-axis) from an octahedral complex MnO 2 + 4NaCl + 4 H2SO 4 →
leads to the following splitting pattern. MnCl 2 + 4NaHSO 4 + 2H2O + Cl 2 (g )
(Z ) pungent gas.
dx2–y 2
21. The pair that has similar atomic radii is

dxy [JEE Main 2019, 12 April Shift-II]
Energy
eg (a) Mn and Re (b) Ti and Hf

(c) Sc and Ni (d) Mo and W
dz2
t2g Exp. (d)
The pair that has similar atomic radii is Mo and
dxzdyz
W. It is due to lanthanoid contraction. The factor
responsible for lanthanoid contraction is the
The single electron in the d 2 2 orbital is imperfect shielding of one electron by another in
x −y
being repelled by four ligands, while the electron the same set of orbitals. Shielding of 4f is very
in the d 2 orbital is only being repelled less due to its diffused shape. As a result,
z
by two ligands. Thus, the energy of the d 2 2 nuclear charge increases. Hence, Mo and W
x −y
increases relative to that of d 2 . A more stable have similar atomic radii.
z
arrangement arises when both the e g electrons
pair up and occupy the lower energy d 2 orbital. 22. The compound used in the treatment of lead
z
This leaves the d 2 2 orbital empty. poisoning is [JEE Main 2019, 12 April Shift-II]
x −y
Thus, four ligands can now approach along (a) D-penicillamine (b) desferrioxime-B
+ x, − x, + y and − y directions without any (c) cis-platin (d) EDTA
difficulty as d 2 2 orbital is empty. However,
x −y
ligands approaching along + z and − z directions Exp. (d)
meet very strong repulsive forces from filled d 2 The compound used in the treatment of lead
z
orbitals. Thus, only four ligands succeed in poisoning is EDTA. Medication occurs through
bonding to the metal. A square planar complex chelation therapy. Calcium disodium
is formed, the attempt to form an octahedral ethylenediamine tetraacetic acid chelates
complex being unsuccessful. divalent metal ion such as Pb 2 + from plasma
and interstitial body fluids.

The metal displaces Ca and is chelated, ∆(CFSE) is measured with help of wavelength of
mobilised and usually excreted. Less then 5% Ca the colour absorbed by the given coordination
Na 2 EDTA is absorbed in the gastrointestinal compound, as
tract and it possibly increases the absorption of c
∆O = hν = h ×
Pb present in the tract. Therefore, it is not λ
recommended for oral use. It is usually given Both the complexes contain three unpaired
intravenously. electrons. Therefore, both are paramagnetic.
23. The coordination numbers of Co and Al in 25. The highest value of the calculated spin only
[CoCl(en)2]Cl andK 3[Al(C 2O4 )3], respectively, magnetic moment (in BM) among all the
are (en = ethane-1, 2-diamine) transition metal complexes is
[JEE Main 2019, 12 April Shift-II] (a) 5.92 (b) 3.87 (c) 6.93 (d) 4.90
(a) 5 and 3 (b) 3 and 3 [ JEE Main 2019, 9 Jan Shift-I]
(c) 6 and 6 (d) 5 and 6
Exp. (a)
Exp. (d) The spin only magnetic moment(µ) (in BM) is given
by
Key Idea The total number of ligands to which
µ(in BM) = n(n + 2 )
the metal is directly attached is called
coordination number. where, n = number of unpaired electrons
The highest value of n in transition metal complex
The coordination numbers of Co and Al in is 5 in its d 5 -configuration.
[Co(Cl)(en)2 ]Cl and K 3 [Al(C 2O 4 )3 ] are 5 and 6 ∴ µ = 5(5 + 2 )BM = 5.916BM
respectively.
In first complex, ‘en’ is a didentate ligand and 26. The complex that has highest crystal field
‘Cl’ is a unidentate ligand.
splitting energy ( ∆ ), is
[Co(Cl)(en)2 ]Cl, coordination number
= 1+ 2 × 2 = 1+ 4⇒5
(a) [Co(NH3 )5 Cl] Cl 2 (b) [Co(NH3 )5 (H2O)]Cl 3
So, the coordination number is 5.
(c) K 3 [Co(CN)6 ] (d) K 2 [CoCl 4 ]
For K 3 [Al(C 2O 4 )3 ], ‘C 2O 24 − ’ is a didentate ligand.
Coordination number = 3 × 2 = 6. Exp. (c)
Hence, coordination number is 6. All of the complex given are the octahedral
complexes of Co (III) except K 2 [CoCl 4 ], which is
24. Two complexes [Cr(H 2O)6 ]Cl 3 (A) and a tetrahedral complex of Co (II) (sp3 -hybridised).
[Cr(NH 3 )6 ]Cl 3 (B) are violet and yellow We know, ∆t < ∆O Q ∆ = 4 ∆ 
 t
9 
O
coloured, respectively. The incorrect
statement regarding them is So, the octahedral complexes (a, b, c) have
(a) ∆o value for (A) is less than that of (B) higher ∆o values than that of tetrahedral,
(b) both absorb energies corresponding to their K 2 [CoCl 4 ].
complementary colours Now, for the complexes, a, b and c,
(c) ∆o values of (A) and (B) are calculated from the the magnitude of ∆O ∝ ligand strength, which is
energies of violet and yellow light, respectively based on their positions in the spectrochemical
(d) both are paramagnetic with three unpaired series.
electrons [ JEE Main 2019, 9 Jan Shift-I] Cl − < H2O < NH3 < CN−
Hence, K 3 [Co(CN)6 ] will have the highest ∆
Exp. (c) value.
‘A’ absorbs yellow light of less energy and emits
violet light of high energy (complementary colour) 27. The transition element having least
because H2O is a weak field ligand. But in case of ‘ enthalpy of atomisation is
B’, due to presence of strong field ligand (NH3 ), it
(a) Zn (b) V (c) Fe (d) Cu
absorbs high energy violet light and emits low
energy complementary yellow colour. [ JEE Main 2019, 9 Jan Shift-II]

Exp. (a) Let, a = F − , b = Cl − , c = S CN− , d = NO −2

For transition metals, SCN− and NO −2 are ambidentate ligands and they
° also show linkage isomerism (structural).
∆HAtomisation ∝ Strength of metallic bonding
Considering both linkage and geometrical
∝ Number of unpaired electrons
isomerism.
in the metal atom

Total number of possible isomers given by the
For the given 3d-transition metals,
complex, = 3 × (2 + 2 ) = 12
V Fe Cu Zn
3d 3 4s 2 3d 6 4s 2 3d 10 4s1 3d 10 4s 0 30. Wilkinson catalyst is
n=3 n=4 n=0 n=0 (a) [(Et3 P)3 RhCl]
[Qn = no. of unpaired electrons] (b) [(Et3 P)3 IrCl](Et = C2H5 )
−1
∆° HAtomisation (kJ mol ) = 515 418 339 130 (c) [(Ph3 P)3 RhCl]
So, absence of unpaired d-electrons and larger (d) [(Ph3 P)3 IrCl]
size of Zn atoms, make the crystal lattice of Zn less [ JEE Main 2019, 10 Jan Shift-I]
closely packed.
Exp. (c)
28. Homoleptic octahedral complexes of a Wilkinson’s catalyst is a σ-bonded organometallic
metal ion ‘M 3 + ’ with three monodentate compound [(Ph3P)3 RhCl] . It is commercially used
ligands L1 , L 2 and L 3 absorb wavelengths in for hydrogenation of alkenes and vegetable oils
the region of green, blue and red (unsaturated).
respectively. The increasing order of the IUPAC name Chloridotris (triphenylphosphene)
ligand strength is [ JEE Main 2019, 9 Jan Shift-II] rhodium (I).
(a) L1 < L 2 < L 3 (b) L 2 < L1 < L 3
(c) L 3 < L1 < L 2 (d) L 3 < L 2 < L1 31. The effect of lanthanoid contraction in the
lanthanoid series of elements by and large
Exp. (c) means [ JEE Main 2019, 10 Jan Shift-I]
In homoleptic complexes, the metal atom/ion is (a) increase in atomic radii and decrease in ionic
linked to only one type of ligand. Assuming, radii
ligands are neutral, the octahedral complexes of (b) decrease in both atomic and ionic radii
M 3+ can be, (c) increase in both atomic and ionic radii
[M(L1 )6 ]3 + ,[M(L2 )6 ]3 + and [M(L3 )6 ]3+ (d) decrease in atomic radii and increase in ionic
(I) (II) (III) radii
λ Absorption Green Blue Red (wavelength)
Exp. (b)
So, λLIII
3 > λL1 > λL 2
I II Lanthanoid contraction in the lanthanoid series
∴∆°absorption : ∆LII2 > ∆LI1 > ∆LIII3 takes place due to the presence of electron(s) in
the 4f-orbitals. f-orbitals have poor shielding effect.
1
[Q Energy (∆, CFSE) ∝ ] As a result, the effective nucleur charge will be
λ more experienced by the 5d and 6s- electrons and
We know, ligand strength ∝ ∆°absorption it will cause contraction or decrease in both atomic
So, the increasing order of the ligand strength will and ionic radii.
be, L3 < L1 < L2
32. The difference in the number of unpaired
29. The total number of isomers for a square electrons of a metal ion in its high-spin and
planar complex [M(F)(Cl)(SCN)(NO 2)] is low-spin octahedral complexes is two. The
(a) 12 (b) 16 (c) 4 (d) 8 metal ion is
[ JEE Main 2019, 10 Jan Shift-I] (a) Mn 2 + (b) Fe2 +
(c) Ni 2 + (d) Co2 +
Exp. (a)
A square planar complex of general formula,
M abcd gives three geometrical isomers only.

Exp. (d) 33. A reaction of cobalt (III) chloride and

The difference in the number of unpaired ethylene diamine in a 1 : 2 mole ratio
electrons of different metal ions in their high spin generates two isomeric products A (violet
and low spin octahedral complexes are given in coloured) and B (green coloured). A can
the table below :
show optical activity, but B is optically

Metal ion Number of e− in high spin complex (n1 ) inactive. What type of isomers does A and B
Mn2 + represent ? [ JEE Main 2019, 10 Jan Shift-II]
3d 4s 4p
(a) Ionisation isomers
(b) Coordination isomers
4d
(c) Geometrical isomers
n1=5
(d) Linkage isomers
2+ Exp. (c)
Fe 3d 4s 4p
According to the situation given in question,
4d reactions are as follows:
III III
CoCl 3 + 2en → [Co(en)2 Cl 2 ]Cl
n1=4 •• 
2+ CH2 — N H2 
Ni 3d 4s 4p
en = ethylene-1, 2-diamine,  
CH2 — NH2 
•• 
4d 
Cl
n1=2 en
Cl
Ni 2 + does not form low spin octahedral III
complexes. Co Cl en Co en Cl
Co 2 + 3d 4s 4p
Cl
en
Cl
4d
‘A’ Optically active ‘B’ Optically inactive
(cis-form) (trans-form)
∴ n1=3 (Violet) (Green)
Number of e− in low spin complax (n2 ) n2 − n1 34. Match the metals (Column I) with the
3d 4s 4p 5−1= 4 coordination compound(s)/enzyme(s)
(Column II).
4d
Column I Column II
n2=1 (A) Co (i) Wilkinson catalyst
3d 4s 4p 4− 0 = 4 (B) Zn (ii Chlorophyll

(C) Rh (iii) Vitamin-B12
4d
(D) Mg (iv) Carbonic anhydrase
n2=0 A B C D
(a) (i) (ii) (iii) (iv)
3d 4s 4p 3−1= 2
(b) (iv) (iii) (i) (ii)
(c) (iii) (iv) (i) (ii)
4d (d) (ii) (i) (iv) (iii)
∴ n1=1

Exp. (c) 4 KOH, O

37. A    
2→ 2B + 2H 2O
(A) Co is present in vitamin-B12 (iii) having (Green)
II
molecular formula, C 63H88 CoN14O14P. 3B  → 2C
4 HCl
+ MnO2 + 2H 2O
(Purple)
(B) Zn is present in carbonic anhydrase (iv) in
2C H → 2 A + 2KOH + D
2O, KI
which three histidine units and the —OH

group coordinate with one Zn (II) ion. In the above sequence of reactions, A and D,
(C) Rh is present in Wilkinson catalyst (i) having respectively, are [JEE Main 2019, 11 Jan Shift-II]
molecular formula [(Ph3P)3 RhCl] . (a) KI and KMnO4 (b) MnO2 and KIO3
(D) Mg is present in chlorophyll (ii) having (c) KI and K2MnO4 (d) KIO3 and MnO2
II
molecular formula C 55H70O 6N4 Mg Exp. (b)
(chlorophyll-b). When MnO 2 (A) is fused with alkali in presence of
air then potassium manganate (B) is formed.
35. The element that usually does not show Potassium manganate (B) is of green colour which
variable oxidation states is disproportionate in a neutral or acidic solution to
(a) Sc (b) Cu (c) Ti (d) V produce potassium permanganate (C). Potassium
[JEE Main 2019, 1 Jan Shift-I] permanganate (C) in presence of acidic medium
oxidises iodide to iodate.
Exp. (a)
The reaction can be shown as:
The most stable oxidation states in the 0
+ 4 4 KOH, O 2 +6 −2 −2
compounds of the given transition metals of
(i) 2Mn O 2 → 2K 2 MnO 4 + 2H2O
3d-series are, (A) ∆ (B)
Sc : + 3; Ti : + 3, + 4; V : +2, + 3, + 4, + 5; Potassium manganate
(Green)
Cu : + 1, + 2 + 6
4HCl
(ii) 3K 2 MnO 4  →
The electronic configuration of Sc (Z = 21) is [Ar]
3d 1, 4s 2 . (B )
+ 7 + 4
Due to the presence of only one 3d-electron 2KMnO 4 + MnO 2 + 2H2O + 4KCl
(no pairing energy) and two 4s-electrons, they easily (C)
Potassium permanganate
ionise to achieve most stable +3 oxidation state. (Purple)
−1
36. The coordination number of Th in + 7 K I , H 2O + 4 +5
K 4[Th(C 2O4 )4 (OH 2 )2] is (C 2O24 − = Oxalato) (iii) 2KMnO4 → 2MnO 2 2KOH + K I O 3
(C ) ( A) (D)
(a) 14 (b) 10 (c) 8 (d) 6 Thus, A and D are MnO 2 and KIO 3 respectively.
38. The number of bridging CO ligand(s) and
Exp. (b) Co Co bond(s) in Co 2(CO)8, respectively
Coordination number is defined as the total are [JEE Main 2019, 11 Jan Shift-II]
number of ligands to which the metal is directly
(a) 2 and 0 (b) 0 and 2 (c) 4 and 0 (d) 2 and 1
attached.
Here, C 2O 24 − is a bidentate ligand, Exp. (d)
O¾
¾ The structure of Co 2 (CO)8 (a polynuclear metal
C¾O ¾ carbonyl) can be written as :
¾
M (Metal)
C¾O ¾
O ¾
¾
and H2O is a monodentate ligand, H2O M OC C CO
So, total number of sites offered by C 2O 24 − and OC——Co——–Co——CO

H2O ligands around Th(IV) = Coordination OC C CO
number of Th (IV)
= 4 × 2 (by C 2O 24 − ) + 2 × 1(by H2O) = 10
Total number of bridging CO ligands = 2
and the Co Co bond = 1

dx2-y2, dz 2
39. Mn2(CO)10 is an organometallic compound
due to the presence of
(a) Mn  C bond (b) Mn  O bond Average dxy, dyz, dxz
d-orbitals
(c) C  O bond (d) Mn  Mn energy of
in free ion the d-orbitals Splitting of d-orbitals
[JEE Main 2019, 12 Jan Shift-I] in a spherical in an octahedral

crystal field crystal field
Exp. (a)
As the d-orbitals, i.e. d and d are vacant.
Mn2 (CO)10 is an organometallic compound due to x2 − y 2 z2
the presence of MnC bond. The metal-carbon Hence, these both orbitals are directly facing the
bond in organometallic compounds possess both ligands in K 3 [Co(CN)6 ].
σ and π-character. The MC σ-bond is formed by
the donation of lone pair of electrons from the 41. The pair of metal ions that can given a
carbonyl carbon into a vacant orbital of the metal. spin-only magnetic moment of 3.9 BM for
The MC π-bond is formed by the donation of the complex[ M (H 2O)6]Cl2, is
pair of electrons from a filled d-orbital of metal into (a) Co2+ and Fe2+ (b) Cr2+ and Mn 2+
vacant antibonding π * orbital of CO. The M  L
(c) V2+ and Co2+ (d) V2+ and Fe2+
bonding creates a synergic effect which
strengthens the bond between CO and the metal.
The structure of Mn2 (CO)10 is shown below : Exp. (c)
CO CO As H2O is a weak field ligand. It readily forms high
CO CO
spin complexes. In [M(H2O)6 ]Cl 2 , M exist in +2
CO Mn Mn CO oxidation state. The arrangement of electrons in
CO CO CO the given metal ions are as follows:
CO
Metal Configuration Number Spin only
40. The metal d-orbitals that are directly facing ions of Magnetic
the ligands in K 3[Co(CN)6 ] are unpaired moment (in BM)
(a) d xz , d yz and d 2
z
(b) d 2 2 and d 2
x −y z
electrons = n(n + 2 )
(c) d xy , d xz and d yz (d) d xz and d 2 2
x −y Co 2+ (d 7 ) = t 25ge g2 3 3.9
Fe 2+ 4
(d 6 ) = t 2ge g2 4 4.9
Exp. (b)
In K 3 [Co(CN)6 ], Co have +3 oxidation state and Cr 2+ (d 4 ) = t 23ge1g 4 4.9
electronic configuration of Co 3+ is [Ar ] 18 3d 6 .
Mn2+ (d 5 ) = t 32ge g2 5 5.9
3d6 4s0 4p0
Co3+= V 2+ (d 3 ) = t 23ge g0 3 3.9
−
As, CN is a strong field ligands so it pairs up
the de − s Therefore, Co 2 + and V 2+ contains same value of
3d6
magnetic moment (3.9 BM).
∴ [Co(CN)6]3–= XX XX XX XX XX XX
42. The magnetic moment of an octahedral
Inner orbital
d2sp3 -hybridised homoleptic Mn(II) complex is 5.9 BM. The
complex
(6e− pairs donated
by 6 CN− ligands) suitable ligand for this complex is
(a) CN− (b) ethylenediamine
In an octahedral complex, the metal is at the
centre of the octahedron and the ligands are at (c) NCS− (d) CO
the six corners. The lobes of the eg orbitals [JEE Main 2019, 12 Jan Shift-II]
(d 2 2 and d 2 ) point along the axes x, y and z
x −y z Exp. (c)
under the influence of an octahedral field, the d- The magnetic moment of the magnitude 5.9 BM
orbitals split as follow. suggest the presence of 5 unpaired electrons in

Mn(II). This can be cross verified by putting the (ii) Oxidation state of Cr in [Cr(C 6H6 )2 ]
value (5) of unpaired electrons in the formula, x + (2 × 0) = 0 or x=0
µ = n(n + 2 ) BM (iii) Oxidation state of Cr in
Thus, the valence electronic configuration of
K 2 [Cr(CN)2 (O)2 (O 2 )(NH3 )]
Mn(II) in the complex is
1 × 2 + x + ( −1 × 2 ) + ( −2 × 2 )
Mn2+= + ( −2 ) + 0 = 0
3d 4s 4p 4d or 2 + x−2 − 4−2 = 0
The octahedral homoleptic complex suggests or x−6=0
sp3d 2 -hybridisation in the complex, i.e.
hence x = + 6
sp3d2-hybridisation
Thus, +3, 0 and +6 is the answer.
Mn2+=
3d 4s 4p 4d 45. Consider the following reaction and
Thus, 5 unpaired electrons are present in the statements : [JEE Main 2018]
complex which suggest the presence of a weak −
[Co(NH 3 )4 Br2] + Br →
+
ligand like NCS − .
[Co(NH 3 )3Br3] + NH 3
43. The correct order of atomic radii is I. Two isomers are produces if the reactant
(a) Ho > N > Eu > Ce (b) N > Ce > Eu > Ho complex ion is a cis-isomer.
(c) Eu > Ce > Ho > N (d) Ce > Eu > Ho > N II. Two isomers are produced if the reactant
[JEE Main 2019, 12 Jan Shift-II] complex ion is a trans-isomer.
Exp. (c) III. Only one isomer is produced if the reactant
complex ion is a trans-isomer.
The correct order of atomic radii is
IV. Only one isomer is produced if the reactant
Europium (Eu) > Cerium (Ce) > Holmium (Ho) complex ion is a cis-isomer.
199 pm 183 pm 176 pm
> Nitrogen (N)
The correct statements are
(a) (I) and (II) (b) (I) and (III)
65 pm
(c) (III) and (IV) (d) (II) and (IV)
Note
(i) N being the member of p-block and second Exp. (b)
period, have the smallest radii. If the reactant is cis isomer than following
(ii) Rest of all the 3 members are lanthanides with reaction takes place.
Eu having stable half-filled configuration thus Br Br
with bigger size than rest two. NH3 NH3
Br Br
(iii) Among Ce and Ho, Ce has larger size which
can be explained on the basis of “Lanthanoid Br–
contraction”.
NH3 NH3 NH3 Br
44. The oxidation states of Cr, in [Cr(H 2O)6 ]Cl 3,
NH3 NH3
[Cr(C 6H 6 )2], and K 2[Cr(CN)2(O)2(O2 )(NH 3 )] Cis-isomer Facial
respectively are [JEE Main 2018]
Br
(a) +3, +4 and +6 (b) +3, +2 and +4 NH3 Br
(c) +3, 0 and +6 (d) +3, 0 and +4
+
Exp. (b)
Let the oxidation state of Cr in all cases is ‘ x’ NH3 NH3
(i) Oxidation state of Cr in [Cr(H2O)6 ]Cl 3 Br
x + (0 × 6) + (−1 × 3 ) = 0 Meridonial
or x + 0 − 3 = 0 or x = + 3
i.e. two isomers are produced.

If the reactant is trans isomer than following Number of moles of ions precipitated
=
reaction takes place. Number of moles of complex
Br Br
0.02
NH3 NH 3
NH3 NH3 = =2
0.01
Br–
∴ 2 Cl − are present outside the square brackets,
i.e. in ionisation sphere. Thus, the formula of

NH3 NH3 NH3 Br complex is [Co(H 2 O) 5 Cl] Cl 2 ⋅ H 2 O.
Br Br
Trans Meridonial
48. Which of the following compounds is
metallic and ferromagnetic?
i.e. only 1 isomer is produced. Thus, statement
(I) and (III) are correct resulting to option (b) as
the correct answer. (a) CrO 2 (b) VO 2 (c) MnO 2 (d) TiO 2
46. In the following reactions, ZnO is Exp. (a)

respectively acting as a/an Only three elements iron (Fe), cobalt (Co) and
(i) ZnO + Na 2O → Na 2 ZnO2 nickel (Ni) show ferromagnetism at room
(ii) ZnO + CO2 → ZnCO3 temperature. CrO 2 is also a metallic and
ferromagnetic compound which is used to make
magnetic tapes for cassette recorders.
(a) base and acid (b) base and base
(c) acid and acid (d) acid and base 49. The pair having the same magnetic moment
is
Exp. (d) [at. no. Cr = 24, Mn = 25, Fe = 26 and Co = 27]
Zinc oxide (ZnO) when react with Na2O it act as [JEE Main 2016 (Offline)]
acid while withCO2 it act as base. Therefore, it is an
(a) [Cr(H2O)6 ]2 + and [Fe(H2O)6 ]2 +
amphoteric oxide.
ZnO +Na 2O → Na 2 ZnO 2 (b) [Mn(H2O)6 ]2 + and [Cr(H2O)6 ]2 +
2 → ZnCO 3
Acid Base Salt
ZnO +CO (c) [CoCl 4 ]2 − and [Fe(H2O)6 ]2 +
Base Acid Salt
47. On treatment of 100 mL of 0.1 M solution of (d) [Cr(H2O)6 ]2 + and [CoCl 4 ]2 −
CoCl 3.6H 2O with excess of AgNO3; 1.2 × 10 22
ions are precipitated. The complex is Exp. (a)

Electronic
(a) [Co(H2O)4 Cl 2 ] Cl ⋅ 2H2O Number of unpaired
Complex ion configuration of
electrons (n)
(b) [Co(H2O)3 Cl 3 ] ⋅3H2O metal ion
(c) [Co(H2O)6 ]Cl 3
[Cr(H 2O)6 ]2 + Cr 2 + ; [Ar] 3 d 4 ;4
(d) [Co(H2O)5 Cl] Cl 2 ⋅ H2O
Exp. (d) [Fe(H 2O)6 ]2+ Fe 2 + ; [Ar] 3 d 6 ; 4
Number of moles of solute

Molarity (M) = [Mn(H 2O)6 ]2+ Mn2 + ; [Ar] 3 d 5 ;5
Volume of solution (in L)
∴Number of moles of complex [CoCl 4 ]2− Co 2 + ; [Ar] 3 d 7 ;3
Molarity × volume (in mL)
=
1000
. × 100
01 50. Which one of the following complexes
= = 0.01 mole shows optical isomerism?
1000
Number of moles of ions precipitate
(a) cis [Co(en)2 Cl 2 ]Cl (b) trans [Co(en)2 Cl 2 ]Cl
. × 1022
12
= = 0.02 moles (c) [Co(NH3 )4 Cl 2 ]Cl (d) [Co(NH3 )3 Cl 3 ]
6.02 × 1023
∴Number of Cl − present in ionisation sphere Exp. (a)

Cl Cl [Pt(Cl) (py) (NH3 ) (NH2OH)]+ is square planar

Cl complex. The structures are formed by fixing a
group and then arranging all the groups.
en Co en Co en
PY NH3 PY NH3
en Pt Pt
Cl
cis-[Co(en)2Cl2]Cl trans-[Co(en)2Cl2]Cl Cl NH2OH HOH2N Cl
(optically active) (optically inactive due
to plane of symmetry) PY Cl
[Co(NH3 )4 Cl 2 ]Cl can exist in both cis and trans Pt

forms that are given below: HOH2N NH3
+ +
Cl NH3 Hence, this complex shows three geometrical isomers.
H 3N NH3 H 3N Cl 53. The colour of KMnO4 is due to [JEE Main 2015]
Co Co (a) M → L charge transfer transition
(b) d − d transition
H 3N NH3 H 3N Cl
(c) L → M charge transfer transition
Cl NH3
(d) σ − σ* transition
trans-[Co(NH3)4Cl2]Cl cis-[Co(NH3)4Cl2]Cl
(optically inactive) (optically inactive) Exp. (c)
KMnO 4 → K+ + MnO −4
[Co(NH3 )3 Cl 3 ] exists in fac and mer-isomeric
∴ In MnO −4 ,Mn has +7 oxidation state having no
forms and both are optically inactive.
electron in d-orbitals.
NH3 NH3 It is considered that higher the oxidation state of
Cl NH3 Cl NH3 metal, greater is the tendency to occur L→ M charge
transfer, because ligand is able to donate the
Co Co
electrons into the vacant d- orbital of metal.
Cl NH3 Cl Cl Since, charge transfer is Laporte as well as spin
Cl NH3 allowed, therefore, it shows colour.
fac-isomer mer-isomer
Time Saving Technique There is no need to check
(optically inactive) (optically inactive) all the four options. Just find out the oxidation state
of metal ion. If oxidation state is highest and ligand
51. The reaction of zinc with dilute and present there is of electron donating nature, gives
LMCT, which shows more intense colour.
concentrated nitric acid, respectively,
produce [JEE Main 2016 (Offline)] 54. Which of the following compounds is not
(a) NO 2 and NO (b) NO and N 2O coloured yellow? [JEE Main 2015]
(c) NO 2 and N 2O (d) N 2O and NO 2 (a) Zn 2 [Fe(CN)6 ] (b) K 3 [Co(NO 2 )6 ]
Exp. (d) (c) (NH4 )3 [As(Mo 3O10 )4 ] (d) BaCrO 4
Zn + 4HNO 3 → Zn(NO 3 )2 + 2H2O + 2NO 2 Exp. (a)
(Conc. )
4Zn +10HNO 3
→ 4Zn(NO 3 )2 + N2O + 5H2O Zn2 [Fe (CN)6 ], K 3 [Co (NO 2 )6 ] and
(Dil. ) [(NH4 )3 As (Mo 3O10 )4 ] show colour due to d-d
52. The number of geometric isomers that can transition while BaCrO 4 is coloured due to charge
exist for square planar [Pt(Cl)(py)(NH 3) transfer phenomenon.
(NH 2OH)]+ is (py = pyridine) [JEE Main 2015] Further, according to spectrochemical series the
strong ligand possessing complex has higher
(a) 2 (b) 3 energy and hence lower wavelength. Therefore,
(c) 4 (d) 6 complexes containing NO 2 , NH4+ , O 2 − etc ligands
Exp. (b) show yellow colour while CN− forces the complex
to impart white colour.

Spectrochemical Series (b) [CoCl (NH3 )5 ]+ + 5H+ → CO 2+

I− < Br − <S2– < SCN− < Cl − <NO −3 < N3− + 5NH+4 + Cl −
< F − < OH− The above equation is correct because amine
< C 2O 24 − ≈ H2O < NCS− < CH3CN < py < NH3 complexes decomposes under acidic
medium. Thus, the complex [CoCl (NH3 )5 ]
< en < bipy decomposes under acidic conditions to give

−
< Phen < NO 2 < PPh3 < CN− ≈ CO ammonium ions.
excess NaOH
(c) [Mg (H2O)6 ]2 + + (EDTA)4 − →
55. The octahedral complex of a metal ion M 3+
with four monodentate ligands L1 , L 2, L 3 [Mg (EDTA)]2 + + 6H2O
and L 4 absorb wavelengths in the region of The above equation is incorrect because the
red, green, yellow and blue, respectively. product formed would be [Mg (EDTA)]2− .
The increasing order of ligand strength of (d) CuSO 4 + 4KCN → K 2 [Cu(CN)4 ]+K 2SO 4
the four ligands is [JEE Main 2014] The above equation is incorrect. Thus, the
correct equation is
(a) L 4 < L 3 < L 2 < L 1 (b) L 1 < L 3 < L 2 < L 4
2KCN + CuSO 4 → K 2SO 4 + Cu + (CN)2
(c) L 3 < L 2 < L 4 < L 1 (d) L 1 < L 2 < L 4 < L 3
(Cyanogen
57. Which of the following complex speciesgas
is)
Exp. (b) not expected to exhibit optical isomerism?
[JEE Main 2013]
Ligand L1 L2 L3 L4
(a) [Co(en)3 ]3 + (b) [Co(en)2 Cl 2 ]+
Coloured region of Red Green Yellow Blue
absorbed wavelength (c) [Co(NH3 )3 Cl 3 ] (d) [Co(en) (NH3 )Cl 2 ]+
Exp. (c)
Coloured regions of visible light (VIBGYOR) are
arranged in the increasing order of wavelength or Optical isomerism is exhibited by only those
decreasing order of energy[Q E ∝ 1 / λ ]. Therefore, complexes which lacks elements of symmetry.
[Co(NH3 )3 Cl 3 ] shows facial as well as meridional
E Red < Eyellow < Egreen < Eblue
( L1 ) ( L4 )
isomerism. But both the forms contain plane of
( L2 ) ( L3 )
symmetry. Thus, this complex does not exhibit optical
This suggests that L4 will absorbs higher energy isomerism.
wavelength followed by L2 , L3 and L1. Since,
higher absorbed energy corresponds to greater 58. Which of the following arrangements does
extent of crystal field splitting and thus, higher field not represent the correct order of the
strength of the ligand. property stated against it? [JEE Main 2013]
Hence, the increasing order of ligand strength of (a) V 2 + < Cr 2 + < Mn 2 + < Fe2 + : paramagnetic
the four ligands is L1 < L3 < L2 < L4 behaviour
56. The equation which is balanced and (b) Ni 2 + < Co 2 + < Fe2 + < Mn 2 + : ionic size
represents the correct product(s) is (c) Co 3 + < Fe3 + < Cr 3 + < Sc 3 + : stability in
(a) Li 2O + 2KCl → 2LiCl + K 2O aqueous solution
(b) [CoCl (NH3 )5 ]+ + 5H+ → CO 2 + (d) Sc < Ti < Cr < Mn : number of oxidation states
+ 5NH+4 + Cl − Exp. (a)
excess NaOH (a) V 2 + = 3 unpaired electrons
(c) [Mg (H2O)6 ]2 + + (EDTA)4 − →
Cr 2 + = 4 unpaired electrons
[Mg (EDTA)]2 + + 6H2O Mn2 + = 5 unpaired electrons
(d) CuSO 4 + 4KCN → K 2 [Cu (CN)4 ] + K 2 SO 4 Fe 2 + = 4 unpaired electrons
Exp. (b) Hence, the order of paramagnetic behaviour
(a) Li 2O + 2KCl → 2LiCl + K 2O should be
The above equation is incorrect because K 2O, V 2 + < Cr 2 + = Fe 2+ < Mn2+
a stronger base cannot be generated by a (b) Ionic size decreases from left to right in the
weaker base, Li 2O. same period.
(c) (As per data from NCERT)

Co 3+ /Co 2+ = 1.97; Fe 3+ /Fe 2+ = 0.77; (c) Ferrous compounds are less volatile than the
corresponding ferric compounds
Cr 3+ /Cr 2+ = – 0.41
(d) Ferrous compounds are more easily
Sc 3+ is highly stable (It does not show + 2). hydrolysed than the corresponding ferric
(d) The oxidation states increases as we go from compounds
group 3 to group 7 in the same period.

Exp. (d)
59. Four successive members of the first row (a) FeO > Fe 2O 3 (basic). Thus, it is correct
transition elements listed below with statement.
atomic numbers. Which one of them is (b) FeCl 2 > FeCl 3 (ionic), larger the charge
expected to have the highest E M ° 3+ 2+ greater the polarizing power. Thus, greater the
/M
value? [JEE Main 2013] covalent nature. Thus, the given statement is
correct
(a) Cr (Z = 24) (b) Mn (Z = 25)
(c) Fe 2+ salts are more ionic thus less volatile than
(c) Fe (Z = 26) (d) Co (Z = 27) Fe 3+ salts. Thus, given statement is correct.
Exp. (d) (d) Greater the covalent nature, more easily they
are hydrolyzed. Thus, FeCl 3 is more
SRP value normally increases from left to right in hydrolyzed than FeCl 2 .
the period of d-block elements. Some SRP value Thus, statement (d) is incorrect.
are exceptionally higher due to stability of
product ion. e.g., E° = + 1.57 V;
62. Which of the following facts about the
Mn 3 + / Mn 2 + complex[Cr(NH 3 )6 ]Cl 3 is wrong? [AIEEE 2011]
E° = +1.97 V (a) The complex involvesd 2 sp 3 hybridization and
Co 3 + / Co 2 +
is octahedral in shape
Thus, E ° 3+ 2+ is highest for Co. (b) The complex is paramagnetic
M /M
(c) The complex is an outer orbital complex
60. Which among the following will be named (d) The complex gives white precipitate with
as dibromidobis- (ethylenediamine) silver nitrate solution
chromium (III) bromide? [AIEEE 2012]
Exp. (c)
(a) [Cr(en)3 ]Br3 (b) [Cr(en)2 Br2 ]Br
[Cr(NH3 )6 ] Cl 3 j
(c) [Cr(en)Br4 ]– (d) [Cr(en)Br2 ]Br 14243 {
Coordinate sphere Ionisable
Exp. (b) [Cr(NH3 )6 ]3+ + 3Cl – →
3 AgNO
AgCl ↓
Two Br, two (en) and one Cr are parts of complex. White precipitate
Charge on the complex is In [Cr (NH3 )6 ]3+ , Cr exists as Cr 3+ ion. The outer
2(Br) = −2  orbital electronic configuration of Cr is 3 d 3 4s 0 .
 The orbital diagram is represented by
2(en) = 0  = +1
3d 3 4s0 4p0
1(Cr) = +3 3+
[Cr] =
Thus, complex ion is [Cr(en)2 Br2 ]+ .
[Cr(NH3)6 ]3+ =
Since, anion is bromide thus, complex is
[Cr(en)2 Br2 ]Br.
d 2sp3
hybridisation
61. Iron exhibits +2 and +3 oxidation states.
Which of the following statements about Here, indicates lone-pair ofNH3 donated to Cr.
iron is incorrect? [AIEEE 2012] Hence,
(a) Ferrous oxide is more basic in nature than the (a) d 2 sp3 -hybridization, octahedral. Thus, correct.
ferric oxide
(b) There are three unpaired electrons, hence
(b) Ferrous compounds are relatively more ionic
paramagnetic Thus, correct.
than the corresponding ferric compounds
(c) d 2 sp3 -inner orbital complex, thus incorrect.

(d) Due to ionizable Cl − ions, white precipitate

with AgNO 3 , thus correct.
65. The outer electron configuration of Gd
(At. no. 64) is [AIEEE 2011]
Therefore, (c) is wrong.
(a) 4 f 3 , 5d 5 , 6s 2 (b) 4 f 8 , d 0 , 6s 2
63. In context of the lanthanoids, which of the (c) 4 f 4 , 5d 4 , 6s 2 (d) 4 f 7 , 5d 1 , 6s 2
following statements is not correct?
(a) There is a gradual decrease in the radii of the

Exp. (d)
members with increasing atomic number in
the series. Gd (64)
(b) All the member exhibit +3 oxidation state. 4f 7
(c) Because of similar properties the separation of [Xe]54

lanthanoids is not easy.
(d) Availability of 4f electrons results in the 5d 1 6s 2
formation of compounds in +4 state for all the
members of the series. [AIEEE 2011]
All the electrons in 4f-orbital are unpaired, hence
Exp. (d) stable. Thus, Gd (64) has EC as
(a) There is a gradual decrease in the radii of the [Xe]54 4 f 7, 5 d 1, 6s 2
lanthanoids with increasing atomic number — Instead of [Xe]54 4f 8 , 6s 2 .
a case of lanthanide contraction, thus true.
(b) Ionisation potential for the formation of Lu3+ is
comparatively low, hence +3 state is
66. Among the ligands NH 3 , en,CN − and CO,
favourable, thus true. the correct order of their increasing field
(c) Due to lanthanoide contraction–Zr and Hf; Nb strength, is [AIEEE 2011]
and Ta, Mo and W have the same size and (a) CO < NH3 < en < CN − (b) NH3 < en < CN − < CO
thus similar properties and thus separation is (c) CN − < NH3 < CO < en (d) en < CN − < NH3 < CO
not easy, thus true.
(d) Formation of +4 state requires very high Exp. (b)
energy, thus incorrect. Based on spectrochemical series, ligands
arranged in increasing order of crystal field
64. The magnetic moment (spin only) of strength are as
[NiCl 4 ]2 – is [AIEEE 2011] NH3 < en < CN− < CO
(a) 1.82 BM (b) 5.46 BM (c) 2.82 BM (d) 1.41 BM
67. Which one of the following complex ions
Exp. (c) has geometrical isomers? [AIEEE 2011]
[NiCl 4 ]2– ; oxidation number of Ni, x − 4 = − 2 (a) [Co (en)3 ] 3 + (b) [Ni (NH3 )5 Br]+
∴ x = + 2, Ni(28) [Ar] 3d 8 , 4s 2
(c) [Co(NH3 )2 (en)2 ]3 + (d) [Cr(NH3 )4 (en)]3 +
sp 3
3d 8 Exp. (c)
Ni 2+[Ar] (c) Complex Isomerism shown
4s 0 4p
(a) |Co(en)3|3+ Optical only
[NiCl4]2– (b) |Ni(NH 3 )5Br|+ No geometrical isomer
sp 3 sp 3 sp 3 sp 3 3+
(c) |Co(NH 3 )2(en)2| Cis and trans
Four sp 3 hybrid orbitals
(d) |Cr(NH 3 )4 (en)|3+ No geometrical isomer
sp3 -hybrid orbitals, tetrahedral
Since, Cl − is a weak ligand, thus unpaired
electrons are not paired. Lone pairs from 4 Cl − are 68. Which one of the following has an optical
accommodated in four sp3 hybrid orbitats. isomer? (en = ethylenediamine) [AIEEE 2010]
n = unpaired electron = 2, paramagnetic (a) [Zn(en)(NH3 ) 2 ]2 + (b) [Co(en) 3 ]3 +
3+
Magnetic moment (spin only) (c) [Co(H2O)4 (en)] (d) [Zn(en) 2 ]2 +
= n (n + 2 ) BM = 8 = 2.828 BM

Exp. (b) 71. Which of the following has an optical

Complex [Co(en)3 ]3+ has no plane of symmetry isomer? [AIEEE 2009]
and centre of symmetry. That’s why, it is optically (a) [Co(NH3 )3 Cl]+ (b) [Co(en)(NH3 )2 ]2 +
active. (c) [Co(H2O)4 (en)] 3+
(d) [Co(en)2 (NH3 )2 ]3 +
en en
Exp. (d)
en en
Co3+ 3+
Co NH3 3+ H 3N 3+
H 2N NH3 H 3N NH2
en en
Co Co
69. The correct order of E °M 2 + /M values with H 2N NH2 H2 N NH2

negative sign for the four successive NH2 NH2
elements Cr, Mn, Fe and Co is [AIEEE 2010]
(a) Mn > Cr > Fe > Co 72. In context with the transition elements,
(b) Cr > Fe > Mn > Co which of the following statements is
(c) Fe > Mn > Cr > Co incorrect?
(d) Cr > Mn > Fe > Co (a) In addition to the normal oxidation state, the
zero oxidation state is also shown by these
Exp. (a) elements in complexes [AIEEE 2009]
Usually across the first transition series, the (b) In the highest oxidation states, the transition
negative values for standard electrode potential metal shows basic character and form cationic
decrease except for Mn due to stable complexes
d 5 -configuration. (c) In the highest oxidation states of the first five
So, correct order : Mn > Cr > Fe > Co transition elements (Sc to Mn), all the 4s and
3d electrons are used for bonding
70. Knowing that the chemistry of lanthanoids (d) Once the d 5 configuration is exceeded, the
(Ln) is dominated by its +3 oxidation state, tendency to involve all the 3d electrons in
which of the following statements is bonding decreases
incorrect? [AIEEE 2009] Exp. (b)
(a) Because of the large size of the Ln (III) ions the As oxidation state increases, electronegativity
bonding in its its compounds is increases thus acidic characteristic increases not
predominantly ionic in character basic.
(b) The ionic sizes of Ln (III) decrease in general 73. Which of the following pairs represents
with increasing atomic number linkage isomers? [AIEEE 2009]
(c) Ln (III) compounds are generally colourless
(a) [Cu(NH3 )4 ][PtCl 4 ] and [Pt(NH3 )4 ][CuCl 4 ]
(d) Ln (III) hydroxide are mainly basic in
(b) [Pd(PPh 3 )2 (NCS)2 ] and [Pd(PPh 3 )2 (SCN)2 ]
character
(c) [Co(NH3 )5 ]NO 3 SO 4 and [Co(NH3 )5 SO 4 ]NO 3
Exp. (c) (d) [PtCl 2 (NH3 )4 ]Br2 and [PtBr2 (NH3 )4 ]Cl 2
The most common oxidation state of lanthanoid is
Exp. (b)
+3. Lanthanoids in +3 oxidation state usually
have unpaired electron in f-subshell and impart Linkage isomers are caused due to the presence
characteristic colour in solid as well as in solution of ambidentate ligands [Pd(PPh3 )2 (NCS)2 ] and
[Pd(PPh3 )2 (SCN)2 ] are linkage isomers due to
state due to f-f transition. (Except lanthanum and
SCN, an ambidentate ligand.
lutetium)
Thus, SCN can linked to Pd by both N as well as S
through their lone pairs.

74. Larger number of oxidation states are CO >CN– > NO –2 > en >NH3 > py >
exhibited by the actinoides than those NCS– > H2O > O 2 − > OX 2– > OH– > F – >
by the lanthanoides, the main reason being
(a) 4f orbitals more diffused than the 5f orbitals Cl – > SCN− > S2 – > Br − > I –
(b) lesser energy difference between 5f and 6d

than between 4f and 5d orbitals
76. Identify the incorrect statement among the
(c) more energy difference between 5f and 6d
following. [AIEEE 2007]
than between 4f and 5d orbitals (a) d-block elements show irregular and erratic
(d) more reactive nature of the actinoides than chemical properties among themselves
the lanthanoides [AIEEE 2008] (b) La and Lu have partially filledd orbitals and no
other partially filled orbitals
Exp. (b) (c) The chemistry of various lanthanoids is very
similar
Lanthanoides : [Xe] 4f1−14 5 d 0 −1 6s 2
(d) 4f and 5f orbitals are equally shielded
Actinoides : [Rn]5f1−14 6 d 0 −17 s 2
Lanthanoides and actinoides use core d and Exp. (d)
f orbitals also to show higher oxidation state. As 4f orbital is nearer to nucleus as compared to 5f
actinoides have comparatively low energy orbital. Therefore, shielding of 4f is more than 5f
difference between f and d orbitals, thus, they orbital.
show more number of oxidation states.
77. The actinoids exhibit more number of
75. The coordination number and the oxidation oxidation states in general than the
state of the element ‘E ’ in the complex lanthanoids. This is because [AIEEE 2007]
[E(en)2 (C 2O4 )] NO2 (where (en) is ethylene (a) the 5f orbitals are more buried than the 4f
diamine) are, respectively [AIEEE 2008] orbitals
(a) 6 and 2 (b) 4 and 2 (c) 4 and 3 (d) 6 and 3 (b) there is a similarity between 4f and 5f orbitals
Exp. (d) in their angular part of the wave function
(c) the actinoids are more reactive than the
en, CH2 NH2 is bidentate ligand lanthanoids
|
(d) the 5f orbitals extend farther from the nucleus
CH2 NH2
than the 4f orbitals
C 2O 2–
4 is also bidentate ligand. Exp. (d)
Hence, coordination number of the element E in The actinoids (5f-element) exhibit more number of
the given complete comes out to be 6. oxidation states in general than the lanthanoids
The complex can be ionised as because 5f orbitals extend farther from the
[E (en)2 (C 2O 4 )] NO 2 → nucleus than the 4f-orbitals.
[E (en)2 (C 2O 4 )]+ NO −2 Thus, the attraction on the 5f electrons in actinoid
Oxidation number x + 0 + (−2 ) = + 1 series decreases. Hence, they can easily
⇒ Oxidation number, x = 3 participate in bonding and therefore, exhibits
more number of oxidation states.
79. In which of the following octahedral
complexes of Co (At no. 27), will the 78. Which one of the following has a square
magnitude of ∆ o be the highest? [AIEEE 2008] planar geometry? [AIEEE 2007]
(a) [Co (CN)6 ]3 – (b) [Co (C2O 4 )3 ]3 – (At. no. Co = 27, Ni = 28, Fe = 26, Pt = 78)
(c) [Co (H2O)6 ]3 + (d) [Co (NH3 )6 ]3 + (a) [CoCl 4 ]2 − (b) [FeCl 4 ]2 −
2−
(c) [NiCl 4 ] (d) [PtCl 4 ]2 −
Exp. (a)
Exp. (d)
CFSE (crystal field splitting energy) for octahedral
complex, ∆o depends on the strength of negative Cl − is a weak ligand but Cl − cause the pairing of
ligand. Spectrochemically, it has been found that electrons with large Pt 2+ and consequently give
the strength of splitting is as follows dsp2 hybridisation and square planar geometry.

79. Lanthanoid contraction is caused due to Exp. (d)

(a) the appreciable shielding on outer electrons The IUPAC name for the complex
by 4f electrons from the nuclear charge [Co(NO 2 )(NH3 )5 ]Cl 2
(b) the appreciable shielding on outer electrons Pentammine nitrito-N-cobalt (III) chloride3
by 5d electrons from the nuclear charge 82. Nickel (Z = 28) combines with a uninegative
(c) the same effective nuclear charge from Ce to Lu monodentate ligand X − to form a
(d) the imperfect shielding on outer electrons by paramagnetic complex [NiX 4 ]2− . The
4f electrons from the nuclear charge number of unpaired electron (s) in the
[AIEEE 2006] nickel and geometry of this complex ion are,
Exp. (d) respectively [AIEEE 2006]
Imperfect shielding on outer electrons by 4f (a) one, tetrahedral (b) two, tetrahedral
electrons from the nuclear charge is due to the (c) one, square planar (d) two, square planar
diffused large shape of 4f-orbitals.
This imperfect shielding is unable to counterbalance
Exp. (b)
the effect of the increased nuclear charge. Hence, 28 Ni = [Ar] 4s 2 , 3 d 8
the net result shows contraction in size. Ni 2+
= [Ar] 3 d 8
80. In Fe (CO)5, the Fe—C bond possesses
(a) π-character only [AIEEE 2006] 3d 4s 4p
(b) both σ and π-characters sp3
(c) ionic character Nickel has two unpaired electrons and geometry
(d) σ-character only is tetrahedral due to sp3 hybridisation.
83. On heating, mixture of Cu 2O and Cu 2S will
Exp. (b) give [AIEEE 2005]
Fe (CO)5 is an organometallic coordinated (a) Cu 2 SO 3 (b) CuO + CuS
compound in which electrons from d-orbital of Fe
(c) Cu + SO 3 (d) Cu + SO 2
are partially transferred to anti-bonding molecular
∗ Exp. (d)
oritals ( π ) of CO. This type of bonding is called
π-backbonding. Following reaction takes place during
bessemerisation.
Fe C=O
2Cu2O + Cu2S → 6Cu + SO 2
σ-bond
electron donation 84. Calomel (Hg 2Cl 2 ) on reaction with
from CO to Fe ammonium hydroxide gives [AIEEE 2005]
(a) HgO (b) Hg 2O
(c) NH2  Hg  HgCl (d) HgNH2Cl
Fe C ≡≡ O
Exp. (d)
Hg 2Cl 2 + 2NH4OH → Hg(NH2 )Cl + Hg ↓
electron donation white black
through π -backbonding +NH4Cl + 2H2O
Thus,Fe (CO)5 possesess both σ and π-character. 85. The value of the ‘spin only’ magnetic
81. The IUPAC name for the complex[Co(NO2 ) moment for one of the following
configurations is 2.84BM. The correct
(NH 3 )5]Cl 2 is [AIEEE 2006]
one is [AIEEE 2005]
(a) nitrito-N-pentamminecobalt (III) chloride
(a) d 5 (in strong ligand field)
(b) nitrito-N-pentamminecobalt (II) chloride
(b) d 3 (in weak as well as in strong fields)
(c) pentammine nitrito-N-cobalt (II) chloride
(c) d 4 (in weak ligand field)
(d) pentammine nitrito-N-cobalt (III) chloride (d) d 4 (in strong ligand field)

Exp. (d) 87. The lanthanide contraction is responsible

5
(a) d in strong field for the fact that [AIEEE 2005]
n = unpaired electron = 1 (a) Zr and Zn have the same oxidation state
(b) Zr and Hf have about the same radius
eg (c) Zr and Nb have similar oxidation state

(d) Zr and Y have about the same radius
t2g Exp. (b)

Due to lanthanoid contraction, the atomic radii of
Magnetic moment = n(n + 2 ) BM the elements belonging to the same group of the
= 3 BM = 1.73 BM 2nd and 3rd transition series becomes same.
Thus, 40 Zr [160 pm] and 72 Hf [159 pm] have
(b) d 3 in strong/weak field almost same radii.
eg 88. The IUPAC name of the coordination
compound K 3[Fe(CN)6 ] is [AIEEE 2005]
t2g (a) tripotassium hexacyanoiron (II)
(b) potassium hexacyanoiron (II)
n=3 (c) potassium hexacyanoferrate (III)
(d) potassium hexacyanoferrate (II)
Magnetic moment = 15 = 3.87 BM
(c) d 4 in weak field Exp. (c)
eg K 3 [Fe(CN)6 ]
Cation Anion
Oxidation state of Fe in anion = + 3
t2g Thus, it is potassium hexacyanoferrate (III).
n=4 89. Which one of the following cyano

Magnetic moment = 24 = 4.90 BM complexes would exhibit the lowest value of
(d) d 4 in strong field paramagnetic behaviour ? [AIEEE 2005]
eg (At. no. of Cr = 24, Mn =25, Fe = 26, Co = 27)

(a) [Co(CN)6 ]3 − (b) [Fe(CN)6 ]3 −
(c) [Mn(CN)6 ]3 − (d) [Cr(CN)6 ]3 −
t2g
Exp. (a)
n=2
Hybridisation Unpaired Magnetic
Magnetic moment = 8 = 2.83 BM electrons moment
86. Which of the following factors may be (a) [Co(CN)6 ]3− d 2 sp3 (0) 0
regarded as the main cause of lanthanide (b) [Fe(CN)6 ]3− d 2 sp3 (1) 3 BM
contraction? [AIEEE 2005] (c) [Mn(CN)6 ] 3− 2 3
d sp (2) 8 BM
(a) Greater shielding of 5d electron by 4f (d) [Cr(CN)6 ]3− d 2 sp3 (3) 15 BM
electrons
(b) Poorer shielding of 5d electron by 4f electrons Thus, least paramagnetism is (a).
(c) Effective shielding of one of 4f electron by 90. Which of the following compounds shows
another in the subshell optical isomerism ? [AIEEE 2005]
(d) Poor shielding of one of 4f electron by (a) [Co(CN)6 ]3 −
another in the subshell
(b) [Cr(C2O 4 )3 ]3 −
Exp. (d)
(c) [ZnCl 4 ]2 −
Lanthanide contraction is due to poor shielding of
one of 4f electron by another in the sub-shell. (d) [Cu(NH3 )4 ]2 +

Exp. (b) 3– Exp. (d)

C2O4
All the given compounds, exhibits geometrical (cis
and trans isomers) but only cis isomer of
C2O4 Cr [CO (en)2 Cl 2 ]+ possess optical isomers (d and l)
due to the presence of symmetrical didentate, en
[ethylediamine].
C2O4
Mirror image is not superimposable, hence optical 94. The correct order of magnetic moments
isomerism is possible. (spin only values in BM) among the
following is
91. Cerium (Z = 58) is an important member of (At. no of Mn = 25, Fe = 26, Co = 27)
the lanthanides. Which of the following [AIEEE 2004]
statements about cerium is incorrect? (a) [MnCl 4 ]2 − > [CoCl 4 ]2 − > [Fe(CN)6 ]4 −
(a) The common oxidation states of cerium are +3
(b) [MnCl 4 ]2 − > [Fe(CN)6 ]4 − > [CoCl 4 ]2 −
and +4 [AIEEE 2004]
(c) [Fe(CN)6 ]4 − > [MnCl 4 ]2 − > [CoCl 4 ]2 −
(b) The +3 oxidation state of cerium is more stable
than the +4 oxidation state (d) [Fe(CN)6 ]4 − > [CoCl 4 ]2 − > [MnCl 4 ]2 −
(c) The +4 oxidation state of cerium is not known
in solutions Exp. (a)
(d) Cerium (IV) acts as an oxidising agent Number of unpaired electrons in [Fe(CN)6 ]4− is
Exp. (c) zero.
Thus, magnetic moment = n (n + 2 ) = 0 BM
+3 and +4 states are shown by Ce in aqueous
solution. Thus, statement (c) is incorrect. (n = unpaired electrons)
n in [MnCl 4 ]2− = 5, 35 BM
92. The coordination number of a central metal
atom in a complex is determined by n in [CoCl 4 ]2− = 3, 15 BM
[AIEEE 2004]
(a) the number of ligands around a metal ion 95. Which one of the following complexes is
bonded by sigma bonds an outer orbital complex? [AIEEE 2004]
(b) the number of ligands around a metal ion (At. no. of Mn = 25,Fe = 26,Co = 27, Ni = 28)
bonded by pi bonds (a) [Fe(CN)6 ]4 − (b) [Mn(CN)6 ]4 −
(c) the number of ligands around a metal ion (c) [Co(NH3 )6 ]3 + (d) [Ni(NH3 )6 ]2 +
bonded by sigma and pi bonds both
(d) the number of only anionic ligands bonded to Exp. (d)
the metal ion
(a) Fe2+ = [Ar]
Exp. (a)
3d6 4s 4p
Coordination number is the maximum covalency Fe2+in
shown by a metal or metal ion. It is the maximum strong = [Ar]
number of ligands attached to metal by sigma ligand
3d6 4s 4p
bonds or coordinate bonds. CN–
[Fe(CN)6 ]4 –
93. Which one of the following has largest [Ar] × × × × × ×
number of isomers? [AIEEE 2004]
(R = alkyl group, en = ethylenediamine) d2 sp3 (inner
+ 2+ d orbital complex)
(a) [Ru(NH3 )4 Cl 2 ] (b) [Co(NH3 )5 Cl]
(c) [Ir(PR 3 )2 H(CO)]2 + (d) [Co(en)2 Cl 2 ]+

(b) Mn2+= [Ar]

97. Which of the following groups of transition
3d5 4s 4p metals is called coinage metals? [AIEEE 2003]
[Mn(CN)6 4 – ]= (a) Cu, Ag, Au (b) Ru, Rh, Pd
(c) Fe, Co, Ni (d) Os, Ir, Pt
[Ar] × × × × × ×
Exp. (a)
d2 sp3 (inner
Cu, Ag, Au are called coinage metals because
d orbital complex)
in the early times, they were used in making
(c) Co3+= [Ar] coins.
3d6 4s 4p 98. Which one of the following nitrates will leave

[Co(NH3)6] 3+
= behind a metal on strong heating?
[AIEEE 2003]
[Ar] × × × × × × (a) Ferric nitrate (b) Copper nitrate
(c) Manganese nitrate (d) Silver nitrate
NH 3 is a d2 sp3 (inner
strong ligand d orbital complex) Exp. (d)
Metal oxides lying below Hg in electrochemical
(d) Ni 2+ = [Ar] series decompose to form metal.
∆
3d8 4s 4p ZnO, MgO, CuO → no effect
∆
In this case also, NH3 is a strong ligand but Ag 2O → Ag + O 2
electrons remain unpaired, since only one orbital ∆
AgNO 3 → Ag 2O → Ag + O 2
is left vacant in 3d. Thus, [Ni(NH3 )6 ] 2+
[Ar] × × × × × ×
99. For making good quality mirrors, plates of
float glass are used. These are obtained by
3d8 4s 4p 4d floating molten glass over a liquid metal
sp3d2 which does not solidify before glass. The
(outer d-orbital complex) metal used can be [AIEEE 2003]
(a) mercury (b) tin
96. Of the following outer electronic (c) sodium (d) magnesium
configurations of atoms, the highest
oxidation state is achieved by which one of Exp. (a)
them ? [AIEEE 2004] Mercury (Hg) solidifies after glass, so used
(a) (n −1) d 8ns 2 (b) (n −1) d 5ns 1 mercury for making good quality mirrors.
(c) (n −1) d 3ns 2 (d) (n −1) d 5ns 2
100. Which one of the following statements is
Exp. (d) correct? [AIEEE 2003]
8 2 4(as in Ni) (a) Manganese salts give a violet borax bead test
(n–1)d ns
in the reducing flame
(n–1)d8 ns2 (b) From a mixed precipitate of AgCl and AgI,
ammonia solution dissolves only AgCl
(n–1)d5ns1 6(as in Cr)
(c) Ferric ions give a deep green precipitate on
5
(n–1)d ns1 adding potassium ferrocyanide solution
(d) On boiling a solution having K + , Ca 2 + and
(n–1)d3ns2 5(as in V) HCO −3 ions, we get a precipitate of K 2Ca(CO 3 )2
3 2
(n–1)d ns Exp. (b)
5 2 7(as in Mn) Ammonia can dissolve precipitate of AgCl due to
(n–1)d ns
5 2
the formation of complex as given below
(n–1)d ns
AgCl + 2NH3 → [Ag(NH3 )2 Cl ]

101. A red solid is insoluble in water. However, Exp. (b)

it becomes soluble if some KI is added to 2CrO 24 − + 2H+ → Cr2O 27 − + H2O
water. Heating the red solid in a test tube
results in liberation of some violet coloured 104. One mole of the complex compound
fumes and droplets of a metal appear on the Co(NH 3 )5Cl 3 , gives 3 moles of ions on
cooler parts of the test tube. The red solid is dissolution in water. One mole of the same
(a) (NH4 )2 Cr2O 7 (b) HgI2 [AIEEE 2003] complex reacts with two moles of AgNO3
(c) HgO (d) Pb3O 4 solution to yield two moles of AgCl(s). The
structure of the complex is [AIEEE 2003]
Exp. (b) (a) [Co(NH3 )5 Cl] Cl 2
HgI2 becomes soluble in water, when KI is added (b) [Co(NH3 )3 Cl 3 ]⋅ 2NH3
to it due to the formation of K 2HgI4 complex which (c) [Co(NH3 )4 Cl 2 ]Cl ⋅ NH3
is soluble in water. (d) [Co(NH3 )4 Cl] Cl 2 ⋅ NH3
HgI2 + 2KI → K 2HgI4
(soluble )
Exp. (a)
But when HgI 2 is heated, HgI2 decomposes to The oxidation state of nickel is
give violet coloured fumes of I2 that deposits on [Co(NH3 )5 Cl] Cl 2 r [Co(NH3 )5 Cl]2+ + 2Cl −
14444244443
the cooler parts of the test tube. three ions
∆
HgI2 → Hg + I2 ↑ 105. In the coordination compound,
K 4[Ni(CN)4 ] the oxidation state of nickel is
102. Ammonia forms the complex ion
[AIEEE 2003]
[Cu(NH 3 )4 ]2+ with copper ions in the
alkaline solutions but not in acidic solutions. (a) −1 (b) 0 (c) + 1 (d) + 2
What is the reason for it? [AIEEE 2003] Exp. (b)
(a) In acidic solutions, hydration protects copper
ions The oxidation state of nickel is
(b) In acidic solutions, protons coordinate with K 4 [Ni(CN)4 ] → 4K+ + [Ni(CN)4 ]4 −
ammonia molecules forming NH+4 ions and [Ni(CN)4 ]4– → x + (4 × − 1) = − 4
NH3 molecules are not available
x − 4 = − 4 or x = 0
(c) In alkaline solutions, insoluble Cu(OH)2 is
precipitated which is soluble in excess of any 106. Most common oxidation states of Ce
alkali (Cerium) are [AIEEE 2002]
(d) Copper hydroxide is an amphoteric substance (a) + 3, + 4 (b) + 2 , + 3
(c) + 2 , + 1 (d) + 3, + 5
Exp. (b)
In acidic solutions, N atoms of NH 3 donates their Exp. (a)
lone pair electrons to protons forming NH +4 ions. Cerium, Ce 58 = [Xe] 4f1 5d 1 6s 2 . Its most stable
Therefore, lone pair electrons of NH3 are not
oxidation state is +3 but +4 is also existing.
available for forming the complex with copper
ions. 107. Type of isomerism shown by
[Cr(NH 3 )5 NO2] Cl 2 is [AIEEE 2002]
103. What would happen when a solution of
(a) optical (b) ionisation
potassium chromate is treated with an
(c) geometrical (d) linkage
excess of dilute nitric acid? [AIEEE 2003]
(a) Cr 3 + and Cr2O 27 − are formed Exp. (d)
(b) Cr2O 27 − and H2O are formed [Cr(NH3 )5 NO 2 ] Cl 2 (Pentamminenitrito chromium
(c) CrO 24 − is reduced to +3 state of Cr (III) chloride) exhibits linkage isomerism as −NO 2
is ambidentate ligand.
Isomer is [Cr(NH3 )5 ONO] Cl 2 .

108. A square planar complex is formed by the

hybridisation of the following atomic 3d6
orbitals [AIEEE 2002]
Number of unpaired electrons = 4
(a) s, p x , p y , p z (b) s, p x , p y , p z , d Ti 22 = [Ar] 4s 2 3d 2
(c) d, s, p x , p y (d) s, p x , p y , p z , d, d
Ti 2+ = [Ar] 3d 2 4s 0
Exp. (c)
A square planar geometry is the result of dsp2
3d2
hybridisation where inner d sub-shell (d 2 2
x −y
orbital) participates. Number of unpaired electrons = 2
Cr24 = [Ar] 3 d 5 , 4s1
Cr 2+ = [Ar] 3 d 4 , 4s 0
109. Which of the following ions has the
maximum magnetic moment? [AIEEE 2002]
3d4
(a) Mn 2 + (b) Fe2 + (c) Ti 2 + (d) Cr 2 +
Exp. (a) Hence, Mn2+ : [Ar] 3 d 5 with five unpaired
Larger the number of unpaired electrons, greater electrons have maximum magnetic moment.
the magnetic moment, µ = n (n + 2 )
where, n = Number of unpaired electrons 110. The most stable ion is [AIEEE 2002]
Mn25 = [Ar] 4s 2 , 3 d 5 (a) [Fe(OH)5 ]3 − (b) [FeCl 6 ]3 −
Mn2+ = [Ar] 3d 5 4s 0 (c) [Fe(CN)6 ]3 − (d) [Fe(H2O)6 ]3 +
Exp. (c)
3d5 Stability of complex increases with increase in
charge on the central metal ion and with increase
in basic strength of ligand.
Fe 26 = [Ar] 4s 2 , 3 d 6
In [Fe(CN)6 ]3− , oxidation state of Fe is +3 and
Fe 2+ = [Ar] 3 d 6 , 4s 0 basicity of CN− is higher than OH– , Cl − and H2O.

14
Environmental Chemistry
These compounds ultimately reach the
1. Which is wrong with respect to our stratosphere where they get broken down by
responsibility as a human being to protect our powerful UV radiations and release chlorine free
environment? [JEE Main 2019, 8 April Shift-I] radical. The chlorine free radicals react with
ozone and cause its depletion by converting it
(a) Restricting the use of vehicles
into chlorine monoxide radical and molecular
(b) Avoiding the use of floodlighted facilities oxygen.
(c) Setting up compost tin in gardens hν •
(d) Using plastic bags CF2Cl 2 (g ) → Cl(g ) + CF2Cl(g )
hν •
Exp. (d) CFCl 3 (g ) → CFCl 2 (g ) + Cl(g )
• •
Using plastic bags is wrong with respect to Cl(g ) + O 3 (g ) → ClO(g ) + O2 (g )
responsibility as a human being to protect our
environment. Plastic bags are non-biodegradable Ozone holes increase the amount of UV radiation
in nature. It remains in the environment as such reaching the earth. These radiations can cause
and does not degraded by bacteria. If it is not skin cancer, sunburns, ageing of skin.
disposed properly then it may lead serious threat
to the environment. The activities that can be 3. The maximum prescribed concentration of
used to protect our environment are as follows: copper in drinking water is
● Restricting the use of vehicles. [JEE Main 2019, 8 April Shift-II]
● Avoiding the use of flood lighted facilities. (a) 5 ppm (b) 0.5 ppm
● Setting up compost tin in gardens. (c) 0.05 ppm (d) 3 ppm
2. Assertion (A) Ozone is destroyed by CFCs in

Exp. (d)
the upper stratosphere. According to W.H.O. and US environmental
protection agency guidelines, maximum
allowable concentration of metals in drinking
Reason (R) Ozone holes increase the amount water are as follows :
of UV radiation reaching the earth.
Metal Maximum concentration
(a) Assertion and Reason are incorrect. (ppm or mg dm−3 )
(b) Assertion and Reason are both correct and
the Reason is the correct explanation for the Cd 0.005
Assertion.
Mn 0.05 (option-c)
(c) Assertion and Reason are correct, but the
Reason is not the explanation for the Assertion. Al 0.2
(d) Assertion is false, but the Reason is correct.
Fe 0.2
Exp. (c)
Cu 3.0 (option-d)
Ozone is destroyed by CFCs in the upper
stratosphere. Zn 5.0 (option-a)

Environmental Chemistry 193
4. Excessive release of CO2 into the atmosphere combine to produce photochemical smog which
results in [JEE Main 2019, 9 April Shift-I] mainly contains peroxyacetyl nitrate (PAN).
O
(a) formation of smog (b) depletion of ozone ||
(c) polar vortex (d) global warming CH3 C O O NO 2 (PAN)
Exp. (d)
8. The noble gas that does not occur in the
The effect of release of CO 2 gas into atmosphere atmosphere is [JEE Main 2019, 10 April, (Shift II)]
is global warming.
(a) Ra (b) Kr (c) He (d) Ne
5. The layer of atmosphere between 10 km to Exp. (a)
50 km above the sea level is called as Radium (Ra) is a radioactive element. Ra
[JEE Main 2019, 9 April, Shift-II] belongs to group 2 (alkaline earth metals), it is
(a) stratosphere (b) mesosphere not a noble gas.
(c) thermosphere (d) troposphere Note In question noble gas which does not exist
Exp. (a) in the atmosphere is asked and answer is Ra.
But Ra (radium) is an alkaline earth metal and
The atmosphere between the heights 10 to not noble gas. It can be Rn (radon) and is
50 km above the sea level is stratosphere. misprint in JEE Main Paper.
Atmosphere is not of the same thickness at
heights. 9. The correct set of species responsible for the
photochemical smog is
6. The regions of the atmosphere, where clouds
[JEE Main 2019, 12 April, (Shift I)]
form and where we live, respectively, are
(a) N 2 , NO 2 and hydrocarbons
[JEE Main 2019, 10 April, Shift-I]
(b) CO 2 , NO 2 , SO 2 and hydrocarbons
(a) stratosphere and stratosphere
(b) troposphere and troposphere (c) NO, NO 2 , O 3 and hydrocarbons
(c) troposphere and stratosphere (d) N 2 , O 2 , O 3 and hydrocarbons
(d) stratosphere and troposphere Exp. (c)
Exp. (b) The correct set of species responsible for the
The lowest region of atmosphere is troposphere photochemical smog is NO, NO 2 , O 3 and
which extends upto the height of 10 km (approx) hydrocarbons. Photochemical smog appears in
from sea level. We live in the tropospheric region. warm, dry and sunny climate which are obtained
It contains air, water vapour and dust which can by the action of sunlight on unsaturated
form clouds with the help of strong air movement. hydrocarbons and nitrogen oxides. Following
reactions are involved during the formation of
Above the troposphere, stratospheric region
photochemical smog.
extends upto 50 km from sea level. It contains
mainly N2 , O 2 , O 3 and little water vapour. O 3 in (i) N2 (g ) + O 2 (g ) → 2NO(g )
the stratosphere absorbs 99.5% of the sun’s (Originates from
burning of fossil fuels)
harmful UV raditions and thus protects the lives
Sunlight
on the earth. (ii) 2NO(g ) + O 2 (g ) → 2NO 2 (g )
hν
7. Air pollution that occurs in sunlight is NO 2 (g ) → NO(g ) + [O]
Nascent oxygen
[JEE Main 2019, 10 April, Shift-II]
(iii) O (g ) + O 2 (g ) - O (g ) 3
(a) acid rain (b) oxidising smog
Reacts rapidly with NO
(c) fog (d) reducing smog
O 3 (g ) + NO(g ) → NO 2 (g ) + O 2 (g )
Exp. (b) Brown gas (in high
concentration form haze)
In sunlight oxidising smog or photochemical
smog or Los-Angeles smog is formed. This 3CH4 (g ) + 2O 3 (g ) → 3CH2 == O(g )
smog is brown in colour. It occurs in warm, dry (Unburnt Formaldehyde
hydrocarbon)
and sunny climate. In presence of sunlight, NO x + CH2 == CHCH == O +H2O
(N-oxides), O 2 and unburnt hydrocarbons of air Acrolein

10. The primary pollutant that leads to Metal Max. concentration in ppm
photochemical smog is Zn 5
(a) acrolein Mn 0.05
(b) nitrogen oxides

Fe 0.2
(c) ozone
(d) sulphur dioxide Cu 3
Exp. (b) As the concentration of Mn in the given water sample
The primary pollutant that leads to photochemical is more than the recommended concentration. Thus,
smog is nitrogen oxides. Burning of fossil fuels it makes water unsuitable for drinking.
such as petrol and diesel in automobiles,
reaction between nitrogen and oxygen and other 12. The condition for methemoglobinemia by
such reactions result in a variety of pollutants, drinking water is [ JEE Main 2019, 9 Jan Shift-II]
two main of which are hydrocarbons (unburnt fuel) (a) > 50 ppm nitrate (b) > 50 ppm chloride
and nitric oxide (NO). (c) > 50 ppm lead (d) > 100 ppm sulphate
N2 (g ) + O 2 (g ) diesel

In petrol and
engines
→ 2NO(g ) Exp. (a)
When the concentration of these pollutants is According to EEC (European Environment
sufficiently high, a chain reaction initiate because Commission), excess of NO−3 (> 50 ppm) in
drinking water may lead to methemoglobinemia
of the interaction of sunlight with oxides of
(‘Blue baby syndrome’). It also may cause
nitrogen. stomach-cancer.
2NO(g ) + O 2 (g ) Sunlight
→ 2NO 2 (g )
NO 2 (g )  hν
→ NO(g ) + [O] 13. The pH of rain water, is approximately
Nascent
oxygen
(a) 7.5 (b) 6.5 (c) 5.6 (d) 7.0
O 3 (g ) + NO(g ) → NO 2 (g ) + O 2 (g ) [ JEE Main 2019, 9 Jan Shift-II]
Brown gas
Exp. (c)
11. A water sample has ppm level concentration of
the following metals: Fe = 0.2; Mn = 5.0 ; In clean air, rain water picks up some acidic oxides
like CO 2 and SO 2 (obtained from volcanic eruptions).
Cu = 3.0; Zn = 5.0. The metal that makes the
These substance make the rain slightly acidic
water sample unsuitable for drinking is
(pH = 5.6 − 6).
(a) Cu
But, when rain falls through polluted air, it consumes
(b) Fe
oxides of sulphur (SO x ) and oxides of nitrogen (NO x ),
(c) Mn
mists of HCl etc. They make the rain more acidic
(d) Zn
(called acid rain) of pH range 3.5 to 5.6.
Exp. (c) 14. Water filled in two glasses A and B have BOD
values of 10 and 20, respectively. The correct
For drinking water, the maximum recommended statement regarding them, is
levels of some metals, set by European Environment [ JEE Main 2019, 10 Jan Shift-I]
Commission (EEC) is
(a) A is more polluted than B
(b) A is suitable for drinking, wherease B is not
(c) Both A and B are suitable for drinking
(d) B is more polluted than A

Exp. (d) Exp. (b)

BOD is defined as the amount of oxygen required by Dissolved oxygen (DO) is the oxygen dissolved in
bacteria to break down the organic matter present in a water either from atmosphere or by photosynthesis.
certain volume of a sample of water. Clean water or The lower the concentration of DO in a water sample,
drinking water has a BOD value < 5 ppm. the more polluted is the water sample.
So, water filled with A, BOD = 10 ppm is polluted and The concentration range of dissolved oxygen (DO) in
water filled with B, cold water reaches upto 10 ppm, but that in normal
BOD = 20 ppm, is also polluted. water (at room temperature) is within 5 ppm.
But, B is more polluted than A.
17. Peroxyacetyl nitrate (PAN), an eye irritant is
15. The reaction that is not involved in the ozone produced by [JEE Main 2019, 11 Jan Shift-I]
layer depletion mechanism in the stratosphere (a) organic waste
is (b) acid rain
(a) CH4 + 2O3 → 3CH2 == O + 3H2O (c) classical smog
• • (d) photochemical smog
(b) Cl O(g ) + O(g ) → C l(g ) + O2 (g )
hν • • Exp. (d)
(c) HOCl(g ) → OH(g ) + Cl(g )
hν • • Molecular formula of peroxyacetyl nitrate (PAN) is
(d) CF2Cl 2 (g ) → Cl(g ) + CF2Cl(g ) O
[ JEE Main 2019, 10 Jan Shift-II] 
CH 3 C O O NO 2. It is a secondary pollutant.
Exp. (a)
It is present in photochemical smog (oxidising or Los
CH 4 is not present in the stratosphere and also it Angeles smog). PAN is a powerful lachrymator or tear
cannot diffuse or escape into the stratosphere like producer and it also causes breathing troubles.
freon-12 (CF2Cl 2 ) from the atmosphere.
In the stratosphere, ozone layer depletion take place 18. The higher concentration of which gas in air
mainly by chlorofluorocarbons (CFCs) like CF2Cl 2 and can cause stiffness of flower buds?
the mechanism of ozone layer depletion can be (a) SO 2 (b) CO
shown as:
• •
(c) CO 2 (d) NO 2
hν
(i) CF2Cl 2 (g ) → C l(g ) +CF2Cl(g ) [JEE Main 2019, 11 Jan Shift-II]
[Option, (d)]
• Exp. (a)
(ii) C l(g ) + O 3 (g ) → ClO •(g ) + O 2
Organic pigments (colourents) present in flower buds
(iii) ClO •(g ) + O(g ) → Cl •(g ) + O 2 (g ) retain their colour in the oxidised form of the pigment
[Option (b)] as their nature is itself oxidising in nature. When they
•
(iv) C l(g ) + H2O(g ) → HOCl(g ) + H•(g ) comes in contact with moist SO 2 (acid rain) of higher
[Present in the concentration, they get decoloured and stiff.
stratosphere]
SO 2 + H2O → H2SO 4
•
hν
(v) HOCl(g ) → OH(g ) + Cl •(g ) H2SO 4 → H+ + HSO 4−
[Option (c)] HSO −4 → H+ + SO 24 −
⇒ One Cl • can destroy or deplete 105 O 3 molecules. Due to the release of H + ion (acid), the flower get
As (i) reaction is involved in the formation of decoloured and stiff.
photochemical smog, not in ozone layer depletion. As a result, flower eventually falls off from plants.
So, option (a) is correct.
19. The molecule that has minimum/no role in the
16. The concentration of dissolved oxygen (DO) in formation of photochemical smog, is
cold water can go upto (a) N2 (b) CH2 == O
(a) 14 ppm (b) 10 ppm (c) NO (d) O3
(c) 8 ppm (d) 16 ppm

Exp. (a) Exp. (a)

N 2 molecule has minimum role in the formation of Freons or CFCs or chlorofluoro carbons, i.e. CF2Cl 2 is
photochemical smog. While CH 2 == O, O 3 and NO not the common component of photochemical smog.
has major role. When fossil fuels are burnt, a variety of This smog is produced as the result of tropospheric
pollutants are emitted. Two of them are hydrocarbons pollution while freons are the components of
(unburnt) and NO. When these pollutants build upto stratospheric pollution. These are infact considered
high levels, a chain reaction occurs from their as the major cause of ozone layer depletion.
interaction with sunlight. The reactions involved in the
formation of photochemical smog are as follows: 22. The upper stratosphere consisting of the
ν
NO 2( g ) h → NO( g ) + O( g ) ozone layer protects us from the sun’s
radiation that falls in the wavelength region of
O( g ) + O 2( g ) 1 O 3( g )
(a) 600 - 750 nm (b) 400 - 550 nm
NO( g ) + O 3( g ) → NO 2( g ) + O 2( g ) (c) 08
. -1.5 nm (d) 200 - 315 nm
O 3 reats with unburnt hydrocarbons to produce [ JEE Main 2019, 12 Jan (Shift-II)]
chemicals such as formaldehyde, acrolein and PAN.
3CH 4 + 2O 3 → 3CH 2== O + 3H 2O
Exp. (d)
Sun emits UV-radiations, which according to following
+ CH 2 == CCH == O + CH 3 COONO 2
EM categorisation have the wavelength range from 1

O nm to 400 nm.
(PAN)
Type Wavelength range

20. Water samples with BOD values of 4 ppm and
Radio wave > 0.1 m
18 ppm, respectively, are
(a) clean and clean Microwave 0.1 m to 1 mm
(b) highly polluted and clean Infrared wave 1 mm to 700 nm
(c) highly polluted and highly polluted
Visible rays 700 nm to 400 nm
(d) clean and highly polluted
[ JEE Main 2019, 12 Jan Shift-I] Ultraviolet rays 400 nm to 1 nm
Exp. (d) X-rays 1 nm to 10− 3 nm

The amount of oxygen required by bacteria to break
Gamma rays < 10− 3 nm
down the organic matter present in a certain value of a
sample of water is called biochemical oxygen Thus, option (d) with 200-315 nm range is the correct
demand (BOD). The amount of BOD in the water is a option.
measure of the amount of organic material in the
water, in terms of how much oxygen will be required to 23. A water sample has ppm level concentration of
break it down biologically. Clean water would have following anions : [JEE Main 2017 (Offline)]
BOD value of less than 5ppm whereas highly polluted
water would have BOD value of 17 ppm or more. F − = 10; SO24 − = 100; NO3− = 50
BOD value of clean water = 4 ppm The anion/anions that make/makes the water
BOD value of highly polluted water = 18 ppm. sample unsuitable for drinking is/are
(a) Only NO −3 (b) Both SO 24 − and NO −3
21. The compound that is not a common (c) Only F −
(d) Only SO 24 −
component of photochemical smog is
(a) CF2Cl 2 (b) H3C C OONO 2 Exp. (c)
(c) CH2 == CHCHO (d) O 3  NO 3− The maximum limit of nitrate (NO −3 ) in drinking
O
[ JEE Main 2019, 12 Jan Shift-II] water is 50 ppm and its source is fertilisers. If the
maximum limit is increased in water it will cause
methemoglobinemia (blue baby syndrome.)

SO 24 − The maximum limit of sulphate (SO 24 − ) the atmosphere but nitrogen oxide in not formed
according to WHO is 500 pm and its sources are acid under ordinary conditions.
rain, industries. Excess SO 24 − has laxative effect. But when temperature is high enough i.e. ≈ 2000 K, it
F − The maximum limit of fluoride (F − ) is about reacts with oxygen to form nitrogen oxide.
1.5 ppm. Its higher concentration converts enamel to ≈ 2000 K
N2 +O 2 → 2NO
more harder fluorapatite. Concentration (>2ppm)
causes brown mottling of teeth and high Thus, Assertion and Reason are true and Reason is
concentration (>10 ppm) are harmful for bones and the correct explanation of the Assertion.
teeth.
∴ SO 24 − (100 ppm) and NO −3 (50 ppm) in water is 26. The gas leaked from a storage tank of the
suitable for drinking but the concentration of Union Carbide plant in Bhopal gas tragedy was
F − (10 ppm) makes water unsuitable for drinking. [JEE Main 2013]
(a) Methylisocyanate (b) Methylamine
24. The concentration of fluoride, lead, nitrate and (c) Ammonia (d) Phosgene
iron in a water sample from an underground
lake was found to be 1000 ppb, 40 ppb, 100 Exp. (a)
ppm and 0.2 ppm, respectively. This water is Methylisocyanate CH 3 N == C == O (MIC gas) gas
unsuitable for drinking due to high was leaked from the storage tank of the union carbide
concentration of [JEE Main 2016 (Offline)] plant in Bhopal gas tragedy.
(a) lead (b) nitrate
27. What is DDT among the following?
(c) iron (d) fluoride
(a) Green house gas [AIEEE 2012]
Exp. (b) (b) A fertilizer
This water is unsuitable for drinking due to high (c) Biodegradable pollutant
concentration of nitrate. In drinking water, maximum (d) Non-biodegradable pollutant
permissible concentration of
Lead ~− 50 ppb
Exp. (d)
− 50 ppb
Nitrate ~ DDT is a non-biodegradable pollutant. It is the first
− 0.2 ppm
Iron ~ chlorinated organic insecticide.
− 1 ppm
Fluoride ~
28. Identify the incorrect statement from the
25. Assertion (A) Nitrogen and oxygen are the following [AIEEE 2011]
main components in the atmosphere but these (a) Oxides of nitrogen in the atmosphere can
do not react to form oxides of nitrogen. cause the depletion of ozone layer
[JEE Main 2015] (b) Ozone absorbs the intense ultraviolet
radiations of the sun
Reason (R) The reaction between nitrogen (c) Depletion of ozone layer is because of its
and oxygen requires high temperature. chemical reactions with chlorofluoro alkanes
(a) Both Assertion and Reason are correct and the (d) Ozone absorbs infrared radiations
reason is the correct explanation for the
Assertion. Exp. (d)
(b) Both Assertion and Reason are correct but the NO + O 3 → NO 2 + O 2
reason is not the correct explanation for the
O 3 + hv → O 2 + O
Assertion.
(c) The Assertion is incorrect but the Reason is NO 2 +O → NO + O 2
correct. Net reaction
(d) Both the Assertion and Reason are incorrect. 2O 3 + hν → 3O 2
Exp. (a) Thus, ozone layer is depleted by oxides of
nitrogen.
Nitrogen is an inert gas because of the presence of
Thus, (a) is correct statement.
strong bond. That's why although there is 78% N 2 in

(b) Ozone layer is a protective layer and absorbs

harmful UV rays from the sun. 30. The smog is essentially caused by the presence
Thus, (b) is also correct statement. of [AIEEE 2004]
• (a) O 2 and O 3
(c) Cl +O 3 → ClO + O 2 (b) O 2 and N 2
•
(c) oxides of sulphur and nitrogen
O 3 + hv → O + O 2
• • (d) O 3 and N 2
ClO +O → Cl +O 2
Net reaction
Exp. (a)
Smog is formed by the action of sunlight on
2 O 3 + hv → 3 O 2
unsaturated hydrocarbons and nitrogen oxides.
Thus, ozone layer is also depleted by reaction Smog mainly contains higher concentration of
with freons. Peroxyacetyl nitrate (PAN) formed by the reaction of
Thus, (c) is also correct statement. NO 2, O 3 and unsaturated hydrocarbons.
(d) It is a incorrect statement as ozone layer is hv NO + O
NO 2 →
permeable for UV rays.
O + O2 1 O3
Thus, correct answer is (d).
NO + O 3 → NO 2 + O 2
NO + O 3 + unsaturated hydrocarbons → PAN
29. Identify the wrong statements in the following
[AIEEE 2008]
30. When rain is accompanied by a thunderstorm,
(a) Chlorofluorocarbons are responsible for the collected rain water will have a pH value
ozone layer depletion [AIEEE 2003]
(b) Green house effect is responsible for global (a) slightly lower than that of rain water without
warming thunderstorm
(c) Ozone layer does not permit infrared (b) slightly higher than that when the
radiation from the sun to reach the earth thunderstorm is not there
(d) Acid rain is mostly because of oxides of (c) uninfluenced by occurrence of thunderstorm
nitrogen and sulphur (d) which depends on the amount of dust in air
Exp. (c) Exp. (a)

Ozone layer permits the infrared radiation to pass During thunderstorm, there is formation of NO which
changes to NO 2 and ultimately to HNO 3 (acidrain).
through but doesn’t permit the higher range of
O2
ultraviolet radiation to pass through. N2 + O 2 → NO → NO 2
4NO 2 + O 2 + 2H2O → 4HNO 3 [pH < 7]

15
General Organic
Chemistry
(a) CH3COCH3
1. The IUPAC name of the following compound
(b) CH3COCH2COCH3
is
(c) CH3COCH2COOC2 H5
CH 3 OH (d) CH3COCH2CONH2
 
H 3C  C H C H CH 2 COOH Exp. (b)
[JEE Main 2019, 8 April Shift-I] O OH
(a) 4,4 - dimethyl -3-hydroxybutanoic acid
(b) 2-methyl-3-hydroxypentan-5-oic acid Acetone No additional stability
(c) 3- hydroxy -4- methylpentanoic acid with the ‘enol’ form
(d) 4-methyl-3-hydroxypentanoic acid O O H
O O
Exp. (c)
Acetylacetone
The IUPAC name of the given compound is This enol-form is highly stable
3-hydroxy-4-methylpentanoic acid. because of intramolecular
H-bonding (6-membered stability)
CH3 OH and due to extended conjugation.
5  4 3 2 1
H3 C  CH  CH  CH2  COOH O O (–R)
O O
Principal chain
1 2 O
While naming the compound, the longest chain Ethyl acetoacetate 1 2 NH2
that have principal functional group —COOH is (EAA)
choosen and numbered in such a manner that
In both of the compounds, C-2 of C ==O group is a
the principal functional group gets the lowest O
possible number. —OH act as substituent and 
used as prefix in nomenclature. part of the acid derivative (ester, C OEt and
O
2. Which of the following compounds will  2
show the maximum ‘enol’ content? acid amide, C NH2 ). So, C O does not
[JEE Main 2019, 8 April Shift-II] take part in enolisation, because it is already in
resonance (–R) with the derivative group itself.

3. The correct IUPAC name of the following Carbocation

compound is intermediate
NO2
PE R++X–
–
+Nu
R X
Cl R  Nu
CH3 Progress of reaction
(a) 2-methyl-5-nitro-1-chlorobenzene SN1 reaction has two steps. In the first step, the
(b) 3-chloro-1-methyl-1-nitrobenzene carbon halogen bond breaks heterolytically, with
(c) 2-chloro-1-methyl 1-4-nitrobenzene the halogen retaining the previously shared pair
(d) 5-chloro-4-methyl 1-1-nitrobenzene of electron. In the second step, the nucleophile
reacts rapidly with the carbocation formed in the
Exp. (c) first step.
The IUPAC name of the given compound is In the above graph, the alkyl halide is the only
species that participates in the rate limiting step.
NO2 Here, the rate of reaction depends on the
4 concentration of the alkyl halide and does not
Incorrect
Correct
3 depend on the concentration of nucleophile.

way
way
2
5. The principle of column chromatography is
1 Cl
CH3 [JEE Main 2019, 10 April Shift-I]
2- chloro-1-methy l-4-nitrobenzene (a) differential absorption of the substances on
the solid phase
Here, the given compound contains two or more (b) differential adsorption of the substances on
functional groups. So, the numbering is done in the solid phase
such a way that the sum of the locants is the (c) gravitational force
lowest.
(d) capillary action
4. Which of the following potential energy (PE) Exp. (b)
diagrams represents the SN 1 reaction? In column chromatography, separation of
mixture of compounds (adsorbate) takes place
[JEE Main 2019, 9 April Shift-II] over a column of solid adsorbent (silica gel and
Al 2O 3 ) packed in a glass tube.
When an appropriate eluant (liquid) is allowed to
(a) PE (b) PE
flow down the column, the compounds present
in the mixture get adsorbed to different extent on
the adsorbent column and thus complete
Progress of reaction Progress of reaction
separation takes place.
Thus, column chromatography is based on the
differential adsorption of the substance on the
(c) PE (d) PE
solid phase.
6. In chromatography, which of the following

Progress of reaction Progress of reaction
statements is incorrect for R f ?
Exp. (b) [JEE Main 2019, 10 April Shift-II]
The potential energy (PE) diagram for SN1 (a) R f value depends on the type of
reaction is
chromatography
(b) Higher R f value means higher adsorption

General Organic Chemistry 201
(c) R f value is dependent on the mobile phase

8. An organic compound A is oxidised with
(d) The value of R f can not be more than one
Na 2O2 followed by boiling with HNO3. The
Exp. (b) resultant solution is then treated with
In chromatography, the expression of retention ammonium molybdate to yield a yellow
factor (R f ) is precipitate.
Distance travelled by the
Based on above observation, the element
compound from origin
Rf = <1 present in the given compound is
Distance travelled by the
solvent from origin [JEE Main 2019, 12 April Shift-I]
The value of R f signifies the relative ratio of (a) nitrogen

migration of each component of the mixture with (b) phosphorus
respect to the developing solvent used. R f value (c) fluorine
depends on the type of adsorption (d) sulphur
chromatography like TLC (Thin-Layer
Chromatography), paper chromatography etc. Exp. (b)
The R f value is also the characteristic of a
compound (sample) for a given developing Organic compound ‘A’ contain phosphorus as it
solvent at a given temperature. gives positive test with ammonium molybdate.
Phosphorus present in organic compound ‘A’
When the compound in the sample (usually less get oxidised with Na 2O 2 and form Na 3PO 4 .
polar) is weakly adsorbed the spot will travel a
shorter distance from the origin and hence the R f 2P + 5Na 2O 2 → 2Na 3PO 4 + 2Na 2O
Compound Sodium phosphate
value will be decreased.
Na 3PO 4 in presence of HNO 3 form H3PO 4 and
7. The increasing order of nucleophilicity of NaNO 3 .
the following nucleophiles is Na 3PO 4 + 3HNO 3 → H3PO 4 + 3NaNO 3
(1) CH3 CO2È (2) H2O Upon cooling, a few drops of ammonium
È molybdate solution are added. A yellow ppt.
(3) CH3 SO3È (4) O H confirms the presence of phosphorus in the
[JEE Main 2019, 10 April Shift-II] organic compound.
(a) (1) < (4) < (3) < (2) (b) (2) < (3) < (1) < (4) H3PO 4 +12 (NH4 )2 MoO 4 + 21HNO 3 →
(c) (4) < (1) < (3) < (2) (d) (2) < (3) < (4) < (1) (NH4 )3 PO 4 .12MoO 3 ↓ +21NH4NO 3 +12H2O
Yellow ppt
Exp. (b) 9. The IUPAC name for the following
Higher the basicity of a base, stronger will be its compound is [JEE Main 2019, 12 April Shift-II]
nucleophilic power. CH3
Again we know, a weaker acid produces a H3 C CH
stronger base (conjugate), i.e. a stronger
nucleophile.
− H⊕
CH3
Acid → Conjugate base
CH2
H3O+ H2O
CH3SO 3H CH3SO 3È (a) 3-methyl-4-(3-methylprop-1-enyl)-1-heptyne
CH3CO 2H CH3CO È2 (b) 3, 5-dimethyl-4-propylhept-6-en-1-yne
H2O È
OH (c) 3-methyl-4-(1-methylprop-2-ynyl)-1-heptene
Acid Base strength (d) 3, 5-dimethyl-4-propylhept-1-en-6-yne
strength ≡ Nucleophilicity
Thus, the correct order of nucleophilicity of given Exp. (d)
nucleophiles are as follows : The IUPAC name for the given compound is 3,
−
H2O(2) < CH3SO −3 (3) < CH3CO −2 (1) <OH(4) 5-dimethyl-4-propylhept-1-en-6-yne.

CH3 (c) DCM and H2O will be miscible clearly

H 3C 7 CH (d) DCM and H2O will make turbid/colloidal
5
Longest possible
4 6 chain containing mixture [JEE Main 2019, 10 Jan Shift-I]
2 3
double and
CH3 triple bond Exp. (a)
1
CH2 Dichloromethane, DCM (CH2Cl 2 ) is heavier
(density = 1.3266 g cm−3 ) than water
If both double and triple bonds are present in the (density = 1g cm−3 ). So, DCM and H2O will stay as
compound, the endings like-en-yne, a (numeral) lower and upper layer respectively in the
dien-(numeral)-yne etc., are used. Numbers as separating funnel (SF).
low as possible are given to double and triple
bonds as a set.
12. Which hydrogen in compound ( E ) is easily
10. Which amongst the following is the replaceable during bromination reaction in
strongest acid? presence of light?
(a) CHBr3 (b) CHI3 CH3  CH2  CH == CH2
(c) CHCl 3 (d) CH(CN)3 δ γ β α
(E)
(a) β-hydrogen (b) δ-hydrogen
Exp. (d) (c) γ-hydrogen (d) α-hydrogen
We know, a stronger acid produces its stable or [JEE Main 2019, 10 Jan Shift-I]
weaker conjugate base. Here, CH(CN)3 produces
the most stable conjugate base (NC)3 C − . Exp. (c)
Stronger −R and −I effects of the CN − group, The compound (E ) has two allyl-hydrogen atoms
make the carbanion (conjugate base) very (γ ). When E reacts with Br2 / hν, it readily undergoes
stable. The resonance hybrid structure of allylic free radical substitution and forms 3,
[(NC)3 C]− is as follows: 3-dibromobut-1-ene
δ γ β α Br /
CN 2 hν
CH3 CH2 CH == CH2   →
δ– δ+ –HBr
But -1-ene
(NC)3C H NC C y
+H ⊕
(–I) Br
C N (–R) |
CH3  CH CH == CH2
δ γ β α
– 3-bromo-but -1-ene
(NC)2C C N
Br
Br 2 / hν
|
 → CH3  C γ CH == CH2
–HBr δ | β α
y Br
N
3,3- dibromobut-1-ene
C
N C C
13. What is the IUPAC name of the following
C
N compound ?
CH3 CH3
Resonance hybrid structure of [NC)3 C]–
H
H
11. If dichloromethane (DCM) and water (H2O) Br
CH3
are used for differential extraction, which [JEE Main 2019, 10 Jan Shift-II]
one of the following statements is correct?
(a) 3-bromo-3-methyl-1,2-dimethylprop-1-ene
(a) DCM and H2O would stay as lower and upper
(b) 3-bromo-1,2-dimethylbut-1-ene
layer respectively in the S.F.
(c) 2-bromo-3-methylpent-3-ene
(b) DCM and H2O would stay as upper and lower
(d) 4-bromo-3-methylpent-2-ene
layer respectively in the separating funnel (SF)

Exp. (d) Exp. (a)

While naming the compound, alkene gets priority The correct option is :
over functional group ( Br) and numbering (A) → (Q); (B) → (R); (C) → (S)
starts from alkene side. Hence, IUPAC name: (A) H2 O and sugar mixture They do not react
4-bromo-3-methylpent-2-ene chemically. On heating, solubility of sugar in
1
CH3 H 2 O increases and on rapid cooling of
CH3 saturated solution, sugar recrystallises (Q).
2
3
H (B) H2 O and aniline mixture Aniline is steam
4 volatile but insoluble in H2O. So, steam
H distillation (R) is employed for their separation.
CH3 Br
5 (C) H2 O and toluene mixture Toluene is steam
non-volatile and also insoluble in H2O. So,
14. An organic compound is estimated through differential extraction method (S) can be used
Dumas method and was found to evolved to separate them.
6 moles of CO2, 4 moles of H 2O and 1 mole of
nitrogen gas. The formula of the compound is 16. The correct order for acid strength of
(a) C6 H8 N (b) C12H8 N compounds
(c) C12H8 N2 (d) C6 H8 N2 CH ≡≡ CH,CH3 –– C ≡≡ CH and CH 2 == CH 2
[JEE Main 2019, 11 Jan Shift-I] is as follows :
Exp. (d) (a) CH3  C≡≡ CH > CH2 == CH2 > HC≡≡ CH
(b) CH3 −− C ≡≡ CH > CH ≡≡ CH > CH2 == CH2
In Dumas method, organic compound is heated
(c) HC ≡≡ CH > CH3 −− C ≡≡ CH > CH2 == CH2
with dry cupric oxide in a combustion tube in the
(d) CH≡≡ C H > CH2 == CH2 > CH3 −− C≡≡ CH
atmosphere of CO 2 . Upon heating, C and H
present are oxidised to CO 2 and water vapours [ JEE Main 2019, 12 Jan Shift-I]
while N2 is set free. Let, the molecular formula of
the organic compound (1 mol) be C xHy Nz . In
Exp. (c)
Dumas method, Ethene (H2C == CH2 ) is sp 2 -hybridised and ethyne
(HC ≡≡ CH) is sp-hybridised. In ethyne, the
C xHy Nz +  2 x +  CuO → xCO 2 + H2O + N2
y y z
1 mol
 2 2 2 sp-hybridised carbon atom possesses maximum
y z s-character and hence, maximum
x mol mol mol
2 2 electronegativity. Due to which, it attracts the
+  2 x +  Cu
y shared electron pair of CH bond to a greater
 2 extent and makes the removal of proton easier.
y z Hence, alkyne is much more acidic than alkene.
Now, x = 6, = 4 ⇒ y = 8 and = 1 ⇒ z = 2
2 2 Presence of electron donating group in alkyne
(H3C C ≡≡ CH) decreases the acidic strength of
∴ Molecular formula of the compound is C 6H8N2 .
compound. Hence, the correct order of acidic
15. The correct match between items I and II is strength is:
HC ≡≡ CH > H3C  C ≡≡CH > CH2 == CH2
Item I Item II
(Mixture) (Separation method) 17. Which of the following compounds will be
A. H 2O : Sugar P. Sublimation suitable for Kjeldahl’s method for nitrogen
B. H 2O : Aniline Q. Recrystallisation estimation? [JEE Main 2018]
C. H 2O : Toluene R. Steam distillation NH2
S. Differential extraction (a) (b)
(a) (A) → (Q); (B) → (R); (C) → (S) N

(b) (A) → (Q); (B) → (R); (C) → (P) NO2 N+2Cl–
(c) (A) → (S); (B) → (R); (C) → (P) (c) (d)
(d) (A) → (R); (B) → (P); (C) → (S)

Exp. (b) liquids having very high boiling points. By this

process, liquid is made to boil at lower
Estimation of nitrogen through Kjeldahl’s method
temperature than its boiling point by lowering the
is not suitable for organic compounds containing
pressure on its surface.
nitrogen in ring or nitrogen in nitro or azo groups. It
is because of the fact that nitrogen of these CO2H
compounds does not show conversion to H OH

Ammonium sulphate ((NH4 )2 SO 4 ) during the
20. The absolute configuration of H Cl is
process. Hence, among the given compounds CH3
only aniline can be used suitably for estimation of
nitrogen by Kjeldahl’s method. [JEE Main 2016 (Offline)]
(a) (2S, 3R) (b) (2S, 3S)
18. Which of the following molecules is least (c) (2R, 3R) (d) (2R, 3S)
resonance stabilised? [JEE Main 2017 (Offline)]
Exp. (a)
(a) (b) 1
O COOH
2
H OH
3
(c) (d) H Cl
N 4
CH3
O
For C-2, order of priority of substituents is
Exp. (d) OH > CH(Cl)(CH3 ) > COOH
Aromatic compounds are stable due to resonance For C-3, order of priority of substituents is
while non-aromatics are not. According to Cl > CH(OH)COOH > CH3
Huckel’s rule (or 4n + 2 rule), “For a planar, cyclic
compound to be aromatic, its π cloud must Hence, according to CIP rules,
contain (4n + 2 )π electrons, where, n is any whole 3
COOH
number.” Thus, 1
H OH 2S
2 1
and H Cl 3R
,
O 3 CH
N 3
(6πe– system) (4πe– + 2e– system) (6πe– system)
are aromatic and stabilised by resonance. 21. In Carius method of estimation of halogens,
They follow Huckel’s rule. 250 mg of an organic compound gave 141 mg
of AgBr. The percentage of bromine in the
is non-aromatic, hence, compound is(at. mass Ag= 108, Br = 80)
least stabilised by resonance. [JEE Main 2015]
(a) 24 (b) 36 (c) 48 (d) 60
O
Exp. (a)
19. The distillation technique most suited for Given, Weight of organic compound = 250 mg
separating glycerol from spent lye in the
Weight of AgBr = 141 mg
soap industry is [JEE Main 2016 (Offline)]
∴ According to formula of % of bromine by
(a) fractional distillation
Carius method
(b) steam distillation
Atomic weight of Br
(c) distillation under reduced pressure % of Br =
(d) simple distillation Molecular weight of Ag Br
Weight of AgBr
× × 100
Exp. (c) Weight of organic bromide
Glycerol with high boiling point (290°C) can be 80 141 1128000
∴ % of Br = × × 100 = = 24 %
separated from spent lye by distillation under 188 250 47000
reduced pressure. This process is used to purify

22. The order of stability of the following 24. Consider thiol anion (R Ss ) and alkoxy anion
carbocations (R Os ) . Which of the following statements is
+ + correct? [AIEEE 2011]
CH2 CH  CH2 ; CH3—CH2 CH2; (a) R S s is less basic and less nucleophilic than
(I) RO s
(II)
+ (b) R S s is less basic but more nucleophilic than
CH2 RO s
(c) R S s is more basic and more nucleophilic than
is RO s
(d) R S s is more basic but less nucleophilic than
(III) RO s
[JEE Main 2013] Exp. (b)
(a) III > II > I (b) II > III > I
Nucleophilic strength depends on the
(c) I > II > III (d) III > I > II electronegativity of the atom. Lower the
electronegativity of an atom, larger the
Exp. (d) nucleophilic strength of an atom and more readily
The order of stability of carbocation will be it will donate electrons to the electrophilic (e −
CH2 deficient) species.
Since, electronegativity decreases down the
group, thus nucleophilic strength increases down
> CH2 CH CH3 > CH3 CH2 CH2
the group. Hence, RS− is more nucleophilic than
Benzyl carbocation Allylcarbocation Propylcarbocation RO − due to less electronegativity of S than O.
(more resonance (resonance (stabilised by On the other hand, basic strength of an atom
stabilised) stabilised) +I effect) depends upon the tendency to accept a proton
more readily. Since, O H bond is longer than
23. Identify the compound that exhibits S H bond, thus RO − has a greater tendency to
tautomerism [AIEEE 2011] accept a proton than RS − . Hence, RO − is a
stronger base than RS − .
(a) 2-butene
Thus, basic strength of the central atom
(b) lactic acid
decreases down the group.
(c) 2-pentanone
Hence, RS − is more nucleophilic but less basic
(d) phenol
than RO − .
Exp. (c), (d)
25. The correct order of increasing basicity of
Tautomerism is due to spontaneous the given conjugate bases (R = CH 3 ) is
interconversion of two isomeric forms with – – – –
different functional groups into one another. The (a) RCOO < HC == C < R < N H2 [AIEEE 2010]
– – – –
term tautomer means constitutional isomers that (b) R < HC ≡≡ C < RCOO < N H2
undergo such rapid interconversion that can’t be – – – –
(c) RCOO < N H2 < HC ≡≡ C < R
independently isolated. – – – –
O H OH (d) RCOO < HC ≡≡ C < N H2 < R
C C C CH Exp. (d)
O−
Keto H Enol  
R— ←→ R — C == O
O O In carboxylate ion, the negative charge is present
on oxygen, a most electronegative element here,
Keto Enol in phenol thus it is resonance stabilised.
HC ≡≡ C − : Carbon is sp hybridised so its
Thus, (c) 2-pentanone and (d) phenol exhibit electronegativity is increased higher relative to
tautomerism. nitrogen.

– Cl
NH2 : Nitrogen is more electronegative than sp3 s
s
hybridised C-atom. From the above discussion, it Cl C > —–CH2
is clear that the order of the stability of conjugated
bases is as Cl
– (–I effect of phenyl group as well as
RCOO − > HC ≡≡ C − > NH2 > R − (3-I effect exerting
group of Cl) delocalisation of electrons)

and higher is the stability of conjugated bases,
lower will be basic character. Hence, the order of
CH3
CH3
basic character is as > s
– > s CH3 C
RCOO − < HC ≡≡ C − < NH2 < R − CH3 CH
CH3
26. Out of the following, the alkene that exhibits (+ I effect of (+ I effect of
2-CH3 group) 3 - CH3 groups)
optical isomerism is [AIEEE 2010]
(a) 3-methyl-2-pentene
(b) 4-methyl-1-pentene 28. The alkene that exhibits geometrical
isomerism is [AIEEE 2009]
(c) 3-methyl-1-pentene (d) 2-methyl-2-pentene
(a) propene (b) 2-methyl propene
Exp. (c) (c) 2-butene (d) 2-methyl-2-butene
Optical isomerism is shown by the carbon Exp. (c)
compounds which possess atleast one chiral
carbon. Geometrical isomerism is shown by those alkenes
Thus, 3 −methyl−1 −pentane possess a chiral only in which atoms or groups attached to each
carbon, hence it shows optical isomerism. carbon atom are different. Thus,
H CH3 H CH3 H
 C C C C
CH3 — CH2 —C* —CH == CH2
 H H H C H
3
CH3 Propene
3-methyl-1-pentene [three atoms (H) linked
to doubly bonded 2-methyl propene
(It has one chiral centre) (no geometrical isomerism)
C-atoms are same, thus
– – no geometrical isomerism]
27. Arrange the carbanions, (CH 3 )3 C , C Cl 3 ,
– – H3C CH3 H3 C
(CH 3 )2 C H, C 6H 5 C H 2 , in order of their H
decreasing stability [AIEEE 2009] C C C C
– – – – H H H
(a) C6 H5 C H2 >CCl 3 > (CH3 )2 C > (CH3 )2 C H CH3
– – – – cis 2-butene
(b) (CH3 )2 C H > CCl 3 > C6 H5 C H2 > (CH3 )3 C trans-2-butene
(methyl group and H-atom (methyl groups and
– – – – linked to doubly bonded
(c) CCl 3 > C6 H5 C H2 > (CH3 )2 C H > (CH3 )3 C H-atom lie on opposite
C-atom lie on same side, side to one another,
– – – – hence cis isomer)
(d) (CH3 )3 C > (CH3 )2 C H > C H2 > CCl 3 hence trans isomer)
H 3C CH3
Exp. (c)
C C
− I effect [e − withdrawing] exerting groups
H 3C H
stablises carbanion by the dispersal of their −ve
charge while + I effect exerting [e − releasing] 2-methyl-2-butene
(no geometrical isomerism)
groups destablises the carbanion by increasing
electron density on them.
On the other hand, resonance stablised
29. The number of stereoisomers possible for a
carbanion are stable due to the involvement of
compound of the molecular formula
their lone pair of electron with the delocalisation of CH 3 — CH == CH — CH(OH) — Me is
π −electrons of attached phenyl group. Thus, (a) 3 (b) 2 [AIEEE 2009]
(c) 4 (d) 6

Exp. (c)
33. The IUPAC name of is
There are four stereoisomers.
cis —R, cis—S
trans—R trans—S [AIEEE 2007]
(a) 1, 1-diethyl-2, 2-dimethylpentane

30. The IUPAC name of neopentane is (b) 4, 4-dimethyl-5, 5-diethylpentane
(a) 2-methylbutane [AIEEE 2009] (c) 5, 5-diethyl-4, 4-dimethylpentane
(b) 2,2-dimethylpropane (d) 3-ethyl-4, 4-dimethylheptane
(c) 2-methylpropane
(d) 2,2-dimethylbutane Exp. (d)
6 2
Exp. (b) 4
7 3 1
The neopentane 5
CH3

3 2 1
CH3 —C —CH3 3-ethyl-4, 4-dimethylheptane

CH3
34. Which one of the following conformations
IUPAC name : 2,2 -dimethyl propane
of cyclohexane is chiral ? [AIEEE 2007]
(a) Twist boat
31. The correct decreasing order of priority for
the functional groups of organic (b) Rigid
compounds in the IUPAC system of (c) Chair
nomenclature is [AIEEE 2008] (d) Boat
(a)  COOH,  SO 3 H, CONH2 ,  CHO
Exp. (c)
(b)  SO3 H, COOH, CONH2 ,  CHO
(c)  CHO,  COOH,  SO 3 H,  CONH2
(d)  CONH2 ,  CHO,  SO 3 H,  COOH
Chair form is unsymmetrical and has absence of
Exp. (a)
any element of symmetry.
The correct decreasing order of priority for the
functional groups of organic compounds in the 35. Which of the following molecules is
IUPAC system is expected to rotate the plane of polarised
 COOH > SO 3H >  COOR > COCl light ? [AIEEE 2007]
> CONH2 > CN > CH == O CHO
32. The absolute configuration of
HO2C CO2H (a) HO H (b)
SH
CH2OH
HO H H OH [AIEEE 2008]
COOH
(a) S, S (b) R , R H2N NH2
(c) R , S (d) S , R (c) H H (d) H2N H
Ph Ph
Exp. (b) H
2 2
COOH COOH Exp. (a)
HOOC
3 3
H OH or H OH R The molecule, which is optically active, has chiral
HOR H1 HO H R centre, is expected to rotate the plane of polarised
1
COOH light.

CHO
38. The increasing order of stability of the
HO * H following free radicals is [AIEEE 2006]
• • •
(a) (CH3 )2 CH < (CH3 )3 C < (C 6 H5 )2 CH
CH2OH •
< (C 6 H5 )3 C
One chiral centre ⇒ optically active • • • •

(b) (C 6 H5 )3 C < (C 6 H5 )2 CH < (CH3 )3C < (CH3 )2 CH
H2N NH2 • • •
H H (c) (C 6 H5 )2 C H < (C 6 H5 )3 C < (CH3 )3 C
•
Ph Ph < (CH3 )2 CH
• • •
Two chiral centres, but plane of symmetry within (d) (CH3 )2 C H < (CH3 )3 C < (C 6 H5 )3 C
molecule ⇒ optically inactive. •
< (C 6 H5 )2 C H
36. Which of the following is the correct order of
decreasing S N 2 reactivity? (X = a halogen) Exp. (a)
(a) R CH2 X > R3C X > R2CH X [AIEEE 2007] Free radicals stability
• •
(b) R CH2 X > R2CHX > R3 CX C 6H5 C C 6H5 > C 6H5  CH
(c) R3CX > R2CHX > R CH2 X  
C 6H5 C 6H5
(d) R2CH2 X > R3C X > R CH2 X
(highly stable by delocalisation
Exp. (b) of 3 phenyl groups)
• •
SN2 reactions are greatly controlled by steric > CH3 C  CH3 > H3C  C  H
factor.  
CH3 CH3
R CH2  X, R 2 CH  X, R 3 C  X (9-hyperconjugative
1° 2° 3°
hydrogens and + I effect
SN2 reactivity decreases as bulkyness of alkyl
of 3 alkyl group)
group increases.
37. The IUPAC name of the compound shown 39. Increasing order of stability among the three
main conformations (i.e., Eclipse, Anti,
below is [AIEEE 2006]
Gauche) of 2-fluoroethanol is [AIEEE 2006]
Cl
(a) Eclipse, Gauche, Anti
(b) Gauche, Eclipse, Anti
(c) Eclipse, Anti, Gauche
(d) Anti, Gauche, Eclipse
Br
(a) 2-bromo-6-chlorocyclohex-1-ene Exp. (b)
(b) 6-bromo-2-chlorocyclohexene HO CH2 CH2 F
(c) 3-bromo-1-chlorocyclohexene
H
(d) 1-bromo-3-chlorocyclohexene
H H
Exp. (c)
Unsaturation (double bond) is given priority over
halogen. So, the correct IUPAC name is
3-bromo-1-chlorocyclohexene. H Fδ–
O Hδ+
Gauche conformation is comparatively more
stable due to hydrogen linkage in between F and
H (at O-atom), hence order is eclipse, anti
(staggered), gauche.

40. The correct order of increasing acid strength 42. Due to the presence of an unpaired electron,
of the compounds is [AIEEE 2006] free radicals are [AIEEE 2005]
(A) CH3CO 2 H (B) MeOCH2CO 2 H (a) cations (b) anions
Me (c) chemically inactive (d) chemically reactive
(C) CF3CO 2 H (D)  CO 2 H Exp. (d)

Me Free radicals have unpaired electrons, so are
(a) B< D< A< C neutral and reactive.
• •
(b) D< A< C< B
CH3 +CH3 → CH3 CH3
(c) D< A< B< C
(d) A< D< C< B 43. Tertiary alkyl halides are practically inert to
Exp. (c) substitution by SN 2 mechanism because of
(a) steric hindrance (b) inductive effect
Acidic strength of the compound depends on the
(c) instability (d) insolubility
ease of release of proton. I effect exerting groups
[e − withdrawing] increases the acidic strength [AIEEE 2005]
while + I effect exerting group decreases the Exp. (a)
strength of an acid.
In SN2 reaction, attack of nucleophile and breaking
Thus,
O O of C Br bond takes place in one step.
Me R R R
CH C OH < CH3 C OH < 
R C Br + Nu− → Nu.. .....C..... .Br
Me  
[+I effect group of R R
[ 2+I effect exerting
groups, increases e– density  CH3 group] Since, tertiary carbon is sterically hindered, thus
on O-atom, thus the release the attack of nucleophile becomes difficult.
of ease of proton becomes Hence, tertiary alkyl halides undergo SN2 reaction
difficult (least acidic)] very rarely.
O O 44. Among the following acids which has the

F lowest pK a value? [AIEEE 2005]
MeO CH2 C OH < F C C OH (a) CH3CH2COOH (b) (CH3 )2 CH COOH
F (c) HCOOH (d) CH3COOH
[CF3 exerts more
–I effect than Meo Exp. (c)
(most acidic)] Stronger the acid, lower is their pK a value.
Thus, out of the given acids, strongest acid is
41. The number and type of bonds between two HCOOH.
carbon atoms in calcium carbide are
Hence, HCOOH possess lowest pK a value.
[AIEEE 2005]
(a) two sigma, two pi 45. The decreasing order of nucleophilicity
(b) two sigma, one pi among the nucleophiles [AIEEE 2005]
(c) one sigma, two pi (A) CH3 C  O − (B) CH3O − (C) CN −
(d) one sigma, one pi  O
O
Exp. (c) (D) H3C S O
–
CaC 2 (calcium carbide) is ionic.
CaC 2 → Ca 2+ + C 22 − O
−
C ≡≡ C − (a) (C), (B), (A), (D) (b) (B), (C), (A), (D)
C 2−
2 has one σ and two π-bonds. (c) (D), (C), (B), (A) (d) (A), (B), (C), (D)

Exp. (b) O O
 
Weaker the acid, more stable is their conjugate R C  Cl + Nu− → R C  Nu + Cl −
base and greater is their nucleophilicity. Thus, (X ) (X − )
nucleophilicity order of the conjugate bases is
opposite to their acidic strength. 47. Which type of isomerism is shown by
2, 3-dichlorobutane? [AIEEE 2005]

Conjugate bases Acids (a) Structural (b) Geometric
CH 3 C  O − CH 3 C  OH (c) Optical (d) Diastereo
 
O O Exp. (c)
CH 3O − CH 3OH * *
CH3  CH CH CH3
−
CN HCN  
O O Cl Cl
− There are two chiral C-atoms (*).
CH3— —S—O CH3— —S—OH Thus, it shows optical isomerism.
O O 48. The IUPAC name of the compound is
Since, alcohols and cyanides are weaker acid

than sulphonic and carboxylic acids. Thus, the
HO [AIEEE 2004]
order of acidic strength of the given species are
O (a) 3, 3-dimethyl-1-hydroxy cyclohexane
(b) 1, 1-dimethyl-3-hydroxy cyclohexane
H3C— —S—OH >CH3 C OH (c) 3, 3-dimethyl-1-cyclohexanol
(d) 1, 1-dimethyl-3-cyclohexanol
O O
>CH3 OH> HCN Exp. (c)
5
Hence, the decreasing order of nucleophicity of 6 4
the given nucleophiles is as follows 1 3
O HO
2
H3C— —S—O – <CH3 C O–
Carbon with —OH group is given C1, thus it is
3, 3-dimethyl-1-cyclohexanol.
O O
<CN – < CH3O
49. Which one of the following does not have
sp 2 hybridised carbon? [AIEEE 2004]
46. The reaction
O O (a) Acetone (b) Acetic acid
  (c) Acetonitrile (d) Acetamide
R C  X + Nu s → R C  Nu + X s
Exp. (c)
is fastest when X is [AIEEE 2005, 2004] O O
 
(a) OCOR (b) OC2 H5 (a) CH3  C CH3 (b) CH3  C OH
(c) NH2 (d) Cl sp 3 sp 2 sp 3 sp 2
sp 3
O
Exp. (d) 
Poor the nucleophile, better is the leaving group (c)CH3  C ≡≡ N (d) CH3  C NH2
ability. Among the given species, Cl − is a poor sp3 sp sp3 sp2
nucleophile, thus it will act as a better leaving Acetonitrile does not contain sp 2
hybridised
group. Thus, X will be Cl and hence, the given
carbon.
reaction will be fast in the presence of Cl.

50. For which of the following parameters, the 52. Amongst the following compounds, the
structural isomers C 2H 5OH and CH 3OCH 3 optically active alkane having lowest
would be expected to have the same values? molecular mass is [AIEEE 2004]
(Assume ideal behaviour) [AIEEE 2004] (a) CH3 CH2 CH2 CH3
(a) Heat of vaporisation CH3

(b) Vapour pressure at the same temperature 
(b) CH3 CH2 CH  CH3
(c) Boiling points H
(d) Gaseous densities at the same temperature |
and pressure (c) CH3 C 
|
Exp. (d) C2 H5
In CH3CH2OH, there is intermolecular H-bonding (d) CH3 CH2 C ≡≡ CH
while it is absent in isomeric ether CH3OCH3 .
Exp. (c)
Larger heat is required to vaporise CH3CH2OH, as
*
compared to CH3OCH3 thus (a) is incorrect. CH3—CH—
|
CH3CH2OH, is less volatile than CH3OCH3 , thus CH2CH3
vapour pressures are different, thus (b) is
incorrect. contains asymmetric carbon atom, thus optically
Bp of CH3CH2OH > CH3OCH3 , thus (c) is active.
incorrect.
53. Which of the following will have a
mass
Density = , due to ideal behaviour at a meso-isomer also? [AIEEE 2004]
volume (a) 2-chlorobutane
given temperature and pressure, volume and
(b) 2, 3-dichlorobutane
molar mass are same. Hence, they have same
vapour density. (c) 2, 3-dichloropentane
(d) 2-hydroxypropanoic acid
51. Which of the following compounds is not Exp. (b)
chiral ? [AIEEE 2004]
*
(a) 1-chloropentane (a) CH3 C H CH2CH3
(b) 2-chloropentane 
Cl
(c) 1-chloro-2-methyl pentane
One asymmetric carbon atom, forms d-and
(d) 3-chloro-2-methyl pentane l-optical isomers.
Exp. (a) CH3
|
Chiral carbon has all the four different groups *
H—C—Cl
(b) Plane of
attached to it. symmetry |
*
H—C—Cl
(a) CH3CH2CH2CH2CH2Cl (no chiral carbon atom)
|
(b) CH3 CHCH2CH2CH3 (one chiral carbon atom) CH3
 *
meso due to
Cl 2CH2 CHC
(c) CH3CH H2Cl (one chiral carbon atom) internal compensation
 Two asymmetric carbon atoms, forms d-, l-
CH3
and meso forms.
* * * *
(d) CH3  CH CHC  H2CH3 (c) CH3 C H C H CH2CH3
   
CH3 Cl Cl Cl
(two chiral carbon atoms)
Two asymmetric carbon atoms but does not
have symmetry. Hence, meso form is not
formed.

*
(d) CH3 C H COOH 56. In the anion,HCOO− the two carbon-oxygen
 bonds are found to be of equal length. What
OH
One asymmetric carbon atom, meso form is
is the reason for it ? [AIEEE 2003]
not formed. (a) Electronic orbits of carbon atom are
hybridised
54. The IUPAC name of CH 3COCH(CH 3 )2 is (b) The C = O bond is weaker than the C—O bond
(a) isopropylmethyl ketone [AIEEE 2003] (c) The anion, HCOO − has two resonating
(b) 2-methyl-3-butanone structures
(c) 4-methylisopropyl ketone (d) The anion is obtained by removal of a proton
(d) 3-methyl-2-butanone from the acid molecule
Exp. (d) Exp. (c)

O
 O O–
CH3 C CH  C H3

H—C H—C
1 2
 3 4 O–

O
CH3
3 -methyl butan-2 -one O–

or 3 -methyl-2 -butanone HC
O

O
 Resonating (canonical)
keto ( C  ) functional group is given priority. structures of formate ion
Due to resonance, C O bonds are found to be of
55. Among the following four structures I to IV equal length.
CH 3 O CH 3
   57. Which of the following compounds has
C 2H 5 CH  C 3H 7 CH 3 C CH  C 2H 5 incorrect IUPAC nomenclature? [AIEEE 2002]
(I) (II)
O
H CH 3 
(a) CH3CH2CH2 C OC2 H5
  ethyl butanoate
H C ⊕ C 2H 5 CH  C 2H 5
 (b) CH3 CHCH2CHO
H 
(IV) CH3
(III)
3-methyl butanal
It is true that [AIEEE 2003] O

(a) all four are chiral compounds (c) CH3 CHC CH2CH3
(b) only I and II are chiral compounds 
CH3
(c) only III is a chiral compound
(d) only II and IV are chiral compounds 2-methyl-3-pentanone
(d) CH3C H CH CH3
Exp. (b)  
HC OH
Chiral compounds are those which have one 3
chiral centre i.e., all four atoms or groups attached 2-methyl-3-butanol
to same carbon are different. Here, I and II are
chiral but III and IV are achiral compounds.

Exp. (d) 60. SN 1 reaction is feasible in [AIEEE 2002]

4 3 2 1
incorrect
CH3CHCHCH3 (a) Cl + KOH
numbering 1 2 3 4
| | Correct numbering
CH3 OH functional group Cl
Correct name 3-methyl butan-2-ol should be given (b) + KOH

priority
or 3-methyl-2-butanol
58. Underlined carbon is sp 3 hybridised in (c) Cl + KOH

(a) CH3 C H == CH2 [AIEEE 2002]
(b) CH3 C H2 NH2
(d) CH2CH2Cl + KOH
(c) CH3 C ONH2
(d) CH3CH2 C N
Exp. (a)
Exp. (b)
SN1 (unimolecular nucleophilic substitution)
H reaction is favoured with stability of carbocation.
|
(a) CH3— C == CH2 (b) CH3— C —NH2 (a) r 3° carbocation
| sp2 | sp3
H H
(b) 1° carbocation
O r

(c) CH3— C — NH2 (d) CH3— CH2 — C N (c) r 1° carbocation
sp2 sp
r
59. In the following benzyl/allyl system (d) CH2 CH2
unstable
R CH == CH 2 or R
1° carbocation
(due to the presence of − I
(R is alkyl group)
effect exerting phenyl group)
decreasing order of inductive effect is
[AIEEE 2002]
(a) (CH3 )3 C  > (CH3 )2 CH  > CH3CH2  61. Following reaction,
(b) CH3CH2  > (CH3 )2 CH  > (CH3 )3 C  (CH 3 )3CBr + H 2O → (CH 3 )3COH + HBr is
(c) (CH3 )2 CH  > CH3CH2  > (CH3 )3 C  an example of [AIEEE 2002]
(a) elimination reaction
(d) (CH3 )2 C  > CH3CH2  > (CH3 )3 CH 
(b) free radical substitution
Exp. (a) (c) nucleophilic substitution
(d) electrophilic substitution
Both where R is attached to vinylic (≈ arylic)
system, positive inductive effect occurs in the Exp. (c)
following order
(CH3 )3 C Br + H2O → (CH3 )3 C OH + HBr
O − > COO − > (CH3 )3 C  >
Here, Br is substituted by  OH− (nucleophile)
(CH3 )2 CH  > CH3CH2  > CH3 
→ SN 1 reaction (unimolecular substitution
reaction)

62. Following types of compounds (as I, II) 63. Racemic mixture is formed by mixing two
(a) isomeric compounds [AIEEE 2002]
(I) CH 3CH == CHCH 3 (II) CH 3  CH OH
(b) chiral compounds

CH 2CH 3 (c) meso compounds
(d) enantiomers with chiral carbon

are studied in terms of isomerism in
[AIEEE 2002] Exp. (d)
(a) chain isomerism (b) position isomerism Racemic mixture is an equimolar mixture of
(c) conformers (d) stereoisomerism enantiomers.
Exp. (d) 64. Geometrical isomerism is not shown by
H3 C CH3 H 3C H (a) 1, 1-dichloro-1-pentene [AIEEE 2002]
C C and C C (b) 1, 2-dichloro-1-pentene
H H H CH3 (c) 1, 3-dichloro-2-pentene
(cis) geometrical isomers (trans) (d) 1, 4-dichloro-2-pentene
(cis-trans)
H H Exp. (a)
CH3 C C CH3 Cl CH2CH2CH3

OH HO C==C
CH2CH3 CH3CH2 Cl H
molecule is optically active At least two groups or atoms attached to doubly
enantiomers bonded carbon atoms should be different.
Geometrical isomers and enantiomers both are
stereoisomers.

16
Hydrocarbons and Their

Halogen Derivatives
δ+ δ–
1. Which one of the following alkenes when CH3O — CH —
— CH2
H—Cl
CH3O — CH — CH3
+
treated with HCl yields majorly an (+R) –

Cl
anti Markownikov product? Fast
CH3O — CH — CH3
δ– δ+ Cl
(a) Cl CH == CH2 (b) H2 N CH == CH2 Cl — H
(c) CH3O CH == CH2 (d) F3C CH == CH2 HCl r
< CH —
F3C — — CH2 Slow F3C — CH2 — CH2
Exp. (d) (– I) – Cl
s
s
Attachment of electron donating group (+ R or + I) Cl
F3C — CH2CH2Cl
with sp2-carbon of an unsymmetrical alkene supports Slow
Markownikov’s addition rule through
electrophilic-addition-pathway. 2. The major product of the following reaction is
But, attachment of electron-withdrawing group CH3
(− R or − I) for the same will follow anti-Markownikov’s
pathway (even in absence of organic peroxide which (1) Cl2/hν
favours free radical addition) through electrophilic (2) H2O,∆
addition pathway.
The product formed by given alkenes when treated
Cl
with HCl.
+R δ+ δ–
H—Cl r — Cl– CHCl2 CO2H
Cl — CH —
— CH2 Cl — CH — CH3
Slow fast
Cl (a) (b)
Cl — CH — CH3
Similarly, Cl Cl
δ+ δ– CH2 OH CHO
·· H—Cl +
H2N — CH —
— CH2 NH2 — CH — CH3
(+R) Cl
(c) (d)
–
Cl
NH2 — CH — CH3
Fast
Cl Cl

Exp. (d) Through aromatic electrophilic substitution mechanism

CH3
(ArSE 2) when mono-alkylation (Friedel- Craft’s reaction)
is performed, we get mono-alkylated benzene. As, the
alkyl group is ring activating (towards ArSE 2 ) in nature,
again o- and p-substituted alkyl benzene will be
obtained and so on. e.g.
CH2CH3
Cl
hν/benzylic free radical C2H5Cl (1 eqv.)
substitution with Cl2
AlCl3 (anhyd.)
Cl2(1 eqv.) Cl2(2 eqv.) Cl2(excess)
—HCl
C2H5
–HCl –2HCl –3HCl
C2H5Cl (excess)
CH2Cl CHCl2 CCl3
AlCl3 (anhyd.)
Cl Cl Cl C2H5 C2H5
s s
s s –3H –3OH(aq) C2H5
–Cl OH(Cl) –2HCl 2H2O/∆
C2H5Cl
OH +
AlCl3
OH
CH2OH CH C OH
O—H C2H5
OH C2H5 C2H5
Cl Cl Cl H5
H5C2 C2H5 C2 C
(Option-c) Gem-diol 2H5Cl
–H2O
(unstable) OH + AlCl3
–H2O C O (Minor)
C2H5
CH O (Major)
Cl
Cl as COO
–
4. The increasing order of reactivity of the
(Option-d)
following compounds towards aromatic
electrophilic substitution reaction is
Cl
in basic medium
Cl OMe Me CN
H3Or
COOH
Cl A B C D
(Option-b)
− (a) A < B < C < D (b) B < C < A < D
So, considering the second reaction condition, Cl ,
H 2O, ∆ in the statement of the question, the correct (c) D < A < C < B (d) D < B < A < C
answer is option (d).
Exp. (c)
3. Polysubstitutiion is a major drawback in Aromatic electrophilic substitution reactions are fast in
those compounds in which the attacking site possess
[JEE Main 2019, 8 April Shift-II] high electron density. Electron withdrawing groups
(a) Friedel-Craft’s alkylation (EWGs) reduces the electron density in the benzene
(b) Reimer-Tiemann reaction ring due to its strong –I effect and makes further
(c) Friedel-Craft’s acylation substitution difficult. Hence, called as deactivating
groups. While electron releasing groups (ERGs)
(d) Acetylation of aniline increases the electron density in the benzene due to
resonance. Therefore, activates the benzene ring for
Exp. (a) the attack by an electrophile.
Hence, called as activating groups.

Hydrocarbons and Their Halogen Derivatives 217
In given options,
•• 6. The major product of the following reaction is
Activating groups are — CH 3 < —OCH 3 (i) DCl (1 equiv.)
•• CH3C ≡≡ CH     
→
( + I, + R ) Strong + R -effect (ii) DI
Deactivating groups are — CN > — Cl [JEE Main 2019, 9 April Shift-I]
Strong – I -effect ( − I > − R)
(a) CH3CD(Cl)CHD(I) (b) CH3CD2CH(Cl)(I)

So, the correct order is (c) CH3CD(I)CHD(Cl) (d) CH3C(I)(Cl)CHD2
CN Cl Me OCH3
Exp. (d)
The major product obtained in the given reaction is
< < <
CH 3C (I) (Cl) CHD 2.
1. DCl (1 equiv. )
D A C B CH 3C ≡≡ CH → CH 3C(I)(Cl)CHD 2
2. DI
5. The major product of the following reaction is Addition in unsymmetrical alkynes takes place
according to Markovnikov’s rule.
1. KOH (alc.) Reaction proceed as follows :
Cl
2. Free radical DCl
Cl polymerisation (1 equiv.)  DI
Cl CH 3 C ≡≡ CH → CH 3 C == CHD 
Prop -1-yne
[JEE Main 2019, 9 April Shift-I] Cl
CH3 
CH 3  C  CHD 2
(a) (b) 
n I
n Product
7. Increasing order of reactivity of the following

Cl compounds for S N1 substitution is
CH3
Cl CH2 Cl
CH3 H3C Cl
CH3
(A ) (B)
(c) (d)
n Cl Cl
n
H3CO
(C) (D)
OH (a) (A) < (B) < (D) < (C) (b) (B) < (C) < (D) < (A)
OH
(c) (B) < (A) < (D) < (C) (d) (B) < (C) < (A) < (D)
Exp. (b)
In presence of alc. KOH, the given halide undergoes
Exp. (c)
elimination reaction. Reactivity of substitution nucleophilic unimolecular
(SN 1) reaction depends on the formation of
Alc. KOH carbocation. Greater the stability of carbocation,
greater will be its ease of formation of alkyl halide and
Cl faster will be the rate of reaction. So, the correct order
Cl Cl
of (SN 1) reactivity is
The alkene produced undergoes polymerisation via
free radical mechanism. This process involve three CH2Cl CH2—Cl
steps, i.e. initiation, propagation and termination.
> > > CH3 CH2Cl
Polymerisation n Cl
OCH3
(+R)
Cl Cl
(C) (D) (A) (B)
Polymer

In compound C, the carbocation formed is stabilised I CH3

by activating group ( OCH 3 ). Compound D forms r ⇒ Highly
benzyl carbocation (C 6H 5 CH+2 ) that is stabilised by –I
s
stable
resonance. Compound A produces a primary rds
carbocation that further rearranges itself to secondary CH3O CH3O
(D)
carbocation. Additional +R effect from

p-position (DN)
Nus Rearrangement
r r Stability of intermediates will follow the order
Cl B′ > A′ > C′ > D′
1° carbocation 2° carbocation
Compound B produces primary carbocation which is
(–I) (–HPC=3) (+HPC=6)
(+HPC=3
+R=1 (
least stable among all the given options. So, the rate of SN 1 reaction with the given compounds
will be, B < A < C < D
8. Increasing rate of S N 1 reaction in the following
9. The major product of the following reaction is
compounds is [JEE Main 2019, 10 April Shift-I] CH3
I I
 CH OH
MeO CH3  C  CHCH3  3→
(A) (B)
 
H Br [JEE Main 2019, 10 April Shift-I]
I CH3 CH3
 
I (a) CH3  C == CHCH3 (b) CH3  C  CH == CH2
(C) (D) 
H
H 3C H3CO
CH3 CH3
(a) (A) < (B) < (C) < (D) (b) (B) < (A) < (C) < (D)  
(c) (A) < (B) < (D) < (C) (d) (B) < (A) < (D) < (C) (c) CH3  C  CHCH3 (d) CH3  C  CHCH3
  
Exp. (b) OCH3 H OCH3
More stable the carbocation intermediate, higher will Exp. (c)
be the rate of SN 1 reaction. In the given question, the substrate is a 2º-halide
The reaction involving carbocation intermediate (bromide) and the medium, CH 3OH (as well as a poor
formation for the given compounds are as follows: nucleophile) is protic in nature, So, the reaction will
Three positive follow mainly SN 1 pathways via the formation of a
I CH3 carbocation intermediate (I).
hyperconjugation
r
2°-benzyl carbocation Me
–I s Me Me–Br r Me
⇒ Stable r CH3OH
rds C CH r
Me rds Me –H Fast
(A )
H (2°)
+R H Br H (I) Me
(AN) CH—CH—Me
I CH3 Me
OCH3
MeO
s
MeO r ⇒ Less (Minor)
–I stable
rds
The intermediate, I can be rearranged into the more
stable form I′ (3°) by α-hydride shift.
–I effect
(B)
from m-position I ′ will give the major product.
(BN)
Me r s Me r
I α-H shift
CH3 C CHMe C—CH2—Me
r ⇒ More stable Me Me
–I
s I′ CH3OH –Hr
H
rds (3° carbocation)
H3C H 3C I Me
(C) (2° carbocation)
C—CH2Me
Additional Me
three hyperconjugation
(C′) OCH3
(Major)

Br
10. The increasing order of the reactivity of the (a) Br (b)
following compounds towards electrophilic
aromatic substitution reaction is
[JEE Main 2019, 10 April Shift-I] HO
(c) (d)
Cl CH3 COCH3
Br
Exp. (b)
The given reaction takes place as follows :
(I) (II) (III)
Cl
EtONa/∆
(a) III < I < II H
β-H for β-elimination
(b) II < I < III Saytzeff elimination –HCl
(c) III < II < I CH2
H β-H for
(d) I < III < II Hoffmann elimination
Markownikov’s
Exp. (a) centre for Brs
+
Key Idea In electrophilic aromatic substitution
3-methyl but-2-ene 3-methyl-but-1-ene
(Ar S E 2 ) reaction, the aromatic (benzene nucleus minor
major (X)
here) compound (substrate) acts as a nucleophile (Saytzeff product) (Hoffmann product)
which gets attacked by an electrophile in the rate
determining step (rds). Electrophilic addition
HBr (Markownikov’s rule)
Higher electron density on the nucleophile, i.e. Br
benzene nucleus will fasten the rate of the reaction.
Br +
Electron-donating groups (EDG) will increase electron
density in benzene nucleus by any or both of their +R/ 2-bromo-3-methyl 2-bromo-2-
+ M and hyperconjugative (HPC) effects. butane (minor) methyl butane
(major) (Y)
Now, let us consider the given substrte.
12. Which of these factors does not govern the

Cl –I-effect dominates the +R-effect
stability of a conformation in acyclic
O compounds? [JEE Main 2019, 10 April, Shift II]
(a) Electrostatic forces of interaction
(I) C—CH3 –R effect
(b) Torsional strain
(c) Angle strain
CH3 + HPC
(III) (d) Steric interactions
(II)
Exp. (c)
The four types of strains viz (a) electrostatic force of
As –R effect is more powerful than –I effect, the order attraction, (b) torsional strain, (c) angle strain, (d)
of their reactivity, towards an electrophile will be steric stain, are responsible for the stability or energy
barriers of conformers. In cyclic compounds, all types
III I II
of strains may be present.
(–R) < (–I>+R) < (+ HPC)
Compound Type of strains/forces
11. The major productY in the following reaction is a+c
Cl EtONa HBr a+ b+c

Heat
X Y
OH F a+ b+c+d

In a cyclic or open-chain compounds, angle strain (c) CHO

is absent. e.g. O3 CHO |
| + (CH2)2
Me2S
Compound Types of strains/forces CHO |
H CHO
H a
14.
The major product of the following addition

H
reaction is
H H Cl / H O
H H3 C  CH == CH2 →
2 2
CH3 a+ b [JEE Main 2019, 12 April Shift-I]

H CH3 (a) CH3  CH  CH2 (b) CH3  CH  CH2
   
H H Cl OH OH Cl
H O
OH a+ b+d O
H OH (c) H3C (d) H3C CH3
H H Exp. (b)
H The major product of the given addition reaction is
H3C  CH  CH2 . In this reaction,
13. The major product(s) obtained in the following  
reaction is/are [JEE Main 2019, 12 April, (Shift I)] OH Cl
H 2O is used as a solvent and the major product of the
(i) KOtBu reaction will be a vicinal halohydrin. A halohydrin is an
(ii) O3/Me2S organic molecule that contains both OH group and a
halogen. In a vicinal halohydrin, the OH and halogen
Br are bonded to adjacent carbons.
CHO and OHC  CHO H 3C  CH == CH 2 →
2 2Cl /H O
H 3C  CH  CH 2 +
(a) OHC  
(b) OHC OH Cl
CHO A chlorohydrin (major product)
(c) OHC CHO CH3  CH  CH2 + HBr

 
OtBu Cl Cl
(Minor product)
(d) OHC
The reaction proceeds through following mechanism :
CHO +
Exp. (a) Cl
Slow H 2O
3 Step II CH3—CH=
=CH2 + Cl—Cl CH3—CH—CH2
CHO Fast
Step I O3/Me2S
2 OHC Chloronium –
KOtBu Ozonolysis + Cl
ion
1 and OHC CHO
Br Cyclohex-1, H2O +
3-diene CH3—CHCH2—Cl Fast
CH3CH—CH2—Cl + H3O
+
| |
In step-1 dehydrohalogenation reaction takes place. OH OH
Here, hydrogen is eliminated from β-carbon and the | Chlorohydrin
halogen is lost from α-carbon atom. As a result diene H
is formed.
15. But-2-ene on reaction with alkaline KMnO4 at
H – elevated temperature followed by acidification
OtBu
Br Cyclohex-1,3-diene will give [JEE Main 2019, 12 April Shift-I]
(a) CH3 CH CH— CH3
Cyclohex -1, 3-diene on ozonolysis gives
 
butane-1, 4- dial and ethane- 1, 2- dial. OH OH

(b) one molecule ofCH3CHO and one molecule of Exp. (c)

CH3COOH
Heating of 2-chloro-1-phenylbutane with EtOK/EtOH
(c) 2 molecules of CH3COOH gives 1-phenyl but-1-ene(X). Reaction of X with
(d) 2 molecules of CH3CHO Hg(OAc)2 / H 2O followed by NaBH 4 gives 1-phenyl
butan-1-ol (Y). Reaction involved is as follows:
Exp. (c)
Cl –+
But-2-ene on reaction with alkaline KMnO 4 at
EtOK
elevated temperature followed by acidification will
Ph EtOH Ph
give acetic acid (CH3COOH). Hot alkaline solution OH
of potassium permanganate followed by 1. Hg (OAc)2,H2O
acidification oxidatively cleaved alkenes. The 2. NaBH4
Ph
reaction proceed as follows : (Y)
Alk. KMnO 4 , heat Mechanism
CH3 CH==CH CH3 → 2CH3COOH Cl OAc
H O+ 3 Acetic acid s
OEt
+ Hg OAc
16. In the following skew conformation of ethane, Ph dehydro- Ph
halogenation
H′ C C  H′′ dihedral angle is H
Oxymercuration
H OAc
H H′ 29°
H
Hg+
Ph
H
H′′ H C H
[JEE Main 2019, 12 April Shift-II] H H C2H5

(a) 58° (b) 149° (c) 151° (d) 120°
H 2O
Exp. (b) Ph CH CH Hg OAc
A dihedral angle is the angle between two C—H
bonds projected on a plane orthogonal to the C—C OH C2 H5
bond. In the given skew conformation, having
Newman’s projection the dihedral angle is H
H′ C C H′′ = (H′ C C Ha ) + (Ha C C H′′ ) s
OAc
= 29 °+120 ° = 149 °
H Ph CH CH HgOAc
H H′ OH C2H5
29º (ethane, C2H6)
Ha
Demercuration NaBH4
120º s
H′′ H Ph CH CH2 + AcO
b
OH C2H5 (Y)
17. Heating of 2-chloro-1-phenyl butane with
EtOK/EtOH gives X as the major product. 18. An Assertion and a Reason are given below.
Reaction of X with Hg(OAc)2 / H2O followed by Choose the correct answer from the following
NaBH4 givesY as the major product.Y is options. [JEE Main 2019, 12 April Shift-II]
[JEE Main 2019, 12 April Shift-II] Assertion (A) Vinyl halides do not undergo
OH nucleophilic substitution easily.
Reason (R) Even though the intermediate
(a) Ph (b) Ph carbocation is stabilised by loosely held
π-electrons, the cleavage is difficult because of
OH strong bonding.
OH (a) Both (A) and (R) are wrong statements.
(b) Both (A) and (R) are correct statements and (R)
(c) Ph (d) Ph is correct explanation of (A).

(c) Both (A) and (R) are correct statements but (R) O
O
is not the correct explanation of (A).
(c) (d)
(d) (A) is a correct statement but (R) is a wrong
statement. HO
Br
Exp. (c)

Vinyl halide (CH 2== CH  Cl) do not undergo Exp. (a)
nucleophilic substitution reactions. This is because it
⊕
forms highly unstable carbocation (CH 2== CH). It Key Idea The reaction involves hydrolysis or
cannot delocalise its π-electron. In vinyl halide C—Cl nucleophilic substitution in first step followed by
bond possess double bond character also. oxidation and dehydration in last step. The most
s r important fact is that, the Br group attached directly
CH2 CH Cl CH2 CH Cl to aromatic ring will not undergo substitution in step 1.
The road map of the given reaction is as follows:

(i) Br2
aq. KOH CrO3/H+
(ii) EtOH
Br OH
SN2
Br OEt Br Br
OEt It is aryl halide, remains unaffected
under ordinary SN2 reaction conditions
(a) (b)
OEt OEt O
OEt Br O
H OH H2SO4/∆
(c) (d) –H2O
(Intramolecular
Br dehydration)
[ JEE Main 2019, 9 Jan Shift-I] Br
Exp. (d) 21. Which of the following compounds is not
The road map of the given reaction is : aromatic?
Br
Br
Isolated C=C
* (a)
Br2 /CCl4
* (b)
Anti-addition (electrophilic) N
of Br2 with the isolated EtOH (Polar protic
H
(non-aromatic) C==C medium as well
–
SN1,–Br as nucleophile) (c) (d)
OEt
2°-benzyl
* Br carbocation N
(Stable)
* ⊕ [ JEE Main 2019, 9 Jan Shift-II]
EtOH Br
⊕
Racemised ± as well as –H * Exp. (b)
inverted (+ and –)
Aromaticity of a compound can be decided by
20. The major product of the following reaction is Huckel’s rule. In cyclopentadienyl cation (b),
resonance takes place as follows:
Br
(i) KOH (aq.)
⇒
(ii) CrO3/H+
(iii) H2SO4/∆ Resonance
Br H hybrid
O O
Hence, is anti-aromatic does not follow
(a) (b)
Huckel’s rule as it has conjugated 4 π-electron
Br ( 4nπ, n = 1) system. Rest of the species are aromatic
HO
as each of them belongs to 6 π-electron
[( 4n + 2 ) π, n = 1] system.


Exp. (d)
The reaction follows α, β-elimination mechanism to
CH3O give a more substituted stable alkene as a major
CH2Cl
(i) AlCl3 (anhyd.) product. As the substrate is a α, γ -dibromo (1, 3-)
(ii) H2O compound it gives a conjugated diene.
(a) CH3O (b) CH3O Br

HOs H Alc. KOH
CH3 D
–2HBr
OCH3 Ph H (It is very stable because
(c) CH3 (d) CH3O Br sOH the conjugated diene
system present. It is
further conjugated with
the benzene ring.)
Exp. (d) 24. Which compound(s) out of the following is/are
In the given reaction, AlCl 3 act as Lewis acid and not aromatic?
helps in generation of carbocation. The resulting
carbocation (1°) rearranges itself to stable
carbocation (3°).
MeO Cl r
AlCl3(anhy.) r s
r s (A) (B) (C) (D)
MeO Cl AlCl3
(a) (B), (C) and (D)
s
–AlCl4
(b) (C) and (D)
(c) (B)
MeO (d) (A) and (C)
a-Hs shift H r (1°)
(H2O)
MeO
r
Exp. (a)
A compound is considered to be aromatic, if it follows
three rules:
3° carbocation, more stable (a) Must be cyclic and planar.
Protic medium, H2O supports the
rearrangement of carbcation (b) Must have conjugated system in it.
Intramolecular (c) It must follow Huckel rule which states that
ArSE2 pathway number of π-electrons = (4n + 2 )
r
Me O MeO
–Hr
(A) ⇒2 π-e − system [(4n + 2 )π, n = 0]
H ⇒ Aromatic
23. The major product of the following reaction is (B) ⇒4π-e − system [4nπ, n = 1]
Br ⇒ Anti-aromatic
KOH alc. (excess)
∆
Ph
(C) ⇒8π-e − system [4nπ, n = 2 ]
Br
⇒ Anti-aromatic
(a) Ph (b) Ph
(D) ⇒ The sp3 -carbon does not support
sp3 conjugation and also devoids
(c) Ph (d) Ph planarity.
[ JEE Main 2019, 10 Jan Shift-I] ⇒ Non-aromatic

Only ionic halides ( X − ) give precipitate of AgX with

25. The major product of the following reaction is AgNO 3 solution. So, an organic bromide able to
Cl produce R ⊕ (stable carbocation) and Br − in aqueous
(i) HBr solution will give precipitate of AgBr with AgNO 3.
(ii) alc. KOH (+ R-effect)
O (a) —Br + Br
OH Cl
(Bond energy Unstable
(a) (b) also increases) (Aryl carbocation)
O O
Cl (b) —Br + Br
(c) (d) Stable carbocation

(Aromatic, 6π system)
O
OH
[ JEE Main 2019, 11 Jan Shift-I] (c) —Br + Br
(Unstable carbocation)
Exp. (c)
In presence of HBr, reactant containing (+R-effect)
C==C undergoes electrophilic addition reaction (d) —Br + Br
and give substituted alkyl halide. On further reaction N N
with alc. KOH, α,β-elimination takes place that give Unstable
(Aryl carbocation)
corresponding diene. The diene undergoes
enolisation to give stable product (phenol). Br
Cl –I effect at a-position to C==C Cl H So, only produces a precipitate of

AgBr with AgNO 3 solution.
HBr
—Br Acidic
β–H
27. Among the following four aromatic
Carbocation formation in the H compounds, which one will have the lowest
electrophilic addition of HBr
–HCl Alc. KOH melting point?
–I-effect at b-position to C==C O
–HBr (α, β–elimination)
OH
Enolisation to H Conjugated (a) (b)
OH
attain aromaticity H diene, stable
OH O
[Very stable, phenol] CH3
OH
26. Which of the following compounds will (c)
O
(d)
produce a precipitate with AgNO3 ? O
Br CH3 [ JEE Main 2019, 12 Jan Shift-II]
Br
(a) (b) Exp. (b)
N Melting point of a compound depends on size and
Br force of attraction between the molecules. Compound
Br (c) has largest size and also possess weak
intermolecular association due to dipole-dipole
(c) (d) interactions.
Compound (a) is a dicarboxylic acid and possess
[ JEE Main 2019, 11 Jan Shift-II] high melting point due to intermolecular hydrogen
bonding.
Exp. (a) As a result, it exist as associated molecule.
Compound (d) is an alcohol and possess

intermolecular H-bonding. No interactions are

present in hydrocarbon (naphthalene) compound (b). 29. The major product of the following reaction is
Hence, melting point is lowest for naphthalene (i) KOH alc.
CH3CH 2 CH CH 2    →
− 80° C ), i.e. compound (b).
(~
  (ii) NaNH2
Br Br in liq. NH3
28.
The major product of the following reaction is

(a) CH3CH2 CH  C H2
CH3O  
(i) Cl2/CCl4 NH2 NH2
(ii) AlCl3 (anhyd.) (b) CH3CH == CHCH2NH2
(c) CH3CH == C == CH2
Cl
(d) CH3CH2C ≡≡ CH
CH3O CH3O
(a) (b) Exp. (d)
Cl
Cl Key Idea Both alc. KOH and NaNH 2 in liquid NH 3 are
dehydrohalogenating reagents. On comparative
CH3O terms NaNH 2/liquid NH 3 is stronger in action.
(c) (d) CH3O
The reaction proceeds as :
Cl
Alc. KOH
CH3 CH2 CH CH2 CH3 CH2 CH CH2
[ JEE Main 2019, 12 Jan Shift-I] Br Br Br

NaNH2/liquid NH3
–
Exp. (c) CH3 CH2 C CH CH3CH2C CNa+
H+
The given reactant in presence of Cl 2/CCl 4 , given Thus, option (d) is the correct answer.
vicinal dihalide. Chlorine adds up to alkene via
electrophilic addition reaction involving cyclic
chlorinium ion formation.
H3CO
Cl2/CCl4 H 3C
CH2
Cl HCl
H3CO H
CH2 Cl
Cl
CH3
(a)
The vicinal dihalide in presence of anhyd. AlCl 3
results in the formation of carbocation that rearranges H
itself to form a cyclic compound. CH3
Cl CH2 Cl
H3CO (b)
+ AlCl3
(Anhyd.)
H
Cl Cl CH3
H3CO CH3
+ –
r + AlCl (c)
4
H
Cl
CH3O CH3O CH3
–H+
CH3
Cl Cl (d) Cl
H
H

Exp. (d) The road map of complete reaction is as follows:

It is a simple case of Markownikoff addition. The CH3 O CH CH CH3
reaction proceeds as:
CH3 CH3 H+ HBr excess/Heat
CH2 + CH3
+ H
+
CH3 O CH CH2 CH3
H H
3° stable Br–
carbocation
CH3 O CH CH2 CH3

Cl–
CH3 Br
CH3
Br– H+
Cl
H
H
d– +
BF d BB d–
The structure of options given may confuse an Br C O CH CH2 CH3
aspirant with ring expansion but that is seen as the BF
minor product only [Due to the formation of a 3° stable H H H d+ Br
carbocation in the process] the major product is Transition state
CH3 SN2 Reaction
CH3 (Zeisel’s Method)
Cl CH3Br + HO CH CH2 CH3
H
Br
Product
31. The major product in the following conversion Here, BB = Bond breakage, BF = Bonf formation
is
HBr (excess)
CH3O CH CH CH3 Heat ? 32. The major product of the following reaction is
CH2CH3
(a) CH3O CH CH2 CH3
NaOEt
H3C C Cl ∆
Br
(b) HO CH2 CH CH3 COOCH2CH3
Br (a) CH3CH2 C == CH2


(c) CH3O CH2 CH CH3 CO 2CH2CH3
Br (b) C O 2CH2CH3

(d) HO CH CH2 CH3 CH3C == CHCH3
CH2CH3
Br
(c) H3C C OCH2CH3
Exp. (d)
COOCH2CH3
Key Idea The excess of HBr and high
temperature in given reaction serves for dual OCH2CH3
purpose:
(i) Hydrolysis of ether via SN2 mechanism, (d) H3CH2C C CO2CH2CH3
i.e. Zeisel’s method.
CH3
(ii) Markownikoff addition at double bond of
the branch. [ JEE Main 2019, 12 Jan Shift-II]

Exp. (b) OMe

Presence of strong base (EtO − ) and heat indicates (a) (b)
elimination.
Thus, the compound undergo dehydrohalogenation
OMe
and alkene is produced. As per the position of Cl in

substrate, following 2 alkenes are formed as (c) (d)
product:
(i) CH3CH2 C ==CH2 Exp. (b)

COOCH2CH3 Complete reaction can be represented as
(ii) CH3CH ==C CH3 Br +–
 NaOMe
COOCH2CH3 + NaBr + MeOH
MeOH
In accordance with Saytzeff rule H
CH3CH == C CH3 Thus, the given reaction is dehydrohalogenation
 which is a β-elimination proceeding through E2
COOCH2CH3 mechanism.
will be the major product. Mechanism The reaction proceeds through the
formation of following transition state with
33. The trans-alkenes are formed by the simultaneous removal of Br and H atoms.
reduction of alkynes with [JEE Main 2018]
(a) H2 -Pd/C, BaSO 4 (b) NaBH4 Na+ Na+Br–
BF (Product)
(c) Na/liq. NH3 (d) Sn-HCl
BB Br
Exp. (c)
Here, BB = Bond breakage
BF
Sodium metal in liquid ammonia reduces alkynes BF = Bond formation
with anti stereochemistry to give trans alkenes. BB –
(Product) H BF
OMe
The reduction is selectively anti since the vinyl (Transition
radical formed during reduction is more stable in State)
MeOH (Product)
trans configuration.
R R H
H–NH2
RC CR′ C C –NH2 C C 35. The increasing order of reactivity of the
Na Na+ R′ R′ following halides for the SN 1 reaction is
Vinylic
Sodium atom donates an electron to radical I. CH 3CH(Cl)CH 2CH 3
alkyne which after H-abstraction from II. CH 3CH 2CH 2Cl
NH3 forms vinylic radical. Transfer of
another electron gives a vinylic anion, III. p - H 3CO  C 6H 4  CH 2Cl
which is more stable in trans form. [JEE Main 2017 (Offline)]
This in turn gives trans-alkene after Na Na+
(a) (III) < (II) < (I)
H-abstraction from NH3 .
(b) (II) < (I) < (III)
R H R H (c) (I) < (III) < (II)
H–NH2
C C –NH2 – C C (d) (II) < (III) < (I)
H R′ R′
Vinylic anion Exp. (d)
34. The major product of the following reaction
is [JEE Main 2018] / (i) The rate of S N1reaction depends only upon
Br the concentration of the alkyl halide.
NaOMe (ii) S N1reaction proceeds through the
MeOH formation of carbocation.

The reactivity is decided by ease of dissociation of O – + O

tert–BuONa
alkyl halide.
RX R⊕ + X È
- Br
(Unsaturated)
+ (decolourise Br2 water)
Higher the stability of R (carbocation), higher
would be the reactivity towards SN 1 reaction.
O O
p-H3CO  C 6H4 CH2 ⊕ is the most stable – +
tert–BuONa
carbocation due to resonance and then
Br
CH3 CHCH2CH3 (2° carbocation) while (Unsaturated)
⊕
⊕ (decolourise Br2 water)
CH3CH2 CH2 (1°) is least stable.
37. 3-methyl-pent-2-ene on reaction with
Thus, the correct increasing order of the reactivity
HBr in presence of peroxide forms an
of the given halides towards the SN1reaction is
addition product. The number of possible
CH3CH2CH2Cl < CH3 CH CH2CH3 stereoisomers for the product is
| [JEE Main 2017 (Offline)]
(II)
Cl
(I) (a) six (b) zero
< p - H3CO  C 6H4  CH2Cl (c) two (d) four
(III) Exp. (d)
36. Which of the following, upon treatment with The number of stereoisomers in molecules
tert-BuONa followed by addition of bromine which are not divisible into two equal halves and
water, fails to decolourise the colour of have n number of asymmetric C-atoms = 2 n .
bromine ? [JEE Main 2017 (Offline)] 3-methyl-pent-2-ene on reaction with HBr in
presence of peroxide forms an addition product
O C6H5
i.e. 2-bromo-3-methyl pentane. It has two chiral
(a) (b) centres. Therefore, 4 stereoisomers are possible
Br Br
Br
O 2 4 2 4
O 1 3 5 HBr 1 3 5
(c) (d) Peroxide
3-methylpent-2-ene Anti-Markownikoff's addition
Br Br
Four stereoisomers are possible
(As molecule has two chiral
Exp. (a) centres and asymmetric).
To show decolourisation, compound must be 38. The major product obtained in the
unsaturated.
following reaction is [JEE Main 2017 (Offline)]
O – + O Br
tert-BuONa H t
BuOK
C6H5 ∆
Br O—tBu C6H5
(Saturated) (a) ( ± ) C6 H5CH(O t Bu)CH2C6 H5
(cannot decolourise Br2 water)
(b) C6 H5CH == CHC6 H5
C6H5 – + C6H5 (c) ( + ) C6 H5CH(O t Bu)CH2C6 H5
tert–BuONa (d) ( − )C6 H5CH(O t Bu)CH2C6 H5
Br Exp. (b)
(Unsaturated)
(decolourise Br2 water) An alkyl halide in presence of a bulkier base
removes a proton from a carbon adjacent to the

carbon bonded to the halogen. This reaction is Exp. (a)

called E2 ( β-elimination reaction).
δ– δ+
HO—Cl +
Br — 2
CH3—CH—CH CH3—CH—CH2—Cl
H C6H5 (Electrophilic
t-BuO–K+ H (Intermediate)
C6H5 C==C addition)
C6H5 H C6H5
H –
H + tert-BuOH + Br– OH
CH3—CH—CH2—Cl
39. 2-chloro-2-methylpentane on reaction with
sodium methoxide in methanol yields OH
41. Which of the following compound will
CH 3
exhibit geometrical isomerism?

[JEE Main 2015]
I. C 2H 5CH 2 C  OCH 3
 (a) 1-phenyl-2-butene
CH 3 (b) 3-phenyl-1-butene
II. C 2H 5CH 2 C == CH 2 (c) 2-phenyl-1-butene
 (d) 1, 1-diphenyl-1-propane
CH 3
Exp. (a)
III. C 2H 5CH == C  CH 3
Alkene in which different groups are attached with
 the double bonded carbon atoms, exhibit
CH 3 geometrical isomerism.
(a) Both I and III (b) Only III
H H
(c) Both I and II (d) All of these Ph
H
1-phenyl -2-butene = Ph
Exp. (d)
H
− trans cis
/ Strong nucleophile (OMe) in polar solvent
(MeOH) gives elimination products over It will show geometrical isomerism.
substitution products but all products are H
possible in different yields.
3-phenyl-1-butene H
Cl
– +
Same group, does not show H Ph
MeONa
CH3—C—CH2CH2CH3 geometrical isomerism.
MeOH
CH3 OCH3 Ph
CH3—C—CH2—CH2—CH3 + H
2-phenyl-1-butene
CH3 Same group, does not show
H
(Less yield) geometrical isomerism.
CH3—C==CH—CH2CH3+CH2 ==C—CH2—CH2CH3 1,1-diphenyl-1-propane being an alkane

(saturated compound) does not show
CH3 CH3 geometrical isomerism.
(More yield) Time Saving Technique We do not need
the check all options, but it should remind that
40. The reaction of propene with HOCl double bonded compounds show geometrical
(Cl 2 + H 2O) proceeds through the isomerism.
intermediate [JEE Main 2016 (Offline)] Thus, (d) is eliminated, (i.e. propane).
+ +
(a) CH3 C HCH2Cl (b) CH3CH(OH)C H2 Now, eliminate the terminal alkene and get the
+ + correct response.
(c) CH3CHClC H2 (d) CH3 C HCH2OH

42. The synthesis of alkyl fluorides is best Exp. (d)

accomplished by [JEE Main 2015] Compound A gives a precipitate with alcoholic
(a) free radical fluorination AgNO 3 (here white is misprinting because the
(b) Sandmeyer’s reaction colour of ppt is light yellow), so it must contains Br
in side chain. On oxidation, it gives C 8H6O 4 , which
(c) Finkelstein reaction

shows the presence of two alkyl chains attached
(d) Swarts reaction
directly with the benzene nucleus.
Exp. (d) Since compound B gives anhydride on heating,
the two alkyl substituent must occupy adjacent (1,
Alkyl fluorides can be prepared by action of
2) position.
mercurous fluoride or antimony trifluorides
(inorganic fluorides) on corresponding alkyl Thus, A must be
halide. This reaction is known as Swarts reaction. CH2Br
CH3Br + AgF → CH3F + AgBr
Methyl fluoride CH3
But, when action of NaI/acetone takes place on
and the reactions are as follows
alkyl chloride or bromide, alkyl iodide forms. This
reaction is called ‘Finkelstein reaction’. CH2Br CH2 OR
Alcoholic
C 2H5Cl →
NaI
C 2H5I + NaCl + AgBr
acetone AgNO3
CH3 CH3
Free radical fluorination is highly explosive reaction. (A)
so not preferred for the preparation of fluoride. Oxidation O
43. The major organic compound formed by the COOH
D
reaction of1, 1, 1 −trichloroethane with silver -H2O
O
powder is [JEE Main 2014] COOH
(B) O
(a) acetylene (b) ethene Phthalic anhydride
(c) 2 −butyne (d) 2 −butene
45. A solution of (–l )-chloro-1-phenylethane in
Exp. (c) toluene racemises slowly in the presence of
Cl a small amount of SbCl 5, due to the
 Ag formation of [JEE Main 2013]
2Cl C  CH3 → CH3  C ≡≡ C  CH3 + 6AgCl
(a) carbanion (b) carbene
 (2 -butyne )
Cl (c) carbocation (d) free radical
(1, 1, 1− trichloroethane ) Exp. (c)
44. Compound ( A ), C 8H 9Br gives a white The given compound, (−l )− chloro-1-phenylethane
in the presence of SbCl 5 forms a carbocation.
precipitate when warmed with alcoholic
SbCl +
AgNO3. Oxidation of (A) gives an acid (B), Cl  CH  CH3 → 5
[Ph CH CH3 ] SbCl −6
Toluene
C 8H 6O4 . (B) easily forms anyhydride on 
heating. Identify the compound (A). Ph
[JEE Main 2013] Since, the carbocation is a planar species,
CH2Br C2H5 therefore it can be attacked by SbCl −6 either from
(a) (b) the front or back side of the carbocation with equal
Br ease. As a result, 50 : 50 mixture of two
CH3 enantiomers of 1−chloro−1 −pheynylethane
undergoes racemization due to the formation of a
CH2Br
carbocation intermediate.
CHB2r +
(c) (d) [Ph CH CH3 ] SbCl 6− → Ph CH CH3 + SbCl 5
CH3 
Cl
CH3 [ d and l forms ]

46. How many chiral compounds are possible Exp. (b)

( b ) Li/NH
on monochlorination of 2-methyl butane? CH3CH2CH2 — C ≡≡ C — CH3 →
3
(a) 8 (b) 2 [AIEEE 2012] 2 -hexyne [Birch reduction]

(c) 4 (d) 6 H CH3
Exp. (b) C == C
CH3CH2CH2 H
2 −methylbutane an monochlorination gives
Trans-2 - hexene
4 isomers, among which I and III are chiral in
nature. (a) Pt /H
*
2-hexyne →
2
n - hexane
Cl 2
CH3 — CH2 —CH — CH3 → (c) Pd/BaSO
 →
4
cis - 2 - hexene
CH3 [Lindlar’s catalyst ]
Cl
 (d) LiAlH
* →
4
no reaction
CH3CH2 —CH — CH2Cl + CH3CH2 — C — CH3
 
CH3 CH 3 49. Iodoform can be prepared from all except
(I) (II) (a) ethyl methyl ketone [AIEEE 2012]
Cl (b) isopropyl alcohol

+ CH3 — CH —CH — CH3 + CH2 CH2 — CH — CH3 (c) 3-methyl-2-butanone
*    (d) isobutyl alcohol
CH3 Cl CH3
(III) (IV) Exp. (d)
Hence, 2 chiral compounds are formed in the
Iodoform reaction is given by alcohols and
above reaction.
O
47. Which branched chain isomer of the 
hydrocarbon with molecular mass 72 u ketones containing CH3 CH  and CH3  C 
gives only one isomer of mono substituted 
OH
alkyl halide? [AIEEE 2012]
(a) Tertiary butyl chloride group, respectively. Thus, among the given
(b) Neopentane compounds, isobutyl alcohol does not contain
(c) Isohexane
CH3 CH  group.
(d) Neohexane 
Exp. (b) OH
Hence, it does not give iodoform reaction on
Molar mass = 72 = C nH2 n + 2 = 12 n + (2 n + 2 )
treatment with I2 / NaOH.
n=5 O
Thus, hydrocarbon is C 5H12 . 
Since, it gives only single C 5H11Cl, This suggests CH3 CH CH3 CH3 C CH2CH3
that C 5H12 is symmetrical.  Ethyl methyl ketone
Hence, it is containing all 12 equivalent H-atoms. OH
CH3 Isopropyl alcohol
CH3
 Cl 2  CH3
H3C — C — CH3 → H3C —C — CH2Cl +HCl O
 ∆
  
CH3 CH3 CH3 C  CH CH3 CH3  CH CH2OH
 Isobutyl alcohol
48. 2-hexyne gives trans-2-hexene on treatment CH3
with [AIEEE 2012] 3-methyl-2 - butanone
(a) Pt / H2 (b) Li / NH3 Hence, compounds (a), (b ) and (c ) will give

(c) Pd / BaSO 4 (d) LiAlH4 iodoform while compound (d ) (isobutyl alcohol)
does not give any iodoform reaction.

50. Ozonolysis of an organic compound gives 52. The non-aromatic compound among the
formaldehyde as one of the products. This following is [AIEEE 2011]
confirms the presence of [AIEEE 2011]
(a) (b)
(a) two ethylenic double bonds
S
(b) a vinyl group

(c) an iso propyl group
(c) (d)
(d) an acetylenic triple bond
Exp. (b) S
Exp. (a)
Alkenes give carbonyl compounds on ozonolysis.
A compound is said to have aromatic character if
3 O / Zn /H O
2→
Alkene   ring system is planar (with p-orbital) and there is
HCHO + other carbonyl compound complete delocalisation of π-electrons (lone pair
(A ) may be taken for delocalisation as relay electrons).
 R1
 This is true only in conjugated cyclic system.
 
C == O

( B)R
 2
 S This pair is used in delocalisation
In order to determine alkene, place carbonyl
compounds with their O-atom face to face. Huckel rule is followed when electrons used in
Replace O-atom by a double bond. delocalisation = (4n + 2 )
R1 (including lone-pair), where, n = 0, 1, 2, 3, K
Replace 2 3
C ==O + O == CH2   →
( B) (A) O -Atom by ( == ) bond
R2 (a) 1 4
R1 5
o- atoms face to face
C == CH2 (1, 3-cyclopentadiene)
R2 —ring is planar
—ring is not conjugated
51. Ozonolysis of an organic compound A
produces acetone and propionaldehyde in —delocalisation of π-electrons is not
possible after C 4
equimolar mixture. Identify A from the
following compounds. [AIEEE 2011] — (4n + 2 ) π-electrons = 4
(a) 2-methyl-1-pentene (b) 1-pentene Hence, it is not aromatic.
(c) 2-pentene (d) 2-methyl-2-pentene
53. One mole of a symmetrical alkene on
Exp. (d) ozonolysis gives two moles of an aldehyde
H3C having a molecular mass of 44 u. The alkene
O /H O / Zn
Alkene  
3 2
→ C == O + CH3CH2CHO is [AIEEE 2010]
H3C (a) propene (b) 1-butene
Acetone Propionaldehyde (c) 2-butene (d) ethene
To identify alkene (from ozonolysis products)
place these products with O-atoms face to face. Exp. (c)
Replace O-atoms by == (double) bond.
The general molecular formula for carbonyl
H3C Replace compound is C nH2 nO.
C == O + O == CHCH2CH3 →
O −atoms by ⇒ C nH2 nO = 44 u
H3C double bond
⇒ C nH2 n = 44 − 16
O-atom face to face
H3C ⇒ C nH2 n = 28 u ⇒ n = 2
2 3 4 5
C == CHCH2 CH3 Thus, the aldehyde comes out to be C 2H4O or
H3C CH3CHO. In order to identify an alkene, place 2
2 -methyl-2 -pentene molecules ofCH3CHO withO −atom face to face.

Then, replace O atom by doube bond.

H
55. In the following sequence of reactions, the

alkene affords the compound ‘B’
CH3 C == O + O == CHCH3 → CH3CH == CHCH3 O3 H 2O
CH 3CH == CHCH 3 → A → B
but - 2 -ene Zn
(symmetrical alkene)
Hence,
The compound B is [AIEEE 2008]
O (a) CH3CH2CHO (b) CH3COCH3
(c) CH3CH2COCH3 (d) CH3CHO
O3
CH3CH ==CHCH3 CH3 CH CH CH3 Exp. (d)
2-butene
O
O O
O3
Zn/H2O CH3CH==CHCH3 CH3 CH CH CH3
2CH3 CHO
O O
Zn , H2O
54. Consider the following bromides, Reductive
Me ozonolysis
(A) Me Br (B) 2CH3 CH==O
Me Br ‘B’
(C) Me
56. The hydrocarbon which can react with
Br [AIEEE 2010] sodium in liquid ammonia is [AIEEE 2008]
The correct order of SN 1 reactivity is (a) CH3CH2CH2C ≡≡ CCH2CH2CH3
(a) (B) > (C) > (A) (b) (B) > (A) > (C) (b) CH3CH2C ≡≡ CH
(c) (C) > (B) > (A) (d) (A) > (B) > (C) (c) CH3CH==CHCH3
Exp. (a) (d) CH3CH2C ≡≡ CCH2CH3
The reactivity of SN1 reaction depends upon the Exp. (b)
stability of the intermediate, carbocation formed
during these reactions. The stabiliIty order of the Only terminal alkynes undergo reduction with
carbocation formed from the given species is sodium (Na ) in liquid ammonia (NH3 ).
Me Me Hence,CH3CH2C ≡ CH reacts withNa in liq. NH3 .
> Na /liq. NH3
+ Me +
CH3CH2C ≡ CH → CH3CH2C ≡ C −Na +
Allylic carbocation 2°carbocation (stabilises ∆
(stabilises through by hyperconjugation
resonance due to due to 6 α-H atoms) 57. The organic chloro compound, which
conjugution) + shows complete stereochemical inversion
CH2 during an SN 2 reaction is [AIEEE 2008]
>
Me + (a) (C2 H5 )2 CHCl (b) (CH3 )3 CCl
1°carbocation (c) (CH3 )2 CHCl (d) CH3Cl
(stablises by hyperconjugation
due to 2 α-H-atoms) Exp. (d)
Hence, the reactivity order of the given bromide Nucleophilic substitution bimolecular (SN2) prefers
towards SN1reaction is less sterically hindered site to attack. Lesser the
Me Me steric hindrance faster theSN2 reaction. So ease of
>
Me reaction is 1° > 2 ° > 3°.
H H
Br Br
(B) (C) Nu
H Cl Nu H
> Me Br
(A) H H

SN2 involves inversion of configuration stereo, Exp. (d)

chemically. (a) CH3 C ≡≡CH + HBr → CH3  C == CH2
Rearrangement +|
Since, 1° alkyl halides are prone to SN2 reactions, ← H3C CH C
therefore CH3Cl undergoes complete BrH2
(Hydride transfer) 
strerochemical inversion. Br  H+
↓
Br
58. The treatment of CH 3Mg X with  Br − +
CH3  C CH3 ← CH3  C CH3
CH 3C ≡≡ C H produces [AIEEE 2008]  
(a) CH3 CH == CH2 (b) CH3C ≡≡ C  CH3 Br Br
2, 2-dibromopropane More stable
H H carbocation
| |
(c) CH3  C == C CH3 (d) CH4 (b) CH3CH==CHBr →
HBr CH3CH2CHBr2
2 HBr
(c) CH ≡≡ CH → CH3CHBr2
Exp. (d)
(d) CH3 CH ==CH2 →
HBr
CH3  CHBr CH3
Terminal alkyne has acidic hydrogen which is
enough to protonate the Grignard reagent. 61. Presence of a nitro group in a benzene ring
CH3MgX +CH3C ≡≡ CH → CH4 +CH3C ≡≡ CMgX (a) activates the ring towards electrophilic
substitution
59. The electrophile, E + attacks the benzene (b) renders the ring basic
ring to generate the intermediate (c) deactivates the ring towards nucleophilic
σ-complex. Which of the following substitution
σ-complex is of lowest energy? [AIEEE 2008] (d) deactivates the ring towards electrophilic
NO2 NO2 substitution [AIEEE 2007]
Exp. (d)
–
(a) + H (b) +  NO 2 group withdraw + O
E electron from the ring, thus N
H E
shows −M effect and makes O
NO2 ring more electron deficient.
H H Hence,  NO 2 deactivates
(c) + E (d) + E the ring for electrophilic substitution.
62. The reaction of toluene with Cl 2 in presence
Exp. (c)
of FeCl 3 gives predominantly
NO 2 being an electron withdrawing group (a) benzoyl chloride [AIEEE 2007]
destabilises the carbocation by decreasing (b) benzyl chloride
electron density form σ − complex. Thus, the (c) o - and p - chlorotoluene
presence of NO 2 group on a benzene ring of σ − (d) m-chlorotoluene
complex decreases their stability. However, the Exp. (c)
carbocation (c) does not contain any NO 2
CH3 CH3
group. Cl2, FeCH3
Thus, it would be highly stable than other
(Cl+)
σ -complexes. Hence, σ -complex (c ) is of lowest Cl
chlorination p-chloro toluene
energy. electrophilic
CH3
60. Which of the following reactions will yield +
2, 2-dibromopropane? [AIEEE 2007]
(a) CH3  C ≡≡ CH + 2HBr → Cl
o-chloro toluene
(b) CH3CH == CHBr + HBr →
(c) CH ≡≡ CH + 2HBr →
(d) CH3  CH == CH2 + HBr →

63. HBr reacts with CH 2 ==CH OCH 3 under The alkene formed as a major product in the
above elimination reaction is [AIEEE 2006]
anhydrous conditions at room temperature
to give [AIEEE 2006] (a) Me (b) CH2 CH2
(a) CH3CHO and CH3 Br Me Me
(b) BrCH2CHO and CH3OH (c) (d)

(c) BrCH2 CH2 OCH3
(d) H3C CHBr OCH3
Exp. (b)
Exp. (d) Compounds bearing a quaternary nitrogen atom
bonded to four alkyl groups when heated in the
HBr
CH2 ==CH OCH3 → CH3  CH OCH3 presence of base like OH− undergo E 2 elimination
 with the formation of less substituted alkene as a
Br major product with the loss of β − H atom.
First protonation occurs, two possible This type of elimination is called Hofmann elimination.
intermediates are B4(H)
H
CH3 → CH → OCH3 CH3
+

H (I) + CH3 β1(H)
N
(−I effect destabilises carbocation) H H CH2 — CH3
+ CH2 — CH2 — CH2 — CH3
and CH3 CH  O CH3
(II) • • β3(H) β2(H)
(+ M effect stabilises carbocation) s
OH CH3
II, is more favourable. Hence, Brs attacks and ∆ +CH2 CH2
product is CH3 CH O CH3 N
CH3

Br CH2 — CH2 — CH2 — CH3
64. Trans-2-phenyl-1-bromocyclopentane on (Major product)
reaction with alcoholic KOH produces CH3
+CH2 CH2CH2CH3
(a) 4-phenylcyclopentene [AIEEE 2006] CH3
N (Minor product)
(b) 2-phenylcyclopentene
(c) 1-phenylcyclopentene CH2 — CH3
(d) 3-phenylcyclopentene
Hence, CH == CH2 will be a major product.
Exp. (b) 66. CH 3Br + Nu − → CH 3  Nu + Br −
H
The decreasing order of the rate of the above
HO reaction with nucleophile (Nu – ) A and D is
Alc.KOH
H Ph
E2
Ph [Nu = ( A ) PhO– ,(B )AcO− , (C )HO− ,
H anti-elimination ( D )CH 3O– ] [AIEEE 2006]
Br H H (a) D > C > A > B (b) D > C > B > A
3-phenylcyclopentene (c) A > B > C > D (d) B > D > C > A
Anti-elimination, means —H and the —Br both Exp. (a)
departing group must be present at dihedral angle Nucleophilicity order is
of 180° (anti).
s O
O
65. Me
CH3 O>H
s
Os > > CH3 C O
s
Me ∆
r (C) (B)
(D)
s N Negative charge
+ I effect (A )
Et Negative charge comparatively
stabilised by stable than
n Bu
resonance phenoxide ion

67. The structure of the major product formed Exp. (c)

in the following reaction is H H Br
| | Br2 |
H3C C C CH3 → CH 3 CH2 C  CH3
| | |
NaCN
H CH3 CH3
DMF 2 -b romo - 2 - methyl butane
[AIEEE 2006]
70. Of the five isomeric hexanes , the isomer
CN Cl which can give two monochlorinated
(a) (b)
compounds, is [AIEEE 2005]
NC (a) 2-methylpentane (b) 2,2-dimethylbutane
CN (c) 2,3-dimethylbutane (d) n-hexane
Cl CN Exp. (c)
(c) (d)
2 Cl
(a) 2-methylpentane → five types of
monochlorinated
CN I compounds
2 Cl
Exp. (d) (b) 2, 2-dimethylbutane → three types...
2 Cl
Cl CN (c) 2, 3-dimethylbutane → two types...
NaCN
DMF 2 Cl
(d) n-hexane → three types ....
71. Elimination of bromine from

2-bromobutane results in the formation of
Chloride present on 1° aliphatic carbon can be
(a) predominantly 2-butyne [AIEEE 2005]
substituted easier than iodide because I is
(b) predominantly 1-butene
attached to benzene ring. Lone pair of e − of I is
involved in delocalisation with π − e − of benzene. (c) predominantly 2-butene
(d) equimolar mixture of 1 and 2-butene
Cl
Exp. (c)
CH3CH2 CHCH3 → CH3CH2CHCH3 →
⊕ −H +

..
Br (2 °carbocation)
−
..
Hence, I is difficult to substitue. CH3CH2CH == CH2 +CH3CH == CHCH3

Less substituted More substituted
68. Alkyl halides react with dialkyl copper II I
reagents to give [AIEEE 2005] Stability of I > II, hence I is predominant.
(a) alkenyl halides (b) alkanes 72. Reaction of one molecule of HBr with one
(c) alkyl copper halides (d) alkenes molecule of 1, 3-butadiene at 40°C gives
Exp. (b) predominantly [AIEEE 2005]
(a) 1-bromo-2-butene under kinetically
R 2CuLi + R ′ X → R  R ′+ R Cu + LiX
controlled conditions
(dialkyl copper lithium )
(b) 3-bromobutene under thermodynamically
69. 2-methyl butane on reacting with bromine controlled conditions
in the presence of sunlight gives mainly (c) 1-bromo-2-butene under thermodynamically
(a) 1-bromo-3-methylbutane [AIEEE 2005] controlled conditions
(b) 2-bromo-3-methylbutane (d) 3-bromobutene under kinetically controlled
(c) 2-bromo-2-methylbutane conditions
(d) 1-bromo-2-methylbutane

Exp. (c) Exp. (a)

CH2 ==CHCH ==CH2 + HBr → Aqueous NaCl is neutral, hence there is no reaction
between ethyl acetate and aqueous NaCl.
CH3 CHCH == CH2 +CH3CH ==CHCH2Br
 76. Acetyl bromide reacts with excess of CH 3MgI
1, 4-addition product
Br
1, 2 -addition product
followed by treatment with a saturated
solution of NH 4Cl gives [AIEEE 2004]
Addition is through the formation of allylic
carbocation. (a) acetone (b) acetamide
⊕ ⊕ (c) 2-methyl-2-propanol (d) acetyl iodide
CH2== CH C HCH3 ←→ CH3CH == CHCH2
(2 ° allylic) (1° allylic) Exp. (c)
(more stable) (less stable) O O
 
Under mild conditions (temperature ≈ − 80° C ) H3C C Br + H3CMgI → H3C C CH3
kinetic product is the 1, 2-addition product and O
under vigorous conditions, (temp. ≈ 40° C ) H3C
 |
thermodynamic product is the 1, 4-addition product. H3C C H3C + H3CMgI → H3C C  OMgI
Thus, 1-bromo-2-butene is the major product |
under given condition. H3C
H3C
73. Which one of the following is reduced with |
aq. NH 4Cl
zinc and hydrochloric acid to give the → H3C C OH
corresponding hydrocarbon? [AIEEE 2004] |
(a) Ethyl acetate (b) Acetic acid H3C
(c) Acetamide (d) Butan-2-one 2 -methyl-2 -propanol
Exp. (d) 77. The compound formed on heating

chlorobenzene with chloral in the presence of
Carbonyl compounds are reduced to
corresponding alkanes with (Zn + conc. HCl). It is concentrated sulphuric acid is [AIEEE 2004]
called Clemmensen reduction. (a) gammexane (b) DDT
O (c) freon (d) hexachloroethane
|| Zn(Hg) + HCl
CH3CH2 ⋅ C CH3 →CH3CH2CH2CH3 Exp. (b)
Conc⋅H2SO4
74. Which one of the following has the CCl3CHO + 2 Cl DDT
minimum boiling point? [AIEEE 2004] Chloral
(a) n-butane (b) 1-butyne Chlorobenzene
(c) 1-butene (d) Isobutene 78. On mixing a certain alkane with chlorine
and irradiating it with ultraviolet light, it
Exp. (d) forms only one monochloroalkane. This
H3C alkane could be [AIEEE 2003]
Isobutene C == CH2 has minimum force
H3C (a) propane (b) pentane
of attraction (due to steric hindrance). Thus, (c) isopentane (d) neopentane
minimum boiling point. Exp. (d)
75. On mixing ethyl acetate with aqueous In neopentane, all H are equivalents.
sodium chloride, the composition of the CH3 CH3
resultant solution is [AIEEE 2004]  
(a) CH3COOC2 H5 + NaCl H3C C CH3 →
hv
H3C C CH2Cl
Cl 2
(b) CH3COONa + C2 H5OH  
CH3 CH3
(c) CH3COCl + C2 H5OH + NaOH
(d) CH3Cl + C2 H5COONa

79. Butene-1 may be converted to butane by Exp. (c)
reaction with [AIEEE 2003] NH2
NC
(a) Zn-HCl (b) Sn-HCl (c) Zn-Hg (d) Pd/H2
Exp. (d)
∆
Pd /H +CHCl3 + acl.KOH
CH2 ==CHCH2CH3 → 2
∆ , pressure
CH3CH2CH2CH3
Butene -1 Butane
Other reagents are successful with polar double CH3
bonds. p-toluidine
CH3
This is carbylamine reaction
80. Bottles containing C 6H 5I and C 6H 5CH 2I lost
their original labels. They were labelled A 82. Acetylene does not react with [AIEEE 2002]
and B for testing . A and B were separately (a) Na (b) ammoniacal AgNO 3
taken in test tubes and boiled with NaOH (c) HCl (d) NaOH
solution. The end solution in each tube was
made acidic with dilute HNO3 and then
Exp. (d)
1
some AgNO3 solution was added. Substance CH ≡≡ CH + Na → CH ≡≡ C −Na + + H2
B gave a yellow precipitate. Which one of the 2
following statements is true for this CH≡≡ CH + AgNO 3 → CH ≡≡ C − Ag +
(ammonical) White ppt.
experiment?
(a) A was C6 H5 I [AIEEE 2003] CH ≡≡ CH + HCl → CH2 == CH Cl.
(b) A was C6 H5CH2 I Usually occurs in the presence of Hg 2+ .
(c) B was C6 H5 I CH == CH + NaOH → no reaction
(d) Addition of HNO 3 was unnecessary Because of hard acid, hard base and soft acid,
soft base (HASB) theory. But is reacts withNaNH2 .
Exp. (a)
CH ≡≡ CH + NaNH2 → CH ≡≡ C −Na + feasible.
In tube A
NaOH 83. Acetylene reacts with hypochlorous acid to
C 6H5I → No reaction(QpH –I does not form [AIEEE 2002]
boil
break) (a) Cl 2CHCHO (b) ClCH2COOH
( i ) Dil . HNO 3
→ No (c) CH3COCl (d) ClCH2CHO
( ii ) AgNO 3 yellow ppt. of AgI
Exp. (a)
In tube B
NaOH, boil ( i ) Dil . HNO 3 HC ≡≡ CH + Cl OH
C 6H5CH2I → NaI → AgI (Acetylene) (hypochlorous acid )
−C 6H 5CH 2OH ( ii ) AgNO 3 yellow ppt.
Cl −H2 O

↓ CH CH == ← [Cl CH == CH OH]
(PhCH2I bonds breaks) Cl 2 −chloroeth -1en -1-ol
Thus, A was C 6H5I. (2 , 2 dichloroethanol) Tautomerises
81. The reaction of chloroform with alcoholic Cl CH CH OH
   
KOH and p -toluidine form [AIEEE 2003]
 Cl OH 
(a) H3C CN
84. CH 3MgI is an organometallic compound
due to [AIEEE 2002]
(b) H3C N2Cl (a) Mg—I bond (b) C—I bond
(c) C—Mg bond (d) C—H bond
(c) H3C NHCHCl2 Exp. (c)
CH3MgI contains carbon-metal (C Mg) bond, so
(d) H3C CN classified as organometallic compound.

17
Organic Compounds
Containing Oxygen
(Alcohols, Ethers, Aldehydes, Ketones,
Carboxylic Acids and Their Derivatives)
1. An organic compound neither reacts with OH
neutral ferric chloride solution nor with |
CH3 Neutral
Fehling solution. It however, reacts with FeCl3
no reaction
Grignard reagent and gives positive iodoform (FeCl3 test for phenolic
C—Et
group)
test. The compound is O
O ● Compound gives reaction with
O RMgX as it contains C  Et.
CH3
(a) (b) CH3 
H O
OH
OH OH
O | |
O CH3 RMgX CH3
OH
Grignard R
reagent C2H5
C—Et
C2H5 CH3
(c) (d) O OH
CH3 C2H5
O
Compound with CH3CH  group undergoes
O 
iodoform test in presence of NaOH and I2 .
OH
Exp. (d) OH O
|
According to the given conditions, compound (d) CH3 NaOH+I2
O–Na+
neither reacts with neutral ferric chloride solution CH3I ↓ +
Iodoform
nor with Fehling solution. It however reacts with test Yellow Et
C—Et ppts.
Grignard reagent and gives positive iodoform test.
O
● As the compound does not contain any phenolic O
—OH group. Hence, it gives negative neutral
FeCl 3 test.

OCH3 Step 3 As HBr is in excess, so, reaction will also

Conc. HBr (excess) take place at alkene.
Heat
OH OH
Markownikov’s rule, HBr
CH==CH2 Addition reaction


OH CH=
=CH2 Br CH3
Br
(a) (b)
O Cl
Br—CHCH3 Br—CHCH3
Br OH (i) AlCl3, heat
(c) (d) O+ (ii) H2O
CH2CH2Br CH2CH2Br O
Exp. (b) O
Key Idea Ethers are least reactive functional

groups. The cleavage of C—O bond in ethers take
(a)
place under drastic conditions with excess of HX. Cl
The major product obtained in the reaction is as O

follows : CO2H Cl
OCH3 OH (b)
Conc. HBr (excess)
Heat
O
CH=
=CH2 Br—CH— CH3 O Cl
As conc. HBr is in excess. So, reaction will take
place at both the substituents. (c)
Mechanism
Step 1 Protonation of ether to form oxonium ion.
O
H
|r O
s
O—CH3 O—CH3 + Br
H—Br
(d)
COOH Cl
CH=
=CH2 CH=
=CH2
Oxonium ion Exp. (d)
Step 2 Attack of nucleophile at the protonated ether.
The major product of the given reaction is (d).
H Hs This reaction proceed via Friedel-Craft acylation.
|r |+
O—CH3 O CH3 Here, —Cl group present on chlorobenzene is
|
SN2
Br-+ Slow
ortho and para-directing. It can be easily
Br understood by resonating structures of
chlorobenzene.
CH=
=CH2 CH=
=CH2 O
OH
CH3—Br +
COOH Cl
CH=
=CH2 (d)

Organic Compounds Containing Oxygen 241
adding an H− followed by an H+ . The mechanism

r r r
Cl Cl Cl Cl Cl
of the given reaction is as follows :
s s O O–
C – C—CH2Br
s CH2Br H from NaBH4 H 2O
The given reaction proceed as follows : H

O
OH
O +
C
EtOH, 25°C
C—CH2 — Br
O + AlCl3 – O
O----Al + Cl3 Intramolecular
cyclisation H
O
O
Cl 5. The major product of the following reaction is
O (1) t-BuOK
O (2) Conc. H2 SO4 /∆

O Cl
C [JEE Main 2019, 8 April, Shift II]
H2O
O O
COOH Cl C—O – + Cl (b)
—AlC (a)
l3
O
O O O
Br (c) (d)
NaBH4
MeOH, 25°C
Exp. (d)
–I
OH OH O O
H β-elimination
Br OMe Cl s r /∆
tBuOK
(a) (b) Acidic hydrogen H
–HCl
This benzylic –H activates r

H (Conc. H2SO4)
p-position by +ve Electrophilic addition
for ArSO2
OMe O
H H
(c) (d) O O
2°
r
r 1°
Exp. (d) 1°, but more stable 2°, but less stable carbocation
carbocation because of –I effect of O
Major product obtained in the given reaction is
ArSE 2 ArSE 2
H H
r O r O
O
H 6- membered ring H
NaBH4 in the reaction is used for the reduction by ∆ –Hr (more stable) ∆ –Hr
H
addition of a hydride ion and a proton. Carbon-oxygen O O
double bonds are easily reduced by sodium
borohydride. The actual reducing agent in these
reductions is hydride ion (H− ). Hydride ion adds to Major product 5- membered ring Minor product
the carbonyl carbon and the alkoxide ion that is (option-d) (lon stable) (option-c)
formed is subsequently protonated by water. In
other words, the carbonyl group is reduced by

6 The major product obtained in the following reaction is [JEE Main 2019, 8 April Shift II]
CH3 O
NaOH
OHC ∆
CH3 CH3
CH3 H3C
(a) H (b) H
(c) (d)
O CH3 O CH2
O O
Exp. (c)
It is in intermolecular aldol condensation reaction.
O O O
s 4
OH 6 1 This attack will result 7-membering.
OHC CH2 HC 2 CH2 So, it will not proceed.
–H2O 5 3
7 s
H H
H
Acidic H-atom
O
OH– 4 2
5 1
– H2O O=
=CH 3 s
Less acidic
H s
HO H2O O
∆ 5
4
3
–H2O – OH
s 1 2
(option-c)
O Major O H More acidic O
β-H for
β-elimination

Exp. (c)
1. PBr3 Key Idea PBr3 reagent is used for the substitution
OH 2. KOH (alc.) of —Br group while alc. KOH reagent is used to
carry out elimination reaction.
O
The given reaction proceed in following manner:
[JEE Main 2019, 9 April Shift I] Step I In presence of PBr3 , alcohols undergo
substitution reactions to give halides. Reagent PBr3
(a) (b) OH is usually generated insitu by the reaction of red
phosphorus with bromine.
HO O PBr3
OH Br
(c) (d)
O O
3-bromohexanone
O O

Step II 3-bromohexanone in presence of alc. KOH 9. The major product of the following reaction is
undergoes elimination reaction and gives
cyclohex-2-en-1-one. CH2CH3
Alc. KOH (i) Alkaline KMnO4

Br
(ii) H3 O+
O O
Cyclohex-2-en-1-one [JEE Main 2019, 9 April Shift I]
COOH CH2CHO
CH3 CH == CHCO2 CH3   → LiAlH 4
[JEE Main 2019, 9 April Shift I] (a) (b)

(a) CH 3CH == CHCH 2OH (b) CH 3CH 2CH 2CH 2OH
(c) CH 3CH 2CH 2CO 2CH 3 (d) CH 3CH 2CH 2CHO
COCH3 CH2COOH
Exp. (a)
Key Idea LiAlH4 reagent is used for the reduction of (c) (d)
O

CHO, —C OCH3 . It does not reduce double bonds.
Exp. (a)
The reaction of an ester with LiAlH4 produces two The major product of the given reaction is benzoic
alcohols, one corresponding to the acyl portion of acid (C 6H5COOH). On vigorous oxidation of alkyl
the ester and one corresponding to the alkyl portion. benzene with acidic or alkaline KMnO 4 , aromatic
O acids are obtained. During oxidation of alkyl
 LiAlH 4 benzene, the aromatic nucleus remains intact and
CH3CH == CHC —OCH3 →
the entire chain is oxidised to COOH group
CH3CH == CHCH2OH + CH3OH irrespective of the length of carbon chain.
But -2-en -1-ol Methanol –+
CH2CH3 COOK COOH
Thus, the major product of the given reactant
O
 (i) Alk. KMnO4 (ii) H3O+
CH3CH == CHC OCH3 in presence of LiAlH4 is
CH3CH == CH CH2OH and CH3OH. The reaction Potassium
Ethyl Benzoic acid
proceeds through following mechanism. benzene benzoate
Mechanism
O 10. In the following reaction,
Nucleophilic acyl HCl
– substitution reaction Carbonyl compound + MeOH -acetal Rate
CH3CH CH C OCH3 + H AlH3
of the reaction is the highest for:
s
O (a) Acetone as substrate and methanol in excess
(b) Propanal as substrate and methanol in
CH3CH CH C OCH3 stoichiometric amount
O H (c) Acetone as substrate and methanol in
– stoichiometric amount
CH3CH CH C + CH3O (d) Propanal as substrate and methanol in excess
An aldehyde
H Nu H– – [JEE Main 2019, 9 April Shift II]
c le
op AlH
h
rea ilic a 3 s Exp. (d)
cti dd
on itio O
n
H+ Key Idea Aldehydes are more reactive than
CH3 CH CH CH2OH H 2O
CH3CH CH C H
Primary alcohol ketones in nucleophilic addition reactions.
H

For the reaction, —OH group attached on the benzene ring direct
HCl the incoming group at ortho and para-positions due
Carbonyl compound + MeOH - Acetal to increase in electron density at o and p-positions.
Rate of reaction is the highest for propanal as —OH group also exhibit –I group that reduces the
substrate and methanol in excess. Propanal is an electron density to some extent at o and
aldehyde and more reactive than ketones. When
p-positions. But overall electron density increases

MeOH is taken in excess then reaction moves in at these positions of the ring due to resonance.
the forward direction that results in the formation of Hence, attack of —Br occur at ortho- position.
acetal. Reaction involved is as follows : Resonating structures are as follows:
Et Et OH OH +OH +OH +OH OH
H+/MeOH
C O C
σ σ
H H OMe
Et OMe σ
MeOH
C
Excess 12. The major product of the following reaction is
H OMe
Acetal OH
11. p-hydroxybenzophenone upon reaction with CH2OH H2SO4(cat.)

bromine in carbon tetrachloride gives CO2Et CHCl3
O O O
Br (a) (b)
(a)
HO CO2Et COOH
O
OH OH
Br
(b) (c) (d)
HO OEt O
O
Br O O
(c)
Exp. (d)
HO
Br O Given reaction involves acidic hydrolysis of esters
followed by the intramolecular cyclisation. The
(d) chemical equation is as follows:
HO OH OH
Exp. (b) CH2OH H2SO4(cat.) CH2OH

CHCl3 +C2H5OH
p-hydroxy benzophenone upon reaction with
bromine in carbon tetrachloride gives COEt C OH
3-bromo-4-hydroxy benzophenone.
O O O
O OH OH
Br
Br2 CH2 OH –H2O
CCl4
O
HO
HO C OH
O
O

13. Major products of the following reaction are 14. The major product of the following reaction is
CHO O
(i) 50% NaOH HI (excess)
+ HCHO ∆
(ii) H3O+

(a) CH3OH and HCO2H NC O

COOH
OH I
(b) CH3OH and
(a) (b)
CH2OH NC
NC OH OH
(c) HCOOH and
I OH
(c) (d)
CH2OH COOH
(d) and NC
NC I I
Exp. (d)
Exp. (c)
The given reaction takes place as follows:
The given reaction is a crossed Cannizzaro Cleavage-I
reaction which is a redox reaction too. Oxidation | H+ |
+
number of carbon atom of the CHO groups of O O
HI (excess) H
PhCHO and HCHO are +1 and zero Cleavage-II
respectively. So, HCHO is the stronger reducing Cleavage-I
agent than PhCHO. As a result, HCHO is oxidised
to HCOONa (by donation of hydride, H− ) and
+ H
NC O H+ NC O
PhCHO (H− acceptor) is reduced to PhCH 2 OH. Cleavage-II
+1 0 50% NaOH
Ph C HO + HCHO → ge-
II
va
−1 +2 −+ lea
ia c
Ph C H2OH + H C OONa v SN1 pathway
[via cleavage I]
 +
↓ H 3O
I OH
PhCH2OH + HCOOH + CH3OH + I
s
(Major products) + CH3 CH3I
+
+ CH (CH3)2CHI
The reaction proceed via following mechanism. + (CH3)2CHOH
OH NC OH CH3 CH3 NC I
– | s Slowest
H2C=
=O
OH
H—C—O Product-1 Product-2
Slower
δ+ δ– | Ph—CH=
=O Product-2 is formed because
H (i) Cleavage-I will give more stable aryl carbocation.
More polar and less
–
crowding for H shift (ii) Cleavage- I will give intermediate which is in
nucleophilic addition conjugation with ring.
OH
|
H—C==O + Ph—CH2—Os 15. The major product Y in the following reaction is
Fast Ph CH3
Os
Ö
| NaOCl (i) SOCl2

X Y
H—C==O + PhCH2OH (ii) Aniline
O
Thus, the correct option is (c).

O CH3 CH3
Ph (c) (d)
N HN Ph CH3
O
(a) O (b) O
NH2 NH2
Exp. (c)
O (i) C 9H10O shows positive iodoform test thus,
(c) (d) C CH 3 group is present.
||
Ph
O
(ii) C 9H10O on strong oxidation(KMnO 4 / KOH), gives
O Ph
acid (C 8H 6O 4 ), indicating it can be a dicarboxylic
acid. So, ‘A’ contains COCH 3 and one CH 3
Exp. (b)
group which get oxidised into COOH and
NaOCl (sodium hypochlorite) is the reagent of COOH respectively.
haloform (chloroform formation) reaction.
(iii) In the preparation of phenolphthalein from
2NaOH + Cl 2 → NaOCl + NaCl + H2O phenol, phthalic anhydride is used. So, ‘B’ can be
The given reaction takes place as follows : phthalic acid (benzene-1,2- dicarboxylic acid)
O O which readily forms anhydride.
Thus, the reaction sequence is as follows :
NaOCl s r
Ph—C—CH3 Ph—C—ONa + CHCl3
r CH3
H3O (It is missing in the I2/NaOH
+ CHI3
Keto-methyl statement of the question) CH3 (Iodoform test) – +
group COONa Yellow ppts.
O CH3
C O
Ph—C—OH
Benzoic acid O C
(X) A(C9H10O) (i) [O] OH
+ CO2
KMnO4/KOH OH
O O (ii) H3O
r C
SOCl2
Ph—C—OH Ph—C—Cl O
– SO2 [Acyl SN2 Phthalic acid
(X) Benzoyl
– HCl H N— B(C8H6O4)
chloride 2 pathway]
Aniline –HCl H
∆ –H2O
O
(2 mol)/
O
Conc. H2SO4
—NH—C—Ph
Benzanilide C
OH
(Y) O
–H2O C
16. Compound A (C9 H10O) shows positive O
iodoform test. Oxidation of A with O
Phthalic anhydride
KMnO4 / KOH gives acid B (C8H6O4 ). O
Anhydride of B is used for the preparation of
phenolphthalein. Compound A is
O
CH2 C H CH3 OH OH
(Phenolphthalein
(a) (b) an indicator)
CH3
O CH3

O
17. The major product obtained in the given
reaction is O
CH3 O CH3 AlCl3
CH2 Product (b)
CH2 CH (a)
Cl HO
[JEE Main 2019, 10 April Shift II] HO
CH3 O
(a) CH3 O O
(c) (d)
(b) H3C O CH CH3 Cl

CH2 CH Cl
(c) H3C O Exp. (b)

The major product formed in the reaction is as
follows:
CH3
CH2 HO ==O
(d) H3C O (1) CrO3
CH2 CH CH2 (2) SOCl2/∆
(3)∆
HO HO
Exp. (c) Primary alcohol readily oxidised to corresponding

carboxylic acid with oxidising agent, chromium
The given reaction takes place as follows : trioxide (CrO 3 ) in acidic medium.
CH3 O CH3 O
AlCl3 COOH
Cl – AlCl s
4 HO CrO3
r
Intramolecular
It will stabilise the
ArSE 2-reaction HO HO
carbocation by
(+ve) hyperconjugation
OH group of carboxylic acid get substituted by
Cl in presence of SOCl 2 (Thionyl chloride).
CH3 CH3 O
O
–HCl r COOH COCl
–AlCl3
SOCl2/∆
H
CH3 –
+ SO2↑ + HCl↑
AlCl4
HO HO
18. The major product of the following reaction is Further, heating of product leads to intramolecular
cyclisation.
(i) CrO3 COCl

HO (ii) SOCl2/∆ C==O
∆
(iii) ∆
HO HO HO

Upon hydrolysis, following reaction takes place

19. The major products of the following reaction are
OH O–Na+ OH
H3O+ OH
(1) CHCl3/aq. NaOH OH
+ HCOO–Na+
(2) HCHO, NaOH (conc.)

(3) H3O+
Cl Cl
Cl + HCOOH
OH OH 20. What will be the major product when m-cresol
COOH COOH is reacted with propargyl bromide
(a) and methanol (b) and methanol (HC ≡≡ C CH 2Br) in presence of K 2CO3 in
acetone? [JEE Main 2019, 12 April Shift II]
Cl OH O OH
OH OH (a) (b)
OH OH CH3 CH3
(c) (d)
and formic acid and formic
OH OH
acid
OH Cl (c) (d)
Exp. (d) CH3 CH3

The major products of the given reaction are as
follows:
OH OH
Exp. (a)
The major product when m-cresol reacts with
(1) CHCl3/aq. NaOH OH propargyl bromide (HC ≡≡ C CH2Br) in presence
(2) HCHO, conc. NaOH and HCOOH of K 2CO 3 in acetone is given in the following
(3) H3O+ reaction:
Cl Cl
OH O–
In step-I, substituted phenol undergoes Reimer- Step 2
Tiemann reaction in presence of CHCl 3 /aq. NaOH Step 1
1. K2CO3 Br CH2 C CH
OH OH
–Brs
CHO
(1) CHCl3/aq. NaOH
O CH2 C CH
Cl Cl
The aldehyde obtained in above equation does not
possess α-hydrogen. In presence of formaldehyde Major product
and conc. NaOH it undergoes Cannizaro reaction.
In step 1 K 2CO 3 act as a base and abstract
In this reaction, one molecule of aldehyde is
H-atom from OH group.
reduced to alcohol while another molecule is
oxidised to salt of carboxylic acid. This leads to the formation of substituted
OH O–Na+ phenoxide ion (highly stable).
CHO In step 2 substituted phenoxide ion on reaction
Conc. with Br CH2 C ≡≡ CH gives the required product.
+ HCHO OH
NaOH + HCOO–Na+
Cl Cl

(c) NO2CH2COOH > NCCH2COOH

21. Consider the following reactions,
> FCH2COOH > ClCH2COOH
Ag2O
ppt (d) NO2CH2COOH > FCH2COOH
∆
A Turbidity > CNCH2COOH > ClCH2COOH
Hg2+/H+ NaBH4 ZnCl2
B C within [ JEE Main 2019, 9 Jan Shift-I]
Conc. HCl
5 minutes Exp. (c)
A is [JEE Main 2019, 12 April Shift II] All the given compounds are α-monosubstituted
(a) CH ≡≡ CH (b) CH3 C ≡≡ CCH3 acetic acid derivatives and the α-substitutions have
(c) CH3  C ≡≡ CH (d) CH2 == CH2 been made by strong–I groups/atoms. More powerful
the − I group, stronger will be the acid.
Exp. (c) −I power of different groups is as follows :
NO 2 > CN >  F >  Cl.
According to the given conditions, the compound
Thus, the correct decreasing order for acid strength is:
should be alkyne with triple bond present at the
terminal. The chemical reactions involved are as NO 2CH 2COOH > NCCH 2COOH > FCH 2COOH
follows: > ClCH2COOH.
Step 1 23. Major product of the following reaction is
Ag2O
CH3 C CH CH3 C C Ag
Cl
Prop-1-yne (Precipitates)
Cl NH2
Step 2 + H 2N (i) Et3N
Hg2+ O O (ii) Free radical
CH3 C CH dil. H SO polymerisation
2 4
OH O Cl O O
Tauto-– Cl
merisation (a) n NH2 (b)
CH3 C CH2 CH3 C CH3
O N n
NaBH4
O
H
HN NH2
CH3 CH CH3
Ol Cl Cl
OH
(2° alcohol) (c) (d)
n n
Conc. HCl
+
ZnCl2 HN O
NH2 NH2
CH3 CH CH3 N
O H
O
Cl
Turbidity within 5 minutes [ JEE Main 2019, 9 Jan Shift-I]
(Insoluble in Lucas reagent) Exp. (d)
In step-1, prop-1-yne reacts with Ag 2O to form The analysis of both the substrates :
CH3 C ≡≡ C  Ag, that forms white precipitates. Vinylic centre
In step 2, prop-1-yne in presence of mercuric Cl
sulphate and dil ⋅ H2SO 4 produces carbonyl (+R)
compound (CH3 )2 C == O which produces
(CH3 )2 CH OH in presence of NaBH4 . 2ºalcohol
on reaction with Lucas reagent produces turbidity O Cl
Acyl SN2 centre
in about 5 min.
Acts as
H2N nucleophile
22. The correct decreasing order for acid strength (1°-amine)
is O
This N-atom can
(a) FCH2COOH > NCCH2COOH not act as nucleophile
NH2 + R
> NO2CH2COOH > ClCH2COOH
(b) CNCH2COOH > O2NCH2COOH Amide group
> FCH2COOH > ClCH2COOH

So, the reaction can take place as follows:

25. The products formed in the reaction of
Decrease in the delocalisation of π-bonds
because of which it undergoes free radical
cumene with O2 followed by treatment with
addition (chain growth) polymerisation dil. HCl are
CH3
Cl Cl Free Cl
radical
–Cl – polymerisation
n (a)
absorbed –H O and CH3—OH
by Et3N O C
NH
O Cl NH2 OH
NH2 O
NH2 (b) H 3C CH3
O and
O
NH2
NH2
(c) H 3C CH3
and
24. The compounds A and B in the following
reaction are, respectively OH OH
HCHO+HCl AgCN
A B H 3C CH3
(d) and
(a) A = Benzyl alcohol, B = Benzyl isocyanide
(b) A = Benzyl alcohol, B = Benzyl cyanide [ JEE Main 2019, 9 Jan Shift-I]
(c) A = Benzyl chloride, B = Benzyl isocyanide Exp. (b)
(d) A = Benzyl chloride, B = Benzyl cyanide
The given process is cumene process (Hock process)
to synthesise phenol and acetone industrially. In Hock
p rocess, Ph— group migrate and release H 2O.
Exp. (c)
+ H
The mechanism of the given reaction is as follows: —O—O—H —O—O
H
⊕ y
it is electrophilic substitution O2 hν H+ Ph-group
[CH2==OH]Cl , (Ar SE2): Haloformylation
5 atm migration
–HCl
[CH2==O + H Cl] Cumene
CH2 OH ⊕
OH O O
OH
HCl Hydrolysis H2 O
–H2O (SN1) +
SN2
Ag CN
CH2Cl
More covalent
(Ag—C≡≡N )
–AgCl (A ) 26. The tests performed on compound X and their
(Benzyl chloride) inferences are :
CH2CN CH2NC Test Inference
+
(a) 2, 4- DNP test Coloured precipitate
(Minor) B (Major)
(Benzyl
isocyanide)
(b) Iodoform test Yellow precipitate
Thus, both benzyl cyanide and benzyl isocyanide are (c) Azo-dye test No dye formation
the products of reaction but benzyl isocyanide being
the major product gives the correct option as (c).

Compound ‘X ’ is Compound (c) is an alcohol and does not give positive

2,4-DNP test. Hence, eliminated.
H 3C CH3 H3C CH3
N (a) and (d) does not have —CH 3CO group and does
N
not give iodoform test. Hence, eliminated.
COCH3
(a) CHO
27.
(b) The major product of the following reaction is

HO
NH2 OH NH2 CH3
O AlCl3, ∆
CH3 +
(c) (d) CHO
OH OH
Exp. (b) H3C CH3
Let us study the chemical nature of the functional (a) (b)
groups present in the following compound (b).
It is a 3°-amino group (—NMe2)
though aromatic which will not
respond to diazotisation (NaNO2 + OH
dil. HCl/5°C). So, formation of OH
diazonium ion and its further reaction CH3
CH3
N with alkaline phenol or β-napthol at 5- CH3
CH3 (c) (d)
10°C to produce a precipitate of azo-
dye will not take place.
It is a keto group C==O and so it
responds to 2, 4-DNP test with
(b) Brady’s reagent (2, 4-dinitrophenyl [ JEE Main 2019, 9 Jan Shift-II]
hydrazine) to give a reddish orange
CH3 —— C==O
precipitate. Exp. (c)
O It is an aromatic electrophilic substitution reaction
It is a keto-methyl group —C—CH3
(Ar SE 2).
and hence, it responds to iodoform The reaction follows Ar SE 2 (Aromatic electrophlic
test to give a yellow precipitate of substitution pathway) as shown below :
iodoform (CHI3).
it makes ring activating

It becomes ring activating
and p-directing
and m-directing
H—O HO—AlCl3 HO—AlCl3 O—AlCl3

H 3C
AlCl3 –H /+H
O O
Friedel-Craft's
acetylation H
O reaction
O HO
O Stabilises the complex by −AlCl3
hyperconjugation
OH O O O
O O O –H2O O
H
CH3 H 2O

OH
28. The major product formed in the following (iv) C6H5—C—CH2—C—C6H5
(Self Aldol condensation
reaction is product of C6H5COCH3)
CH3
CH3 –
OH of base will prefer to attack on CH 3 group of
CH 3CHO for the formation of carbanion and as among

H 3C H +
Dil. NaOH the > C == O groups available, the > C == O group of
CH 3CHO is the best carbanion acceptor. Hence, self
O OH condensation product of CH 3CHO will be the major
product.
(a) H 3C 29. The decreasing order of ease of alkaline
OH O hydrolysis for the following esters is
(b) H3C COOC2H5 Cl COOC2H5
I II
OH O
O2N COOC2H5 CH3O COOC2H5
(c) H3C H
O OH III IV
(a) III > II > IV > I (b) III > II > I > IV
(d) H (c) II > III > I > IV (d) IV > II > III > I
H3C
Exp. (b)
[ JEE Main 2019, 9 Jan (Shift-II)] Alkaline hydrolysis of an ester (carboxylic acid
derivative) follows acyl SN 2 mechanism.
Exp. (c)
In aldol condensation, generally aldehydes react at a O s O O
OH
faster rate than ketones towards base. In the given C C + ROs C + ROH
case CH 3CHO will lose OR OH Os
O Rate of SN 2 mechanism depends on the polarity of
group of COOR group. Electron withdrawing group
C
( − R > − I ) increases the rate of SN 2 reaction whereas
CH3
α-hydrogen faster than due electron donating group ( + R > + I ) decreases the
rate of SN 2 reaction.
to one more reason, i.e. conjugation between Here, the nature of functional groups attached para to
benzene ring and C == O group. Along with the benzene ring are: — NO 2 > — Cl > — OCH 3
( − R) (−I) ( + R)
sterically less hindered nucleophile of CH 3CHO will So, the order of hydrolysis will be, III > II > I > IV
also add to the major product formation. ( − R) ( − I) ( + R)
Following four products are possible in the reaction: 30. Which dicarboxylic acid in presence of a
H dehydrating agent is least reactive to give an
(i) CH3—C—CH2—CHO (Self Aldol condensation anhydride?
CH2
of CH3CHO)
OH CO2H CH2 COOH
H (Cross Aldol condensation of (a) (b)
CH3CHO and CH3COC6H5 CH2 COOH
(ii) CH3—C—CH2—C—C6H5 in which >C=O group of CO2H
CH3CHO is carbanion CH2
OH acceptor). O
OH (Cross Aldol condensation of COOH C
CH3CHO and CH3COC6H5 CH2 OH
(iii) CH3—C—C6H5 in which >C=O group of (c) (d)
C6H5COCH3 is carbanion CH2 OH
CH2 COOH C
acceptor).
H—C
O

Exp. (b) 32. The increasing order of the pK a values of the

Heating of (CH ) COOH (adipic acid) with following compounds is
2 4
COOH OH OH OH OH
a dehydrating agent, decarboxylates ( CO 2 ) to give
a ketone (cyclopentanone), not an anhydride.
NO2
COOH D
O NO2 OMe
COOH –CO2
–H2O A B C D
(a) D < A < C < B (b) B < C < A < D
31. The major product ‘X’ formed in the following (c) C < B < A < D (d) B < C < D < A
reaction is [ JEE Main 2019, 10 Jan Shift-I]
O
O
CH2 C OCH3 Exp. (b)
NaBH4 Acidic strength is inversely proportional to pK a value.
X
MeOH The acidity of phenols is due to greater resonance
stabilisation of phenoxide ion relative to phenol.
O
Therefore, any substituent which stabilises the
OH OH
CH2 C OCH3 phenoxide ion more by dispersal of negative charge
CH2 CH2 OH will tend to increase the acidity of phenol.
(a) (b) Electron withdrawing groups ( NO 2 ) increases the
acidic strength of phenol whereas electron donating
O group ( OCH 3 ) decreases the acidic strength of
O OH
CH2 CH2 OH phenol. In case of NO 2 group attached to phenol,
CH2 C H the dispersal of negative charge is more pronounced
(c) (d) at o- and p-position than at m-position.
Thus, order of acidic strength of nitrophenol is:
p-nitrophenol > o-nitrophenol and the correct order of
Exp. (b) the pK a values of give option is
NaBH 4 is a selective reducing agent. It reduces OH OH OH OH
C O
carbonyl group into an alcohol but
cannot reduce an isolated C == C and an ester group < < <
too. NO2
Carbonyl NO2 OMe
group O
O (B) (C) (A) (D)
CH2 C OCH3
NaBH4
Ester MeOH
O CH3
group (i) Dil. HCl/∆
Isolated (ii) (COOH)2/
C C CH3O OH Polymerisation
O
OH
CH2 C OCH3 (a) —O
n
OH

(a) Tollen’s reagent

(b) —O O—
(b) I2 / NaOH
n
(c) Alkaline KMnO 4
(d) CrO 2Cl 2 /CS 2 [ JEE Main 2019, 10 Jan Shift-II]
OH
Exp. (b)
The most suitable reagent to carry out given
(c) —O O n transformation is I2/NaOH
OH

C H 3 C H==C H C H 2 C H  C H 3
OCH3 6 5 4 3 2 1
Strong
 oxidation, [O]
  →
(d) —O O— (Oxidative cleavage)
n O

OCOCH3 C H 3 C H == C HC H 2 C — OH +CHI 3 ↓ + CO 2 ↑
6 5 4 3 2
Here, the haloform reaction will give following
Exp. (c) reaction:
In the given reaction, ester get cleaved in presence of 2 4 6 s s
1 5 I2/OH I2/OH
dil. HCl and readily forms alcohol. This alcohol on 3
reaction with oxalic acid undergoes polymerisation [O]
OH O
reaction.
Hydrolysis of CI3 s 2 4 OH + CHI3
the ester group OH 5
H
1 3 (G)
CH3
O OH O O (Yellow ppt.)
Dil. HCl/D
Me – CH3COOH (i) Tollen’s reagent (AgNO 3 + NH4OH) is a mild
O
O OH
{
Ether group
oxidising agent. It does not react with
O O
remains unaffected CH CH3 group (2°-alcohol).
by dil. HCl (hot)
OH OH C C OH 
OH
Me (ii) Alkaline KMnO 4 cannot perform the oxidative
O O H OH C C OH cleavage, rather it will hydroxylate the C == C.
O O OH

(COOH)2/Polymerisation
CH3 CH == CH CH2 CH  CH3
–H2O 6 5 4 3 2 1
KMnO
 
4
→
O OH −
O OH OH OH
O   
O n CH3 CH  CH  CH2 CH  CH3
6 5 4 3 2 1
OCH3 (iv) CrO 2Cl 2 / CS2 will not react here.
34. Which is the most suitable reagent for the 35. The major product of the following reaction is
following transformation ? CH3
OH
OH
 (i) aq. NaOH
CH3  CH ==CH  CH2  C H  CH3 → (ii) CH3I
CH3  CH == CH  CH2CO2H

CH3 CH3 addition which on hydrolysis followed by heating

OH gives the required product.
OH
(a) (b) More acidic
CH3 CH3 H H
CO2Et O
s r
CH3 CH3 EtONa
O –EtOH s CO2Et
OCH3 OH O O
(c) (d) (Nucleophilic
addition)
CH3 O
H 2O
s CO2Et
[ JEE Main 2019, 10 Jan Shift-II] –OH
s
O
Exp. (c) EtO
s
–H
Substituted phenols react with aq.NaOH to form O cidic b
H
more a
sodium phenoxides which on reaction with CH 3I CO2Et
undergoes SN 2 reaction to give 2-methoxy-1-methyl
a, b-eliminatioin –EtOH OH
benzene.
–OHs
CH3 O
OH CO2Et
NaOH (aq)
Acid-base reaction
–H2O 37. The major product of the following reaction is
CH3 CH3 OH
s r
O Na d+ d– OCH3 Br2 (excess)
CH3 I
SN2 reaction
–NaI 2-methoxy-1- SO3H
methyl benzene
OH OH
36. The major product obtained in the following Br
reaction is (a) (b)
CO2Et Br Br
NaOEt/∆ Br SO3H
OH OH
Br Br Br Br
(b) (c) (d)
(a)
CO2Et
CO2Et Br SO3H

(c) (d) Exp. (c)
CO2Et
OH
CO2Et
[ JEE Main 2019, 10 Jan Shift-II] In , ipso-substitution takes place with the
carbon bearing SO 3H group. After
Exp. (b) the attack of the electrophilic Br + in the
In presence of strong base, acidic H can easily be SO3H rate determining step (rds) of the ArS 2
E
removed that result in formation of anion. The pathway desulphonation ( SO 3 ) takes place with a
resulting anion undergoes intramolecular nucleophilic faster rate.

HO Cl
(+R) O—H O—H OH
(rds) (fast) (a) (b)
Br2/H2O –SO3
(Br ) –H
Br—Br S Br Cl
SO3H Br HO
—Br (c) (d)
H
OH
(i) 2 moles of Br2 [ JEE Main 2019, 11 Jan Shift-II]
Br Br
(ii) Attack at ortho- 1 Exp. (a)
and ortho-2 by Br+
(iii) –2HBr In the given reaction, AlCl 3 helps in the generation of
electrophile that further undergoes ArSE 2 reaction to
Br
A white ppt. of give the required product.
2,4,6-tribromophenol
HO AlCl3
H—Cl
38. The major product of the following reaction is –AlCl s
4
COCH3
(i) KMnO4/KOH,∆ HO
(ii) H2SO4 (dil.)
CH3
COOH COCH3
Intramolecular
(a) (b) ArSE2 reaction
HOOC HOOC H
COOH COCOOH
(c) (d) HO –HCl O
–AlCl3
OHC HOOC AlCls4
H
It does not show SN reaction
Exp. (a) with HCl because of double bond
In presence of alkaline KMnO 4 , vigorous oxidation of nature of the O—C bond, (due
alkyl or acyl benzene takes place. During oxidation, to +R-effect of the —OH group.)
aromatic nucleus remains intact but the entire chain is
oxidised to —COOH group irrespective of the length 40. Which of the following compounds reacts with
of carbon chain. ethyl magnesium bromide and also
Oxidative cleavage decolourises bromine water solution
O==C—CH3 in strong
– – –
O ==C—O K
(MnO4 /OH /D) CN OCH3
KMnO4/KOH/∆ CH2—CO2CH3 CH
Strong oxidation, [O] (a) (b) CH2
CH3 COOK OH
(also H3O+(dil. H2SO4) CN
oxidisable)
COOH
(c) (d)
COOH
Exp. (c)
Ethyl magnesium bromide is a Grignard reagent (GR),
⊕
39. The major product of the following reaction is it constitutes C 2H –5 [C 2H –5 MgBr in ether/aprotic
HO medium] which can act as nucleophile as well as
(i) HCI strong base. Bromine water (Br2/H 2O, red) gets
(ii) AlCl3 (Anhyd.) decolourised with phenol derivatives (option, c),

anisole derivatives (option, b) etc., as C==C is Exp. (b)

present outside the ring (aliphatic, not aromatic). LiAlH 4 acts as a nucleophilic reducing agent that can
δ+ δ– reduce COOH to CH 2OH, C == O
C≡N Et group can react

into C H OH and NO 2 into NH 2, but it
δ+ δ–

(a) CH2—C—OMe
cannot reduce isolated C==C
δ–
O OH isolated C==C OH
(Br2/H2O does not react)
OCH3 Br LiAlH4 (excess)
H CH3
OCH3 Br2/H2O
H
(excess) Br NO2 NH2 OH
(b) EtMgBr Compound
No reaction (b)
OH Br
H
42. The major product obtained in the following
Acidic 'H' Br2/H2O conversion is
H
(excess)
Br CH3
OH
O Mg Br
O Br2 (1 eqv.)
(c)
Et MgBr MeOH
+ C2H6
[Et acts as a base]
δ+ δ– δ–
N≡C
CH3 O CH3 O
δ+
(d) O O OMe
Br
(a) (b)
Et group can react but (Br2/H2O) does not react OMe
Br
41. The major product obtained in the following O O
reaction is
OH CH3 O CH3 O
Br
LiAlH4 O O
(excess)
CH3 (c) (d)
NO2 O Br O
OH OH [JEE Main 2019, 11 Jan Shift-II]
(a) (b)
Exp. (b)
CH3 CH3 In presence of Br2/EtOH, the reactant containing
double bond undergoes electrophilic addition
NO2 OH NH2 OH reaction via the formation of bromonium ion. On
••
OH OH further attack of  OMe on bromonium ion gives the
••
addition product.
(c) (d)
CH3 CH3
NO2 OH NH2 OH

H 3C COMe
O OH
O
Br2(1 eqiv)
in MeOH
O MeOH 
Br 44. CH3CH2 C  CH3 cannot be prepared by
(Protic solvent)

Ph
O
O (a) CH3CH2COCH3 + PhMgX

O (b) PhCOCH3 + CH3CH2MgX
OMe (c) PhCOCH2CH3 + CH3MgX
Br (d) HCHO + PhCH(CH3 ) CH2MgX
(Major)
Exp. (d)
43. The major product of the following reaction is OH

CN CH 3CH 2 C  CH 3 cannot be prepared by HCHO
(i) DIBAL-H 
O (ii) H3O+ Ph
andPhCH(CH 3 )CH 2MgX. This can be easily illustrated
O by following reaction.
CHO CHO
(a) (b) O
O O d– d+ d – d+
H C H + PhCH CH2 MgX Ph CHCH2 CH2 O MgX
O
CH3 CH3
CH NH CHO
(c) (d) H3O+
OH OH
Ph CH (CH2)2 OH
OH
CHO
CH3
The obtained product is not the required substance.
Exp. (d) While option (a), (b) and (c) can readily prepare the
DIBAL-H (Diisobutylaluminium hydride) is a reducing required substance.
agent with formula [λ-Bu2AlH]. At ordinary The reactions are as follows :
temperatures, nitriles give imines which are readily
converted in aldehydes by hydrolysis whereas d – d+
O O MgX
lactones are reduced directly to aldehydes.
d– d+
H Ph C CH2 CH3 + CH3MgX Ph C CH2CH3
Al Al Al
CH3
+ (DIBAL–H) + H (DIBAL–H)
N N
CN OH
C C H H3O+
Ph C CH2CH3
O
O O
CH3
O
O O d – d+
O O MgX
H2O d– d+
Ph C CH3 + CH3CH2MgX Ph C CH3
CHO CHO CHO
+H+ DIBAL–H CH2CH3
(Hs)
OH O O
OH
H
O –O O H3O+
H Ph C CH3
CH2CH3

d – d+
O O MgX 46. In the following reactions, products A and B are
d – d+
CH3CH2 C CH3 + PhMgX CH3CH2 C CH3 O O
Dil. NaOH
H 3C H [A ]
Ph H 3C CH3
H3O+
OH [A] ∆
[B]
H3O+ O O
CH3CH2 C CH3 CH3 CH3
(a) A= CH3 ; B= CH3
Ph
HO
O O
45. In the following reaction, CH3 CH3
Aldehyde + Alcohol  
→ Acetal HCl (b) A= CH3 ; B= CH3
HO
Aldehyde Alcohol
t O
HCHO BuOH O
OH CH3
C
CH3CHO MeOH H H
HC
(c) A= 3 ; B=
The best combination is
(a) CH3CHO and MeOH (b) CH3CHO and t BuOH H 3C
CH3
H 3C
CH3
t
(c) HCHO and MeOH (d) HCHO and BuOH O
O
[JEE Main 2019, 12 Jan Shift-I] OH
C H2 C
H H
Exp. (c) A= H3C ; B=
(d)
Acetal formation is nucleophilic addition reaction due
H 3C H 3C
to the addition of alcohols on aldehydes. CH3 CH3
The reactivity of nucleophilic addition depends on
following two factors.
● Inductive effect Greater the number of alkyl Exp. (b)
group attached to carbonyl group, greater is The reactant in presence of Dil. NaOH undergoes
the electron density on carbonyl carbon. Thus, intramolecular aldol condensation reaction.
lowers the attack of nucleophile. Hence, As a result of this, β-hydroxyketone (A) is obtained
reactivity decreases. which on hydrolysis followed by heating produces
● Steric effect As the number of alkyl group α, β-unsaturated ketone (B)
attached to carbonyl carbon increases, the O O O O
attack of nucleophile on carbonyl group dil.
becomes more difficult due to steric hinderance. H 3C H NaOH s H
H 3C CH3
Thus, the best combination is HCHO and MeOH. The
reaction is as follows: O O
O OH
H2 O
HCl s
H C H + MeOH H C H HO O
D –H O
2 H H
(A)
OMe
O
OMe
MeOH
H C H
OMe (B)
Acetal

O O
47. The increasing order of the reactivity of the  
following with LiAlH4 is > C 2H 5 C OCH 3 > CH 3 C NH 2
(B) Least reactive
O (A)
(A) Note The −I-effect of —Cl and + m-effects of
O
C2H5 NH2
•• 
O  NH 2  O C  C 2H 5 and  OCH 3 groups while
(B) attached to C  group to be reduced
C2H5 OCH3 
O
O Also, add to the group leaving ability.
(C)
C2H5 Cl 48. The aldehydes which will not form Grignard
product with one equivalent Grignard
O O
reagents are
(D)
CHO CHO
C2H5 O C2H5
(A) (B)
(a) ( A ) < ( B ) < (D ) < (C ) HO2C
(b) ( A ) < ( B ) < (C ) < (D ) CHO
CHO
(c) ( B ) < ( A ) < (D ) < (C )
(C) (D)
(d) ( B ) < ( A ) < (C ) < (D )
HO3CO HOH2C
[JEE Main 2019, 12 Jan (Shift-II)
(a) (C ), (D ) (b) ( B ), (D )
Exp. (a)
(c) ( B ), (C ), (D ) (d) ( B ), (C )
All the given compounds are acid derivatives, thus
contain carbonyl group
in them. LiAlH 4 reduces these compounds through
nucleophilic substitution via addition elimination
Exp. (b)
(S NA E) reaction. The rate of reaction depends upon
Key Idea Grignard reagent usually attacks on
the following factors :
> C ==O group as
(i) Size of alkyl group. ( C == O + RMgX →
(ii) Steric hinderance around the > C == O group. '
(iii) (+ ) ve charge on the C-atom of > C == O group. ( C ' OMgX →
Hydration ( C ' OH
The alkyl groups are more or less same in the given ' (R − Mg (OH) X ' (R
(Ionic salt)
compounds. Thus, the reactivity order of given
compounds depends upon 2nd and 3rd factor
written above. The cumulative effect of these two The question is related to above reaction only with the
factors results to leaving group ability (LGA) of the condition that the consumption of RMgX will be more
substituents in the following order : than 1 equivalent in some of the given cases.
O Among the given compounds B, i.e.
 − CHO CHO
Cl − > O − C CH 3 > O CH 3 > NH 2
Good leaving Poor leaving
group group
HO2C and D, i.e. HOH2C
This leaving group ability (weak conjugate
base) corresponds directly to the reactivity order. contain additional groups which can give active
Hence, the correct reactivity order is: hydrogens. Grignard reagents produce alkanes
whenever come in contact with any group or
O O O compound which can give active hydrogen as:
 OR
C 2H 5 C Cl > C2H5 O C2H5 ROH + R ′ MgX Dry→ R ′ H + Mg '
ether (X
Most reactive (D)

These reactions are equivalent to acid-base

reactions. So, in both of these compounds more than
50. Phenol on treatment with CO2 in the presence
one equivalent will be required to form Grignard of NaOH followed by acidification produces
products. Remember these compounds will give 2 compound X as the major product. X on
type of products as: treatment with (CH3CO)2 O in the presence of
(i) from the >C ==O group catalytic amount of H2SO 4 produces:
(ii) from the group which release active hydrogen [JEE Main 2018]
O
The additional reactions involved are:
CHO CHO O
Dry O CH3
(i) + RMg X RH +
ether O CH3
HO2C δ+ δ– C
X MgO (a) (b)
O
CO2H
CHO CHO
Dry CO2H
(ii) + RMg X + RH
ether
HOH2C XMgOH2C O CO2H
O CH3
C
O
49. The major product of the following reaction is (c) OH (d)
O CO2H
NaBH4 O CH3
EtOH
O
OH O Exp. (a)
OH
Followed by
(a) (b) + CO2+NaOH acidification
X
(CH3CO)2O
conc. H2SO4
OH OH (Catalytic amount)
?
(c) (d) The very first reaction in the above road map looks
like Kolbe’s reaction which results to salicylic acid as
OEt
OH OH
[JEE Main 2019, 12 Jan Shift-II] (i) CO2, NaOH
(ii) Acidification
Exp. (a) COOH
Reducing agents like LiAlH 4 , NaBH 4 , i.e. complex Salicylic acid
(X)
hydrides usually does not affect olifenic or π-bonds.
O The salicylic acid with acetic anhydride [(CH 3CO)2O] in
the presence of catalytic amount of conc. H 2SO 4
undergoes acylation to produce aspirin as
Thus, if NaBH 4 is applied to a compound like O
then its ( C == O bond will be reduced only and we CH3 C
' O
O
OH OH + CH3 C
O—C—CH3
Conc.
O + CH3COOH
H2SO4
get as the final product. COOH
COOH
Acetyl salicylic acid (Aspirin)
Aspirin is a non-narcotic analgesic (Pain killer).

Cross conjugation due to which lone pair of

51. Phenol reacts with methyl chloroformate in oxygen 1 will be easily available to ring resulting to
the presence of NaOH to form product A. higher electron density at 2, 4, 6 position with
A reacts with Br 2 to form product B. A and B respect to group. However from the stability point
are respectively [JEE Main 2018] of view ortho positions are not preferred by
substituents as group O C O CH3 is bulky.
OH Br OH
Hence, on further bromination || of SN AE product
(a) and
OCH3 OCH3 para bromo derivative will beOthe preferred product
i.e.
O O O C O CH3 O C O CH3
O O O O
O O
(b) and + Br2 + HBr
O O
Br Br
O O O O
(c) and
52. The major product formed in the following
O O reaction is [JEE Main 2018]
Br
OH OH
(d) and O HI
OCH3 OCH3 Heat
O
O Br O
OH I
Exp. (c) (a) (b)
Given OH I
OH
NaOH
+ Methyl chloroformate A
OH I
Br2 (c) (d)
B I OH
In the above road map, first reaction appears as
acid base reaction followed by SN AE (Nucleophilic Exp. (d)
substitution through Addition and Elimination). Both
the steps are shown below / The reaction given is a nucleophilic
(i) Acid base reaction substitution reaction in which cleavage at
CO bond is visible. The product
formation can be visualised with the help of
following analysis.
These two atoms are directly
(ii) SN AE attached to benzene ring.
O a O Hence, development of
O any charge on these atoms is
–
O O C OCH3 stabilised by the ring itself due
Cl C OCH3 O b to conjugation (Resonance)
If any one properly visualise the fact written

In the product of SN AE the attached group is ortho with figure above, than a conclusion can be
and para-directing due to following cross conjugation made that C O bonds marked (a) and (b) in
the figure will undergo heterolysis during the
O
reaction.
δ–
6 O1 C O 2 CH3
5 1
4 2
δ– 3 δ–

The reaction can be represented as (c) CH3 MgBr, [Ag(NH3 )2 ]+ OH− , H+ / CH3OH
(d) [Ag(NH3 )2 ]+ OH− , CH3 MgBr, H+ / CH3OH
O HI I
Heat Exp. (a)
O
OH
O O O
+ I + CH3OH
[Ag (NH3)2]OH Esterification
Mechanism
Tollen’s reagent CH3OH, H+
Step I The reaction begins with the attack of H+ of
HI on oxygen to form oxonium ion as CHO COOH COOCH3
+
O O CH3MgBr
HI (Excess)
∆ H
O O HO CH3
Oxonium ion
Step II This oxonium ion undergoes lysis and
addition of I − to form two products as
+
O OH
I– I + CH OH
H 3
O O Before final product is formed, intermediate is
Step III Similar pathway is followed at the other HO CH3
oxygen atom, which can be visualised as
I HI I
∆ +
O O O CH3
H
54. Sodium salt of an organic acid ‘X ’ produces
I–
effervescence with conc. H 2SO4 . ‘X ’ reacts
with the acidified aqueous CaCl 2 solution to
I
+ CH3CH2I give a white precipitate which decolourises
O acidic solution of KMnO4 . ‘X ’ is
H
(a) C6 H5COONa (b) HCOONa
Note Mechanism of a reaction is always a logical (c) CH3COONa (d) Na 2C2O 4
sequencing of events which may occur simultaneously as
well. Exp. (d)
53. The correct sequence of reagents for the The reaction takes place as follows
following conversion will be Na 2C 2O 4 +H2SO 4 → Na 2 SO 4 +H2O
[JEE Main 2017 (Offline)] (X ) (conc. ) + CO ↑ + CO 2 ↑
Effervescence
O HO CH3
Na 2C 2O 4 + CaCl 2 → CaC 2O 4 + 2NaCl
(X ) White ppt.
5CaC 2O 4 + 2KMnO 4 + 8H2SO 4 → K 2SO 4

Purple
CHO H3C OH
CH3 + 5CaSO 4 + 2MnSO 4 + 10CO 2 + 8H2O
Hence, X is Na2C2O4 . Colourless
(a) [Ag(NH3 )2 ]+ OH− , H+ / CH3OH, CH3 MgBr
(b) CH3 MgBr, H+ / CH3OH, [Ag(NH3 )2 ]+ OH−

55. The major product obtained in the Exp. (a)

following reaction is [JEE Main 2017 (Offline)] NBS
hν
O
O
Br Br
DIBAL-H
+
COOH
H2O/K2CO3
OH OH HO OH
+
(a) CHO (b) CHO
COOH CHO
57. Which compound would give
5-keto-2-methyl hexanal upon ozonolysis?
(c) CHO (d) CHO
[JEE Main 2015]
COOH CHO CH3 CH3
CH3
Exp. (a) (a) (b)
DIBAL-H (Di-isobutyl aluminium hydride) is a
CH3
reducing agent with formula. This is generally
used for the preparation of aldehydes. Using CH3 CH3
DIBAL H, Lactones are reduced directly to H3C
aldehydes. (c) (d)
O
OH CH3
O
DIBAL–H
CHO Exp. (b)
(a) CH3
COOH
COOH CH3
O3
56. The product of the reaction given below is ∇
[JEE Main 2016 (Offline)] Zn,H2O2
O O
(i) NBS/hν || ||
X CH3 — C —CH2 — CH2 — CH2 — C —CH3
(ii) H2O/K2CO3
Heptan-2,6-dione
(b) CH3
OH O
O3
(a) (b) ∇
Zn,H2O2
CH3
O
CO2H 6 || 5 4 3 2 1
(c) (d) CH3 —C — CH 2 —CH 2 — CH —CH O
|
CH3
5-keto-2-methyl hexanal

(c) CH3
59. Sodium phenoxide when heated with CO2
O3 under pressure at 125°C yields a product
∇ which on acetylation producesC .
Zn,H2O2
H3C ONa +
125°C H
O CH3 + CO2 B C
5 atm Ac2O
|| |
CH3 —C —CH2 — CH — CH2 — CHO [JEE Main 2014]
5-keto-3-methyl hexanal The major productC would be
(d) CH3 OCOCH3 OH
H3C
COOH COCH3
O3
∇ (a) (b)
Zn,H2O2
O CH3 COCH3
|| |
CH3 —C —CH —CH2 — CH2 — CHO OH OCOCH3
5-keto-4-methyl hexanal COOCH3
(c) (d)
58. In the following sequence of reaction,
KMnO SOCl H /Pd COOH
Toluene →
4
A →
2
B →
2
BaSO
C
4
Exp. (a)
The product C is [JEE Main 2015]
s r
(a) C6 H5 COOH (b) C6 H5CH3 ONa Os
(c) C6 H5CH2OH (d) C6 H5CHO +
e + Na
Exp. (d)
− + +
Toluene undergoes oxidation with KMnO 4 , forms O O O
benzoic acid. In this conversion, alkyl part of toluene H O−
converts into carboxylic group. Further, benzoic - O= C= O C
acid reacts with thionyl chloride (SOCl 2 ) to give O
benzoyl chloride which upon reduction with H2 /Pd or
BaSO 4 forms benzaldehyde (Rosenmund
Reduction). OH OH
−
COOH COO
The conversion look like,
H+
O Cl
CH3 COOH C
(B)
OCOCH3
KMnO4 SOCl2
+ SO2 + HCl COOH
(CH3CO)2O
(A) (B)
Toluene Benzoic Benzoyl chloride (C)
acid H2 / Pd (Rosenmund
BaSO4 reaction) 60. The most suitable reagent for the
O H
conversion of R  CH 2  OH → R  CHO
C is [JEE Main 2014]
(a) KMnO 4
(b) K 2Cr2O 7
+ HCl
(c) CrO 3
(d) PCC [Pyridinium chlorochromate]
(C)
Benzaldehyde

Exp. (d) 63. An unknown alcohol is treated with the

Mild oxidising agents like PCC [Pyridinium ‘Lucas reagent’ to determine whether the
chlorochromate] are particularly used for the alcohol is primary, secondary or tertiary.
conversion of R  CH2OH → R  CHO. Which alcohol reacts fastest and by what
mechanism? [JEE Main 2013]
61. In the reaction, (a) Secondary alcohol by S N 1

LiAlH 4 PCl 5 alc ⋅ KOH (b) Tertiary alcohol by S N 1
CH 3COOH → A → B → C (c) Secondary alcohol by S N 2
(d) Tertiary alcohol by S N 2
the productC is [JEE Main 2014]
(a) acetaldehyde (b) acetylene Exp. (b)
(c) ethylene (d) acetylchloride The reaction of alcohol with Lucas reagent is
mostly SN1 reaction and the rate of reaction is
Exp. (c) directly proportional to the stability of carbocation
formed in the reaction.
The complete series of reaction can be
represented as Since 3° R OH forms 3° carbocation (most
LiAlH4 PCl5 stable) hence it will react fastest by SN1reaction.
CH3COOH CH3CH2OH
(A ) 64. Aspirin is known as [AIEEE 2012]
(a) acetyl salicylic acid (b) phenyl salicylate
CH3CH2Cl + POCl3 + HCl
(c) acetyl salicylate (d) methyl salicylic acid
elimination alc.KOH
reaction
Exp. (a)
CH2=CH2
(C) Aspirin is acetyl derivative of salicylic acid.
OH O—COCH3
62. Arrange the following compounds in the
order of decreasing acidity [JEE Main 2013] COOH COOH
OH OH OH OH + CH3COCl
; ; ; Acetyl salicylic acid
Cl CH3 NO2 OCH3

65. Ortho-nitrophenol is less soluble in water
than p- and m-nitrophenols because
I II III IV (a) o-nitrophenol is more volatile steam than
(a) II > IV > I > III (b) I > II > III > IV those of m- and p-isomers.
(c) III > I > II > IV (d) IV > III > I > II (b) o-nitrophenol shows intramolecular
H-bonding
Exp. (c) (c) o-nitrophenol shows intermolecular
OH OH OH OH H-bonding
(d) melting point of o-nitrophenol is lower than
those of m- and p-isomers [AIEEE 2012]
> > >
Exp. (b)
NO2 Cl CH3 OCH3
(strong There is intramolecular H-bonding in o-nitrophenol
(–I (+I,hyper (strong
–M,–I effect) conjugation) +M and thus solubility in water is decreased.
effect) effect) O δ+
Electron releasing group decreases while electron
H
δ– intramolecular H-bonding
withdrawing group increases acidic strength by δ+ O
destabilising and stabilising the phenoxide ion N
formed respectively.
O

66. In the given transformation, which the Exp. (d)

following is the most appropriate reagent? Br 2 is formed by a redox reaction.
[AIEEE 2012] 5Br – + BrO –3 + 6H+ → 3Br2 + 3H2O
CH CHCOCH3 —OH group is the activating group and thus
Reagent activates the benzene towards electrophilic

substitution reaction at o-and p-positions giving
HO yellowish white precipitate of 2,4,6-tribromophenol.
CH CHCH2CH3 OH OH
Br Br
HO + 3Br2 + 3HBr
s
(a) NH2 NH2 , O H (b) Zn -Hg / HCl
Br
(c) Na, Liq. NH3 (d) NaBH4
68. Which of the following reagents may be used
Exp. (a) to distinguish between phenol and benzoic
CH CHCOCH3 acid ? [AIEEE 2011]
(a) (a) Aqueous NaOH
HO (b) Tollen’s reagent
(c) Molisch reagent
(d) Neutral FeCl 3
NH2NH2, OH – glycol
Exp. (d)
CH CHCH2CH3 Reagent Phenol Benzoic acid Conclusion
(a) Aqueous Salt Salt formation No specific
NaOH formation colour change
HO (b) Tollen’s No effect No effect
(Wolff-Kishner) reagent
(c) Molisch No effect No effect
Cl reagent
CHCH2COCH3 (d) Neutral Violet Buff- Thus, FeCl 3 can
Zn(Hg)/HCl FeCl 3 colour coloured be used to
(b) precipitate make distinction
Cl
HCl attacks 2° alcohol as well as (C==C) bond.
69. Trichloroacetaldehyde was subjected to
Cannizzaro’s reaction by using NaOH. The
CH CHCOCH3 mixture of the products contains sodium
Na/NH3
(c) trichloroacetate ion and another
compound. The other compound is
NaO
(a) 2, 2, 2-trichlorethanol [AIEEE 2011]
NaBH4 (b) trichloromethanol
(d) Low yield (c) 2, 2, 2-trichloropropanol
67. Phenol is heated with a solution of mixture (d) chloroform
of KBr and KBrO3. The major product Exp. (a)
obtained in the above reaction is[AIEEE 2011]
(a) 2-bromophenol Cannizzaro’s reaction is given by aldehydes
(RCHO) lacking H at α-carbon or lacking α-carbon
(b) 3-bromophenol
(as in HCHO). With NaOH, there is formation of
(c) 4-bromophenol
acid salt (RCOO – ) by oxidation and alcohol
(d) 2, 4, 6-tribromophenol (RCH2OH) by reduction.

Cl

Exp. (d)
2Cl —— C—— CHO + NaOH → −
C 2H5O Na + s C 2H5O — +Na +
 s
Cl O O
α -carbon without H
Cl O Cl CH3 — C — Cl e CH — C — Cl
| || | 3 r C2H5O–
Cl ——C —— CONa + Cl —— C —— CH 2OH (ethanoyl chloride)
| |
Cl Cl s
(By oxidation) (By reduction 2, 2, 2, O O
trichloroethanol)
CH3 — C — Cl CH3 — C — OC2H5 + Cl–
70. The strongest acid amongst the following
compounds is [AIEEE 2011] O — C2H5
(a) CH3COOH
(b) HCOOH Na + + Cl — → NaCl
(c) CH3CH2CH(Cl)CO 2 H This is by SN reaction. Cl − is a better leaving group
(d) ClCH2CH2CH2COOH than C 2H5O − and the ethyl ethanoate is formed.
Exp. (c) 72. Silver mirror test is given by which one of the
following compounds? [AIEEE 2011]
− I effect exerting (electron withdrawing) groups
increases the acidic strength of an acid by (a) Acetaldehyde (b) Acetone
withdrawing electron density towards itself, they (c) Formaldehyde (d) Benzophenone
weakning OH bond and thus, the release of
H+ ion by an acid becomes easier.
Exp. (a, c)
Whereas +I effect excerting (e − releasing) groups All aldehydes including reducing sugar (as
decreases the acidic strength by donating glucose, fructose) gives Silver-mirror test (with
electron density to O-atom. Further, − I effect Tollen’s reagent)
decreases with distance. Thus, the acidic strength ∆
of the given acids would be RCHO +2[Ag(NH3 )2 ]+ + 3OH–  →
O RCOO – + 2Ag ↓ + 4NH3 + 2H2O

Silver mirror
CH3 CH2 CH C OH
(R= H, CH3 )
O
Cl Thus, acetaldehyde and formaldehyde give
silver-mirror test.
CI  CH2  CH2  CH2 C  OH >
O O
73. The correct order of acid strength of the
following compounds is [AIEEE 2011]
CH3 C  OH > H  C  OH
I. Phenol II. p-cresol
O III. m-nitrophenol IV. p-nitrophenol

Hence, CH3 CH2 CH  C OH is most acidic and (a) III > II > I > IV (b) IV > III > I > II
 (c) II > IV > I > III (d) I > II > IV > III
Cl
Exp. (b)
strongest acid than other given compounds.
OH OÈ
71. Sodium ethoxide has reacted with ethanoyl
chloride. The compound that is produced in +
the above reaction is [AIEEE 2011] I. l + H
(a) diethyl ether (b) 2-butanone
phenoxide
(c) ethyl chloride (d) ethyl ethanoate

Acidic due to resonance stabilisation of

phenoxide ion.
75. From amongst the following alcohols the
one that would react fastest with conc. HCl
O—H
and anhydrous ZnCl 2 is [AIEEE 2010]
(a) 2-butanol (b) 2-methylpropan-2-l
II. (c) 2-methylpropanol (d) 1-butanol
Exp. (b)
CH3 The reaction of alcohol with conc. HCl and
—CH3 group releases electrons, destabilises anhydrous ZnCl 2 follows SN1 pathway, so greater
the phenoxide ion, thus acidic nature is the stability of carbocation formed, faster is the
decreased hence II < I (acidic). reaction.2-methylpropan-2-ol gives 3° carbocation.
OH Hence, it reacts rapidly with conc. HCl and
anhydrous ZnCl 2 (Lucas reagent).
III. 76. The main product of the following reaction is

NO2 Conc. H 2SO 4
C 6H 5CH 2CH(OH)CH(CH 3 )2 → ?
—NO 2 withdraws electrons, stabilises the
phenoxide ion, hence acidity is increased. [AIEEE 2010]
IV. Lower acidity in case of meta-isomer as H5C6 H
compared to para-isomer is explained by the (a) C == C
fact that m-nitrophenoxide is stabilised by
H CH(CH3 ) 2
inductive effect only and no resonance effect
operates with −NO 2 group. C6 H5CH2 CH3
Thus, m-nitrophenol < p-nitrophenol (acidic) (b) C == C
(III) (IV) H CH3
Thus, correct order is IV > III > I > II H5C6 CH(CH3 ) 2
(c) C == C
74. Consider the following reaction, H H
C 2H 5OH + H 2SO4 → Product
H5C6CH2CH2
Among the following, which one cannot be (d) C == CH
H2
formed as a product under any conditions? H3C
(a) Ethyl hydrogen sulphate [AIEEE 2011]
(b) Ethylene
Exp. (a)
(c) Acetylene −
H2SO4 H + HSO4
(d) Diethyl ether
OH
Exp. (c) +
Room temp.
 CH3 H
C6H5  CH2  CH  CH 
C2H5OH + H2SO4 CH3
H
C2H5HSO4 +
Ethylhydrogen sulphate O

 CH3
C6H5  CH2  CH  CH 
0°
17
CH3
–H
14
0°
5O
2
SO
2H
4
C
C6H5  CH  CH  C CH3
C2H5OC2H5 CH2==CH2 CH3
Diethyl ether Ethylene H H
[β1] [β2]
(a), (b), (d) may be formed but (c) is never formed.

By the loss of β1 -H
79. Which of the following on heating with
 CH3
C6H5 — CH == CH — CH 
aqueous KOH, produces acetaldehyde?
CH3 [AIEEE 2009]
Extension of conjugation By the loss of
β2 - H (a) CH3COCl (b) CH3CH2Cl
(More stable)
(c) CH2ClCH2Cl (d) CH3CHCl 2

(Major product)
CH3 Exp. (d)
C6H5 — CH2 — CH == C
CH3 O O
(Less stable)
(Minor product)  KOH ( aq ) 
CH3 C  Cl → CH3  C  OH + KCl
77. A liquid was mixed with ethanol and a drop [SN reaction]
of concentrated H 2SO4 was added. A KOH ( aq )
CH3  CH2  Cl → CH3  CH2  OH
compound with a fruity smell was formed. [S N 2 reaction]
The liquid was [AIEEE 2009]
KOH ( aq )
(a) CH3OH (b) HCHO Cl  CH2  CH2  Cl → CH2  CH2
(c) CH3COCH3 (d) CH3COOH  
OH OH
Exp. (d) [S N 2 reaction]
Conc. H 2SO 4 KOH ( aq )
A liquid +C 2H5OH → Compound CH3  CH  Cl → CH3  CH  OH
(Fruity smell)  
Fruity smell is the characteristic property of ester, Cl OH
thus the above reaction leads to the formation of (unstable)
ester. O
− H 2O 

Conc. H SO → CH3  C  H
CH3COOH + C 2H5OH → 2 4
O (acetaldehyde )

CH3 C — OC 2H5 + H2O 80. In Cannizzaro reaction given below
Ethyl acetate OHs
(Fruity smell) 2PhCHO → PhCH 2OH + PhCOs2
This reaction is called esterification. the slowest step is [AIEEE 2009]
78. The major product obtained on interaction (a) the attack of : : OHs at the carboxyl group
of phenol with sodium hydroxide and (b) the transfer of hydride to the carbonyl group
carbon dioxide is [AIEEE 2009] (c) the abstraction of proton from the carboxylic
(a) benzoic acid (b) salicylaldehyde group
(c) salicylic acid (d) phthalic acid (d) the deprotonation of PhCH2OH
Exp. (c) Exp. (b)
OH OH In Cannizaro reaction, the transfer of H− to a
carbonyl group is a slowest step of the reaction and
—COONa hence, it is a rate determining step of the reaction.
NaOH -
CO2 O O
OH – Ph  CH==O
+ Ph  C  H Ph CH
H (fast) Hydride transfer
(Nucleophilic attack) (slow)
OH OH
O
—COOH
Ph  C  OH + Ph  CH2  O–
+
H
transfer H  OH
Salicylic acid
The above reaction is called Kolbe’s reaction.
Ph  CH2  OH

81. Phenol, when it first reacts with Exp. (c)

concentrated sulphuric acid and then P + I2 Mg, ether
with concentrated nitric acid gives [AIEEE CH3CH2OH → CH3CH2 I →
 H PO A
2008] 3 3
(a) 2, 4, 6-trinitrobenzene O
 OMgI
(b) o-nitrophenol
H  C  H

(c) p-nitrophenol CH3CH2MgI → CH3 CH2  CH2
(d) nitrobenzene B C
OH
Exp. (b) H 2O 
→ CH3 CH2 CH2 + Mg(OH) I
OH OH D
n -propyl alcohol
SO3H
Conc. H2SO4
sulphonation
83. The compound formed as a result of oxidation
of ethyl benzene by KMnO4 is
(a) benzophenone [AIEEE 2007]
SO3H (b) acetophenone
OH (c) benzoic acid
(d) benzyl alcohol
O2N SO3H
Conc. HNO3 H3O+ Exp. (c)
Boil
Any aliphatic carbon with hydrogen attached to it, in
combination with benzene ring, will be oxidised to
SO3H benzoic acid by KMnO 4 / H+.
OH
84. Among the following the one that gives
positive iodoform test upon reaction with I 2
O2N and NaOH is [AIEEE 2006]
(a) CH3CH2CH(OH)CH2CH3
(b) C6 H5CH2CH2OH
O-nitrophenol CH3
First sulphonation is the means to block para (c) H3C

and ortho position and to reduce the reactivity of OH
phenolic ring against strong oxidising agent (d) PhCHOHCH3
HNO 3 . (The use of conc. HNO 3 over phenol
cause the oxidation of ring mainly).  SO 3H Exp. (d)
groups are knocked out on boiling with H2O.
For positive iodoform test, alcohol molecule must
82. In the following sequence of reactions, have CH3 CH  group.

P+I Mg OH
CH 3CH 2OH →
2
A → B
ether Thus, iodoform test is given by only (d)
HCHO H 2O Ph  CH  CH3 while others will not give this test.
→ C → D 
the compound ‘D’ is [AIEEE 2007] OH
(a) butanal I +NaOH
(b) n-butyl alcohol Ph CH CH3 →
2
CHI3 + Ph COO −

(c) n-propyl alcohol OH
(d) propanal

CH3 CH3
85. Phenyl magnesium bromide reacts with
Br
methanol to give [AIEEE 2006] Br2/H2O Br
(a) a mixture of anisol and Mg(OH)Br
(b) a mixture of benzene and Mg(OMe)Br
(c) a mixture of toluene and Mg(OH)Br OH OH

(d) a mixture of phenol and Mg(Me)Br
CH2OH CH2Br
Exp. (b)
PhMgBr can be protonated by any of the protic Br2/H2O
+ HBr
solvent e.g., CH3OH.
Br
Ph MgBr + CH3O H → Ph  H + Mg m-cresol due to phenoxide ion in H2O solvent,
Benzene OCH3 gives tribromoderivative at all ortho and para
Methoxy positions.
magnesium − +
bromide OH O Na
87. + CHCl + NaOH
86. The structure of the compound that gives a CHO
tribromo derivative on treatment with The electrophile involved in the above
bromine water is [AIEEE 2006] reaction is [AIEEE 2006]
CH3 CH2OH ⊕
(a) dichloromethyl cation (CHCl 2 )
(b) dichlorocarbene (: CCl 2 )
(a) (b)
(c) trichloromethyl anion (CCl 3 )
⊕
OH (d) formyl cation (C HO)
CH3 CH3 Exp. (b)
− −
OH + CHCl3 w H O + CCl
2 3
OH −
[from Na+OH ]
(c) (d) −
: CCl2 + Cl
Dichloro
carbene
OH +
(E)
O− O
Exp. (a)
H
CH3 CH3 −
+ : CCl2 CCl2
Br
Br2, H2O
s −
O O
OH OH
CHCl2
s OH
CH 
Br 2NaOH OH
Tribromoderivative − 2NaCl
(unstable)
CH3 CH3
− OH
Br O
OH Br2, H2O
CHO CHO
− H 2O H
OH
Br (2-hydroxybenzaldehyde)
Dibromoderivative

88. The increasing order of the rate of HCN 90. p-cresol reacts with chloroform in alkaline
addition to compounds A-D is [AIEEE 2006] medium to give the compound A which
(A) HCHO (B) CH3COCH3 adds hydrogen cyanide to form the
(C) PhCOCH3 (D) PhCOPh compound B. The latter, on acidic
A< B< C< D (b) D < B < C < A hydrolysis gives chiral carboxylic acid. The
(a)
(c) D< C< B< A (d) C < D < B < A structure of the carboxylic acid is
[AIEEE 2005]
Exp. (c) CH3
Addition of HCN is a nucleophilic reaction. Greater
the electron deficiency of C atom of carbonyl
group, higher the rate of reaction. (a)
O O
  CH2COOH
Hence, Ph C Ph < Ph C CH3
OH
O O
  CH2COOH
< CH3 C CH3 < H C  H
(b)
89. Acid catalysed hydration of alkenes except
ethene leads to the formation of [AIEEE 2005]
(a) mixture of secondary and tertiary alcohols OH
(b) mixture of primary and secondary alcohols
CH3
(c) secondary or tertiary alcohol
(d) primary alcohol
Exp. (c) (c)
Hydration of ethene gives 1° alcohol (ethanol)
while all other alkenes give either 2° or 3° alcohols. CH(OH)COOH
H 2O/H+ OH
CH2 == CH2 → CH3CH2OH
CH3
Ethene
H 2O/H+ CH(OH)COOH
CH3 CH == CH2 → CH3 CH CH3
 (d)
OH
⊕
[(2°alcohol) through 2° carbocation CH3 CHCH3 ]
H O/H+ OH
CH3 C == CH2 → 2
(CH3 )3 COH

CH3 Exp. (c)
⊕
[(3° alcohol) through 3° carbocation (CH3 )3 C] CH3 CH3 CH3
CHCl3 H ¾ CN OH
KOH (aq) (nucleophilic
CHO CHCN
(Riemer addition
CH3 CH3 OH Tieman OH reaction) OH (B)
| H2O/H+ | (p-cresol) reaction) (o-hydroxy
CH3 —CH—CH==CH 2 CH3CH—CH—CH3 p-methyl +
H2O/H
⊕ benzaldehyde) CH3
2° carbocation
1, 2 H– H 2O OH
shift
CH3 2° alcohol
| CHCOOH
H2O
CH3 — C — CH2—CH3 3° alcohol OH
⊕
3° carbocation

(i) PhCOOH
91. The best reagent to convert pent-3-en-2-ol
into pent-3-en-2-one is [AIEEE 2005] (ii) o -NO2C 6H 4COOH
(a) pyridinium chloro-chromate (iii) p -NO2C 6H 4COOH
(b) chromic anhydride in glacial acetic acid (iv) m-NO2C 6H 4COOH
(c) acidic dichromate

(d) acidic permanganate Which of the following order is correct ?
(a) (i) > (ii) > (iii) > (iv) [AIEEE 2004]
Exp. (b) (b) (ii) > (iv) > (iii) > (i)
2° (c) (ii) > (iv) > (i) > (iii)
CH3 CH CH ==CH CH3 →
 (d) (ii) > (iii) > (iv) > (i)
OH
CH3 C CH == CH  CH3 Exp. (d)

Only suitable reagent is chromic anhydride in COOH COOH
O
glacial acetic acid. Other will also effect (C == C)
bond.
(i) (ii)
92. Among the following compounds which can
be dehydrated very easily ? [AIEEE 2004]
(a) CH3CH2CH2CH2CH2OH NO2
OH
 COOH COOH
(b) CH3CH2CH2 CHCH3
NO2
CH3
| (iii) (iv)
(c) CH3CH2 C CH2CH3
| NO2
OH
NO 2 group at any position shows electron
(d) CH3CH2 CHCH2CH2OH withdrawing effect, thus acid strength is

CH3 increased. But o -nitro benzoate ion is stabilised
by intramolecular H-bonding like forces, hence its
Exp. (c)
acid strength is maximum. Thus, the order of acid
Dehydration of alcohol is in the order 1°< 2 ° < 3° strength is (ii) > (iii) > (iv) > (i).
Thus (c), a 3° alcohol is dehydrated very easily. The effect is more pronounced at para position
than meta.
93. Which one of the following undergoes
reaction with 50% sodium hydroxide 95. An ether is more volatile than an alcohol
solution to give the corresponding alcohol having the same molecular formula. This is
and acid? [AIEEE 2004] due to [AIEEE 2003]
(a) Phenol (b) Benzaldehyde (a) dipolar character of ethers
(c) Butanal (d) Benzoic acid (b) alcohols having resonance structures
Exp. (b) (c) intermolecular hydrogen bonding in ethers
(d) intermolecular hydrogen bonding in alcohols
A + NaOH → alcohol + acid
Thus, it is Cannizzaro reaction. Exp. (d)
A is thus aldehyde without H at α-carbon. Alcohol has polar H which makes intermolecular
(as C 6H5CHO, HCHO) H-bonding possible. Ether is non-polar, hence
2C 6H5CHO + NaOH → C 6H5CH2OH has no H-bonding. Lack of H-bonding in ether
+ C 6H5COONa makes it more volatile than alcohol.
94. Consider the acidity of the carboxylic acids :

96. During dehydration of alcohols to alkenes Exp. (a)

by heating with concentrated H 2SO4 the H
C 2H5NC + H2O →
+
HCOOH + C 2H5NH2
initiation step is [AIEEE 2003] Formic acid
(a) protonation of alcohol molecule C 2H5NH2 + H+ → C 2H5NH+3
(b) formation of carbocation Salt

(c) elimination of water 100. Maximum dehydration takes place in that
(d) formation of an ester of [AIEEE 2002]
Exp. (a) O O
Protonation of OH is first step. It involves OH

conversion of poor leaving group (—OH) into (a) (b)
+
good leaving group ( OH2 ).
OH
97. The general formula Cn H 2n O2 could be for OH CH3
open chain [AIEEE 2003]
(a) diketones (b) carboxylic acids
(c) (d)
(c) diols (d) dialdehydes
Exp. (b) OH
OH
C nH2 nO 2 is general formula for open chain
carboxylic acids and esters. Exp. (b)
e.g., n = 3 C 3H6O 2 Dehydration takes place with the formation of
O more stable carbocation. Among the given
 compounds, only compound (b) forms
Acid CH3CH2 C O H conjugated carbocation. Thus, maximum amount
O of dehydration takes place in compound (b).

Ester CH3 C O CH3 O O
H
98. When CH2 == CH COOH is reduced with H2SO4 (conc.)
H
LiAlH4, the compound obtained will be – H 2O
OH
(a) CH3  CH2  COOH [AIEEE 2003]
(b) CH2 == CH CH2OH 101. Picric acid is [AIEEE 2002]
(c) CH3  CH2 CH2OH
COOH COOH
(d) CH3  CH2  CHO
Exp. (b)
(a) (b)
LiAlH4 reduces —COOH to CH2OH without
NO2 OH
affecting C == C bond.
OH COOH
99. Ethyl isocyanide on hydrolysis in acidic
medium generates [AIEEE 2003] O2N NO2
(a) ethylamine salt and methanoic acid (c) (d)
(b) propanoic acid and ammonium salt
NH2
(c) ethanoic acid and ammonium salt
(d) methylamine salt and ethanoic acid NO2

Exp. (c) Cl 2
CH3CH2COOH → CH3 CHCOOH
Picric acid is 2, 4, 6-trinitro phenol. red P 
(HVZ reaction) Cl
OH
Alcoholic KOH
O2N NO2 → CH2 == CHCOOH
(elimination) A crylic acid
103. On vigorous oxidation by permangnate

solution
NO2
Strongly acidic (CH 3 )2C == CHCH 2CHO gives [AIEEE 2002]
(a) (CH3 )2 CO and OHCCH2CHO
102. End product of the following reaction is (b) (CH3 )2 C  CHCH2CHO
 
Cl 2 Alcohlic KOH OH OH
CH 3CH 2COOH → →
red P (c) (CH3 )2 CO and OHCCH2COOH
[AIEEE 2002] (d) (CH3 )2 CO and CH2 (COOH)2
(a) CH3CHCOOH
 COOH
(b) CH2OH
CH
Exp. (d)
2
 C == C bond is cleaved and oxidised to
(c) CH == CHCOOH
OH2 COOH, CHO group is also oxidised to
(d) CH2 CHCOOH COOH.
  (CH3 )2 C == CHCH2CHO → (CH3 )2 C == O
Exp.Cl (c)OH + HOOC CH2 COOH

18
Organic Compounds
Containing Nitrogen
(Amines and Diazonium Salts)
1. In the following compounds, the decreasing In second case, substituted ammonium cation is also
order of basic strength will be stabilised by solvation with water molecules. Greater
[JEE Main 2019, 8 April Shift-I] the size of ion, lesser will be the solvation and less
(a) C2H5NH2 > NH3 > (C2H5 ) 2 NH stabilised is the ion.
(b) (C2H5 ) 2 NH > NH3 > C2H5NH2 OH2
(c) (C2H5 ) 2 NH > C2H5NH2 > NH3
H
(d) NH3 > C2H5NH2 > (C2H5 ) 2 NH | C2H5 H----OH2
+
C2H2—N+—H----OH2 > N
Exp. (c) | C2H5 H----OH2
H
Basic strength can be compared by the reaction of an 2° amine
alkanamine and ammonia with proton. OH2
H H 1° amine
| |
R—N + H+ R—N+—H Considering both steric and solvation effect, it can be
| | concluded that greater the number of H-atoms on the
H H N-atom, greater will be the H-bonding and hence
H H more stable is the ammonium cation. But in case of
| |
H—N + H+ H—N+—H C 2H 5 group, + I-effect predominates over
| | H-bonding. Therefore, order is 2º amine > 1° amine >
H H ammonia, i.e. (C 2H 5 )2NH > C 2H 5NH 2 > NH 3.
Basicity of an amine in aqueous solution depends
upon the solubility of ammonium cation formed by 2. Which of the following amines can be prepared
accepting proton from water. The stability of by Gabriel phthalimide reaction?
ammonium cation depends upon the following [JEE Main 2019, 8 April Shift-I]
factors. (a) n - butylamine (b) triethylamine
(a) + I-effect
(c) t -butylamine (d) neo -pentylamine
(b) Steric effect
(c) Solvation effect Exp. (a)
In first case, on increasing the size of alkyl group + I n- butylamine (CH 3CH 2CH 2CH 2NH 2 ) can be prepared
effect increases and the positive charge of ammonium by Gabriel phthalimide reaction. This method
cation gets dispersed more easily, Therefore, order of produces only primary amines without the traces of
basicity is 2º amine > 1º amine > ammonia. secondary or tertiary amines.

In this method, phthalimide is treated with ethanolic OH OH

KOH, it forms potassium salt of phthalimide which on
heating with alkyl halide followed by alkaline hydrolysis PhN2+
forms corresponding primary amines. OH –
CO CO
N==N
NH+ Alc. KOH –H O N–K+
2
CO CO − +
In the presence of OH ion, ArN 2 exists in equilibrium
nBu—X
with an unionised compound (Ar  N == N  OH) and
s
COO–Na+ CO salts [ArN == N + ]– OH derived from it, which do not
NaOH(aq.)
+ n Bu—NH2 N—R couple.
s NaOH
– +
COO Na
1° amine
CO [Ar  N ≡≡ N] + OH - Ar  N == N  OH
N-alkyl H+ Does not couple
phthalimide NaOH − +
- Ar N == N ONa
+ Does not couple
H
Triethylamine, t -butylamine and neo-pentylamine
cannot be prepared by Gabriel phthalimide reaction. Following conditions are very useful for coupling
reaction to take place.
3. Coupling of benzene diazonium chloride with (a) The solution must be so alkaline that the
1-naphthol in alkaline medium will give concentration of diazonium ion is too low.
[JEE Main 2019, 8 April Shift-I] (b) It must not be so acidic that the concentration of
free phenoxide ion is too low.
OH
4. The major product in the following reaction is
(a) (b) NH2
N N
N Base
N +CH3I
N
N OH N H N
NH2 NH2
N + N
NCH3 N
(a) (b)
N N
H N N
OH CH3
NHCH3 NH2
(c) N
(d) N N
N N
N N (c) (d)
N N N +
H N N
H
CH3
Exp. (*)
OH δ− δ+
N is more electronegative than ‘C’. So, H of N  H
Exp. (c) bond is more acidic than that of C—H bond in the
Coupling of benzene diazonium chloride with ring.
1-naphthol in alkaline medium will give the following Again, sp2-N is more electronegative ( s % = 33.3) than
coupling reaction. sp3-N ( s % = 25) of the NH 2 group.

Organic Compounds Containing Nitrogen 279
sp3 In step (i), 1° amine is converted into isocyanide, when

NH2 NH2
reacts with CHCl 3 / KOH. This reaction is known as
sp2 carbylamine reaction. This reaction is used to detect
N sp2 N
N Base N primary amine in a compound.
N N In step (ii), isocyanide is reduced to secondary amine
N sp2 N and cyanide is reduced to primary amine, and
sp2 s
Non-aromatic
ring H Aromatic carbonyl group to alcoholic group when treated with
ring Both aromatic rings Pd/C/H 2.
s
B Apparently δ+ δ–
sp3 – BH 6. Aniline dissolved in dil. HCl is reacted with
(Base) CH3–I s
(SN2 attack) –I sodium nitrite at 0°C. This solution was added
NH2 dropwise to a solution containing equimolar
Note This C C′
mixture of aniline and phenol in dil. HCl. The
N N
are missing in all structure of the major product is
the option given. [JEE Main 2019, 9 April Shift-I]
N N
CH3 (a) N N NH2
(Option-b)
5. The major product obtained in the following

reaction is (b) N N O
NH2
(i) CHCl3/KOH
(ii) Pd/C/H2 N N OH
(c)
CN O
[JEE Main 2019, 8 April Shift-II] (d) N N NH
H H
NCH3 NCH3
(a) (b)
Exp. (a)
Major product of the reaction is
CN O CN OH
N N NH2
H H
NCHCl2 NCH3
(c) (d) It is obtained by coupling reaction.
Reaction of aniline with dil. HCl and sodium nitrite at
0°C is shown below :
CN OH H 2N OH +–
NH2 N≡≡NCl
Exp. (d)
1° NH2 responds + NaNO2 + Dil. HCl 0°C
NH2 N≡≡C
CHCl3/KOH Diazonium salt
(Carbylamine reaction) Diazonium salt formed when added to equimolar
mixture of aniline and phenol in dil. HCl then aniline
CN O N≡≡C O couples with diazonium salt. Reaction is as follows :
+ +
Pd/C/H2
N≡≡NCl + H2N
NH—CH3 In acidic
H+ medium
N=
=N —NH2 + HCl
H 2N OH

For an effective coupling, the solution must be so

alkaline that the concentration of diazonium ion is too 8. Hinsberg’s reagent is
low. It must not be so acidic that the concentration of [JEE Main 2019, 9 April Shift-II]
free amine or phenoxide ion is too low. That is why (a) SOCl 2 (b) C6 H5COCl
amines couple fastest in mild acidic solution and
phenols couple fastest in mild alkaline solution.
(c) C6 H5 SO2 Cl (d) (COCl)2
7. The major products A and B for the following Exp. (c)

reactions are, respectively Hinsberg’s reagent is C 6 H 5SO 2Cl (benzene sulphonyl
chloride). This reagent is used to distinguish between
O primary, secondary and tertiary amines.
I H2/Pd
KCN
DMSO
[A] [B ] 9. The major product of the following reaction is
OH
[JEE Main 2019, 9 April Shift-II]  Ethyl formate (1 equiv. )
OH CH3 CH CH2CH2NH2 →
O Triethylamine
CN CH2NH2 [JEE Main 2019, 10 April Shift-I]
(a) ; OH

(a) CH3 CHCH2CH2NHCHO
HO CN HO CH2 NH2
(b) CH3CH == CH  CH2NH2
I H
(b) ; OH

(c) CH3  CH  CH == CH2
O O O
CN CH2NH2
(c) ;
(d) O H
HO CH2 NH2 CH3CHCH2CH2NH2

HO CN
I I Exp. (a)
(d) ;
The mechanism of the given reaction is as follows:
O
OH
Exp. (c) H—C—OEt
O O CH3—CH—CH2CH2—NH2
Et3N
I CN [–NH2 is stronger —EtOs
Step I nucleophile than
KCN —OH] OH
DMSO r
CH3—CH—CH2CH2—NH—CH=
=O
[A]
H
Step II H2/Pd
OH EtOs
O
CH2NH2 CH3—CH—CH2CH2—NH—CHO
The basic mechanism of the reaction is acyl
SN 2 because the nucleophile,
[B] CH 3(OH)CH 2CH 2 NH 2 attacks the sp2 carbon of the
ester (H CO 2Et) and gets substituted.
Step I involves the nucleophilic substitution reaction in
which I (Iodine) is substituted by  CN group. 10. Ethylamine (C2 H5 NH2) can be obtained from
In step II, H 2/Pd reagent is used for reduction N-ethylphthalimide on treatment with
process. Here,  CN group reduces itself to
CH 2 NH 2. [JEE Main 2019, 10 April Shift-I]
(a) NaBH4 (b) NH2NH2
(c) H2O (d) CaH2

Exp. (b) O2N

S
The reaction for the production of ethylamine from (C)
N-ethylphthalimide can be takes place as follows: N N
O H HN O
H H
H 3C
NH
N—C2H5 Hydrazinolysis
| + C2H5—NH2 S
NH2—NH2
NH (D)
(Hydrazine) Ethylamine
H HN (An aliphatic N N
O O 1°-amine)
(N-ethylphthalimide) H H
This reaction is the second step of Gabriel phthalimide (a) (A) < (C) < (D) < (B) (b) (C) < (A) < (D) < (B)
synthesis for the preparation of aliphatic 1°-amines
(c) (B) < (D) < (A) < (C) (d) (B) < (D) < (C) < (A)
and amino acid. In this step concentrated alkali can
also be used in place of hydrazine.
Exp. (c)
11. Which of the following is not a correct method
of the preparation of benzylamine from Key Idea pK b value is defined as the minus
cyanobenzene? [JEE Main 2019, 10 April, (Shift II)] logarithm of K b . Smaller the value of pK b ,
stronger is the base and vice-versa.
(a) H 2 /Ni
(b) (i) HCl / H 2O (ii) NaBH 4
(c) (i) LiAlH 4 (ii) H 3O + In the given options, +R effect is shown by —CH 3 and
—OCH 3 group ( OCH 3 > CH 3 ). These group
(d) (i) SnCl 2 + HCl(gas) (ii) NaBH4 increases the electron density at o and p-positions.
Groups such as F and —NO 2 shows – R-effect
Exp. (b) ( NO 2 > F). These group decreases the electron
The preparation of benzylamine from cyanobenzene density at o and p- positions.
using given reagents are as follows : Increase in electron density at p-position makes the
H2/Ni unshared electron pair of ‘N ’ more available and
Ph  C= N ∆ Ph  CH2  NH2 decrease in electron density at
(Cyanobenzene) Benzylamine p-position makes the unshared electron pair of ‘N ’
less available. Compound containing —OCH 3 group
act as strongest base and hence possess lowest
(i) LiAlH4 (ii) NaBH4 value of pK b . So, the correct increasing order of pK b in
(ii) H Or
3
the given compound is
(i) SnCl2 r O2N S
[Ph  CH==NH2[2 SnCl 62-
(ii) HCl (g) >
bis (benzaldiminium )
hexachlorostannate (IV)
N
H N
H
HCl , H O NaBH (C)
PhCN →
2
PhCOOH →
4
PhCH 2OH
–NH 4Cl Benzoic acid Benzyl alcohol F S
>
Thus, option (b) is incorrect. N N
H H
12. The increasing order of the pK b of the following (A)
compound is [JEE Main 2019, 12 April Shift-I] H3C S
F >
S
N
H N
H
(A)
N N (D)
H H H3CO
S
CH3O
S N N
(B) H H
N N (B)
H H

The mechanism of the reaction is as follows:

13. Benzene diazonium chloride on reaction with
H
aniline in the presence of dilute hydrochloric
(sp2) s
acid gives [JEE Main 2019, 12 April Shift-II] Al (DIBAL-H) Al
(An electrophilie)
(a) r
—NH2 R C N H
R C N Hydride donor
(Reducing agent)
(A nucleophile)
[Nitrile]
(b) —N===N— Al
H2N N
H2 O
R CH O CH (An imine)
–NH3
(c) —N===N— —NH2 [Aldehyde] –DIBAL-H
R
So, R C H is the correct answer.
(d) —N===N—NH— 
O
15. Arrange the following amines in the decreasing

Exp. (c) order of basicity:
Benzene diazonium chloride on reaction with aniline in
the presence of dilute hydrochloric acid undergoes
coupling reaction and produces p-amino azobenzene. N N N
In this reaction, benzene diazonium chloride reacts (I)
with aniline in which aniline molecule at its H H
para-position is coupled with diazonium salt to give (II) (III)
p-amino azobenzene (yellow dye).
(a) I > II > III (b) III > II > I
+ – (c) I > III > II (d) III > I > II
N NCl + H NH2 [ JEE Main 2019, 9 Jan (Shift-I)]
Benzene Aniline Exp. (d)
diazonium
salt Key Idea Basicity ∝ Ease of donation of lone pair of
electrons
H +
N N NH2+Cl–+H2O ∝
1
% of s - character of N
p-amino azobenzene 1
(yellow dye) ∝
Electronegativity of N
14. The major product of following reaction is The % of s-character in the given amines are as
(i) AIH(i - Bu)2 follows:
R  C ≡≡ N →?
(ii) H2O
(a) RCHO (b) RCONH 2 N N N
sp2-hybridised sp3-hybridised
(c) RCOOH (d) RCH 2NH 2 [s-character=33.3%] [s-character=25%]
sp2-hybridised H H
[ JEE Main 2019, 9 Jan Shift-I] [s-character=33.3%]
Pyridine Pyrrole Piperidine
Exp. (a) (I) (II) (III)
Therefore, piperidine (III) having minimum
Key Idea DIBAL-H is diisobutyl aluminium hydride,
% s-character is most basic. Among the rest, pyridine
[(CH 3 )2CHCH 2 ]2 AlH. It is a selective reducing agent.
(I) and pyrrole (II) the lone pair of electrons of N in
It reduces carboxylic acids, carboxylic acid
pyrrole (II) is involved in delocalisation and follows
derivatives and nitriles into aldehydes. It is an
( 4n + 2 ) π aromatic ( n = 1) system. So, the N-atom of
electrophilic reducing agent.
pyrrole (II) will show least basicity.

Thus, the order of basicity is as follows: (a) (D) < (C ) < (B) < (A) (b) (A) < (B) < (C ) < (D)
(c) (A) < (B) < (D) < (C ) (d) (D) < (C ) < (A) < (B)
> >
N N N
H H
Exp. (d)
(III) (I) (II) If we consider Lewis basicity (basicity in aprotic

solvents or in vapour phase), the order of basicity will
16. The major product of the following reaction is be.
D A B C
2° 1° 2° 3°
C
NH2 (i) Br2/hν But, this order does not match with the options given.
(ii) KOH (dil.) So, it has been asked on basicity of the amines in
CH2CH3 aqueous solution. When no phase is given, then
basicity of amine is considered in aqueous solution as
they are liquids.
NH
(a) (b) NH In aqueous solution, basicity of 2°-amines (aliphatic)
CH3 is maximum because, of the thermodynamic stability
of its conjugate acid.
CH3 ⊕ È
Et 2NH + H 2O 1 Et 2 N H 2 + OH
( B) Conjugate acid
NH NH ⊕
(c) (d) Et 2 NH 2 is a sterically symmetric tetrahedral ion as it
contains equal number (two) of bulkier Et-group and
[ JEE Main 2019, 9 Jan Shift-II] small size H-atoms. Here, two H-atoms give
Exp. (a) additional stability through hydrogen bonding with
H 2O (solvent) molecules.
In the given reaction,
Responds to Hoffmann's 18. The major product obtained in the following
bromamide degradation and
gets converted into
reaction is
C [NH2 +K2CO3] by Br2/KOH OH
NH2
(CH3CO)2O/pyridine (1 eqv.)
CH2 Undergo benzylic free room temperature
radical substitution with NH2
(i) Br2/hν CH3 Br2/hν to give [CHCH3] COCH3
(ii) KOH (dil.) OH OH
Br
H
N + H (a)
H N NH2 (b)
–Br H NHCOCH3
Br
CH3 OCOCH3
Formation of –H+
2° carbocation (c) (d)
s
by removing Br NH NHCOCH3 NH2
CH3
Exp. (b)
17. The increasing basicity order of the following Rate of acetylation NH 2 > OH because
compounds is N-bases are stronger than O-bases. Size of N-atom is
CH2CH3
larger than O-atom and at the same time, N atom is

less electronegative than O-atom. So, N-atom of the
(A) CH3CH2NH2 (B) CH3CH2NH ••
 N H 2 group can donate its lone pair of electrons
CH3 CH3
(Lewis basicity) more easily than that of O atom of the
  ••
(C) H3C  N  CH3 (D) Ph  N  H  O H group.

OH OH O
s
CH3 CH3COO H2N CH C NH CH COOH
H 2N C HN—COCH3 CH2 C NH2 CH2 OH
O—COCH3 H
s O
O—C—CH3 Asn Ser
OH (Asparagine) (Serine)
Ac2O or (CH3CO)2O (2 moles)
CH3COOH + Et3N
Absorbed –2 AcOH
NHCOCH3
by pyridine O O
N
CH3 C NH CH C NH CH COOH
19. The correct structure of product ‘P’ in the
CH2 CONH2 CH2O C CH3
following reaction is
NEt 3 O
Asn − Ser + (CH3CO)2 O → P
(Excess) 20. The major product formed in the reaction
O given below will be
O NH2 O NH2
H NaNO2
N Aq. HCI, 0-5°C
(a) H3C N OH
H
O OCOCH3
OCOCH3 (a) NO2 (b) OH
O O
NO2 OH
N
(b) H3C N H OH (c) (d)
H NHCOCH3
O
O [ JEE Main 2019, 10 Jan Shift-I]
O
OCOCH3
O
Exp. (*)
H No option is the correct answer. Amines in presence of
N
(c) H3C N OH NaNO 2 + dil. HCl undergoes diazotisation. The
H NH2 diazotised product readily loses nitrogen gas with the
O
formation of carbocation. The resulting carbocation
O rearranges itself to give the expanded ring.
O
NHCOCH3 NH2 NaNO2+dil. HCl
O
O 0-5°C
NH (Diazotisation)
(d) H3C N (1°-amine)
H OH r s
O N2Cl
OCOCH3
Aliphatic diazonium –N2
Exp. (a) salt (unstable)
4
Acetylation by Ac 2O / Et 3N is possible with NH 2 4 r
3 5
(1°-amine) and OH (alcohol) groups only, but not 6
3 5
6
1
Ring expansion r
O 2 2
leads to give 1
 –Hr H2O thermodynamically
with NH 2’ part of  C NH 2 (amide) groups,
‘ more stable
because the lp of nitrogen in amide group is involved carbocation
in resonance with C O part. OH
s
O O
r
C NH2 C NH2 (Major)

OH
21. An aromatic compound ‘A’ having molecular (a) CH3N
formula C7H6O2 on treating with aqueous
ammonia and heating forms compound ‘B’.
(b) CH3NH
The compound ‘B’ on reaction with molecular
bromine and potassium hydroxide provides OH

compound ‘C’ having molecular formula (c) CH3NH
C6H7N. The structure of ‘A’ is
OH
OHC (d) CH3N
(a)
OH [ JEE Main 2019, 10 Jan Shift-II]
CHO Exp. (c)

(b) NaBH4 is a selective reducing agent. It can reduce
OH C==O group into alcohol, N-methyl imine group,
COOH Me N == CH  into 2°-amine but cannot reduce an
(c) isolated C == C .
O
NaBH4
N
H 3C
(d)
CH==CHCHO N-methyl isolated Keto
imine C C group
OH
[ JEE Main 2019, 10 Jan Shift-II] NH
H 3C
Exp. (c)
Using retro-synthesis, to get the required 23. What will be the major product in the following
compounds, A, B and C. mononitration reaction ?
Br
C 6H7 N ←
2
 B A
(C ) KOH [An amide]
Hoffmann (No.of C[Carboxylic acidNH3/∆
[1° -amine] =7)
(No. of C = 6 bromamide C 7H 6O 2 ]
N
So, the reactions
1 carbon less) reaction
can be shown as: HNO3
(step down) H Conc.H2SO4
COOH CONH2
NH3/D
NO2
–H2O (a)
(A) (B) N
[C7H6O2] Benzenamide H
Benzoic NH2
acid Br2/KOH O2N
–K2CO3
–KBr (b)
(C) N
[C6H7N] H
Aniline

(c) O2N N
H
CH3N NaBH4
(d)
N
H
NO2

Exp. (b) Exp. (b)

Here, in mononitration the electrophile produced from Ni/H 2 can reduce —C ≡≡ N into CH 2 NH 2
+
mixed acid (HNO 3 + conc.H 2SO 4 ) is NO 2. (1°-amine) but cannot reduce an ester group
( CO 2Et) whereas DIBAL-H, di-isobutylaluminium
O –R hydride, [(CH 3 )2CH]2AlH reduces the ester group
A +R ( CO 2Et) into —CHO (an aldehyde) and C 2H 5OH.

N
B
H OEt Ni/H2/D OEt
Ring-(A) is activated, i.e. becomes more nucleophilic C≡N DIBAL–H
•• NH2 –EtOH
by the + R effect of the  N H  group and it
becomes o / p-directing towards the electrophile, 1
2 CH
⊕ NH2
N –H2O
NO+2 in the ArS E 2 reaction. For mononitration, NO 2
3 (Nucleophilic addition
will preferably come at p-position, whereas the elimination reaction)
4
O

ring-(B) gets deactivated by −R- effect of the C  25. In the following compound,
group,
a
r NH2
O2N O r dN
NO2 N b
C rds of ArSE2
NH e N N
H c
H the favourable site/s for protonation

O
is/are
O2N
r C (a) (a) and (e) (b) (b), (c) and (d)
NH Fast,–Hr
(c) (a) and (d) (d) (a)
O2N O
Exp. (b)
C All sites (a, b, c, d, e) of the given molecule have lone
NH pair on N-atoms. Higher the ease of donation of lp of
electrons of N, more favourable will be the site for
protonation. Ease of donation of lp of es, i.e. Lewis
24. The major product of the following reaction is basicity inversely depend on the percentage of
s -character in hybridisation of ‘N’ which will decide
O the electronegativity of ‘N’.
OEt (i) Ni/H2 At ‘a’ and ‘e’, N-atoms are sp3 (s% = 25) hybridised,
CN (ii) DIBAL- H whereas at ‘b’, ‘c’ and ‘d’, N-atoms are sp2 (s% = 33)
hybridised. So, ‘b’, ‘c’ and ‘d’ are the favourable sites
NH N for protonation (H + is a Lewis acid, i.e. electrons
(a) (b) acceptor).
H 26. A compound ‘X’ on treatment with
Br2 / NaOH, provided C3 H9N, which gives
O OH
(c) CHO (d) positive carbylamine test. Compound ‘X’ is
NH2
(a) CH3COCH2NHCH3 (b) CH3CH2CH2CONH2
[ JEE Main 2019, 11 Jan Shift-I] (c) CH3CON(CH3 )2 (d) CH3CH2COCH2NH2

Exp. (b) Exp. (b)

The molecular formula, C 3H 9N refers to four structural The reaction of alkyl halide with amine or amides is a
isomers of amines nucleophilic substitution reaction.
(a) CH3CH2CH2NH2 (b) CH3–CH–CH3 More nucleophilic nitrogen is more
reactive with alkyl halide. Compound (A) is
NH2 benzamide and lone pair of ‘N’ of it, is not available in

Primary amine this compound.
s
CH3 O O
+
(c) CH3–NH–CH2CH3 (d) CH3–N–CH3 C NH2 C NH2
Secondary amine Tertiary amine
Here, only a and b (primary amines) can be prepared (A)
from their respective amides by Hoffmann In compound (D), lone pair of ‘N’ are available but in
bromamide (Br2/NaOH) method and can give positive compound (C), the lone pair of ‘N’ are not readily
carbylamine test. available due to the presence of electron withdrawing
group ( CN) attach to benzene ring.
Br2 In compound (B), i.e. pthalimide, ‘N’ is not
⇒ CH3CH2CH2—C—NH2 CH3CH2CH2—NH2 nucleophilic due to the presence of two polar groups
NaOH
–Na2CO3 attached to it that pulls lone pair towards them.
Hence, the correct order is:
H2N—C NH2
( B)< ( A )< (C )< ( D).
Br2/NaOH
⇒ CH3—CH—CH3 CH3—CH—CH3
–Na2CO3
So, ‘X’ can be CH 3CH 2CH 2 CONH 2 (a)
H 3C O (i) NaNO2/H+
or CH 3CH(CONH 2 )CH 3 (b). NH2
Carbylamine test given by (a) and (b) O (ii) CrO3/H+
∆→ (iii) H2SO4 (conc.), ∆
CH CH CH NH + CHCl + 3KOH 
3 2 2 2 3
O
CH 3(CH 2 )2NC + 3KCl + 3H 2
NH 2 (a) CH3 O

CH 3 CH  CH 3 + CHCl 3 + 3KOH  ∆→ O
NC O
 (b) HO
CH 3 CH  CH 3 + 3KCl +3H 2
As (b) is not among the given options So, it is ruled out
and compound (X) is CH 3CH 2CH 2CONH 2. HO
(c)
27. The increasing order of reactivity of the
O
following compounds towards reaction with O
CH3
alkyl halides directly is (d)
O O CN O O
NH2 NH2
NH2
NH Exp. (c)
O Key Idea The reaction involves:
(A) (B) (C) (D) A. Deamination in step (i)
(a) (A) < (C) < (D) < (B) (b) (B) < (A) < (C) < (D) B. Oxidation in step (ii)
(c) (B) < (A) < (D) < (C) (d) (A) < (B) < (C) < (D) C. Hydroysis in step (iii)

The complete pathway of reactions is as follows: This marginally increases the electronegativity of
nitrogen which in turn decreases the electron
H3 C O
donation tendency of nitrogen.
(i) NH2
Thus making compound least basic.
O
NH2
H 3C O Among the rest is totally different

NaNO2/H+ NH
OH from others as in this compound lone pair of one
Deamination O
nitrogen are in conjugation with π bond i.e.
H 3C O
(ii) OH 1
O HN NH2
O
In conjugation
H 3C O
CrO3/H+
Oxidation OH As a result of this conjugation the cation formed
O after protonation becomes resonance stabilised
HO Protonation
H O
H 3C Intramolecular + +
O HN NH2 H 2N NH2 NH2
(iii) dehydration H2 N
O Equivalent resonance
H OH
Hydrolysis
This equivalent resonance in cation makes
Conc. H2SO4/D
Cyclisation
HO most basic among all.
HN NH2
Categorisation is very simple between rest two as
NH2
O (primary amine) is less basic than
Final product
N CH3 (secondary amine)
Thus, option (c) is the correct answer.
H
29. The increasing order of basicity of the Hence, the correct order is
following compounds is [JEE Main 2018] (II) < (I) < (IV) < (III)
NH2 i.e. option (c) is correct.
I. NH
II.
NH2 30. Which of the following compounds will give
III. IV. significant amount of meta-product during
NHCH3
NH mononitration reaction?
(a) (I) < (II) < (III) < (IV) (b) (II) < (I) < (III) < (IV)
(c) (II) < (I) < (IV) < (III) (d) (IV) < (II) < (I) < (III) OH OCOCH3
Exp. (d)
(a) (b)
/ Among the given compounds the basic
nature depends upon their tendency to NH2 NHCOCH3
donate electron pair.
NH (c) (d)
Among the given compounds in ,
Nitrogen is sp2 -hybridised.

COOH
Exp. (c)
Aniline in presence of nitrating mixture
(conc. HNO 3 + conc. H2 SO 4 ) gives significance (a) (b) H3C CH3
amount (≈ 47%) of meta-product because in
presence of H2SO 4 its protonation takes place
CH3
and anilinium ion is formed.
CN CH3
NH2 NH3HSO4
H2SO4 (c) (d)
Aniline Anilinium ion

CH3
Here, anilinium ion is strongly deactivating
group and meta-directing in nature. So, it gives
meta-nitration product.
Exp. (c)
+ –
NH2 N2Cl
NH2 NH3HSO4
Conc.H2SO4 NaNO2 / HCl

0 – 5°C
+Conc.HNO3
NO2 diazotisation
CH3 CH3
31. In the Hofmann-bromamide degradation 4- methyl aniline (D)
reaction, the number of moles of NaOH and 4- methyl diazonium chloride
Br 2 used per mole of amine produced are ∇
CuCN / KCN
CN
(a) four moles of NaOH and two moles of Br2
(b) two moles of NaOH and two moles of Br2
(c) four moles of NaOH and one mole of Br2 + CuCl
(d) one mole of NaOH and one mole of Br2
Exp. (c) CH3

(E)
Hofmann-bromamide degradation reaction is 4- methyl benzocyanide
given as:
RCONH2 + 4NaOH + Br2 → RNH2 33. On heating an aliphatic primary amine with
(1° amine)
chloroform and ethanolic potassium
+ Na 2 CO 3 + 2NaBr + 2H2O hydroxide, the organic compound formed is
Hence, four moles of NaOH and one mole of Br2 [JEE Main 2014]
are used. (a) an alkanol (b) an alkanediol
(c) an alkyl cyanide (d) an alkyl isocyanide
32. In the reaction,
NH2
Exp. (d)
Reaction of aliphatic primary amine with chloroform
NaNO2 / HCl CuCN / KCN and ethanolic potassium hydroxide, leads to the
D ∇ E + N2
0.5°C formation of isocyanides/carbylamines. Thus, this
reaction is called carbylamine reaction.
CH3 ∆
The product E is R  NH2 + CHCl 3 + KOH →
[JEE Main 2015]
R  NC + 3KCl + 3H2O
Alkyl isocyanide

NH3 –+
34. Considering the basic strength of amines in CH3CH2COOH CH3CH2COO NH4
aqueous solution, which one has the (A) (B)
smallest pK b value? [JEE Main 2014]
O
(a) (CH3 )2 NH (b) CH3 NH2 ||
∆
(c) (CH3 )3 N (d) C6 H5 NH2 CH3CH2 — C — Nh2

Hofmann (C)
Exp. (a) bromamide KOH/Br2
It is known that, pK b = − log kb reaction
Thus, larger the value of kb , smaller is the value of CH3CH2NH2
pK b and hence, stronger is the base.
The order of basic strength of amines is as follows 36. A compound with molecular mass 180 µ is
•• •• •• •• acylated with CH 3COCl, to get a compound
(CH3 )2 NH > CH3 NH2 (CH3 )3 N > C 6H5 NH2
with molecular mass 390 µ. The number of
The basic strength of amines depends on the amino groups present per molecule of the
inductive effect as will as steric hinderance of alkyl former compound is [JEE Main 2013]
••
groups. Hence, (CH3 )2 NH [secondary amine] (a) 6 (b) 2 (c) 5 (d) 4
possess the smallest value of pK b .
Exp. (c)
35. An organic compound A on reacting with During acetylation, one H atom with atomic mass
NH 3 gives B. On heating B gives C . C in the 1 amu of  NH2 group is replaced by an acetyl
presence of KOH reacts with Br2 to give group CH3 CO [molecular mass = 434µ]. Thus,
CH 3CH 2NH 2. A is [JEE Main 2013]
 NH2 + CH3COCl →  NHCOCH3 + HCl
(a) CH3  CH  COOH The above equation suggests that, the acylation

of each  NH2 group increases the mass by 42 µ
CH3
[43 − 1]. If the molecular mass of the organic
(b) CH3CH2CH2CH2COOH compound is 180 µ while that of the acylated
(c) CH3CH2COOH product is 390 µ, then the increase in the mass
(d) CH3COOH due to acylation is given by
Exp. (c) 390 − 180 = 210 µ
210 µ
NH ∆ KOH /Br2 Hence, the number of  NH2 groups = =5
A →
3
B → C → CH3 CH2 NH2 42 µ
The reaction of C with KOH/Br 2 to give amine is
called Hofmann bromamide reaction. This 37. In the chemical reaction,
reaction is give by acid amides only in which NH2
O
 NaNO2 CuCN
R  CH2  C NH2 group undergoes HCl 278K
A ∆ B,
rearrangement along with the loss of CO 2
molecule. Thus, the compound C must be acid compounds A and B respectively are
amide with three carbon atoms. Hence, the (a) fluorobenzene and phenol [AIEEE 2011]
O
(b) benzene diazonium chloride and benzonitrile

compound C is CH3  CH2  C NH2 . (c) nitrobenzene and chlorobenzene
(d) phenol and bromobenzene
Since, all the options shows that A is an acid and it
forms acid amide on reaction with NH3 . Thus, acid Exp. (b)
must contain three carbon atoms. Hence, the
compound A is CH3CH2 COOH. The complete Formation of A is by diazotisation and formation of
series of reaction can be represented as B from A is by SN reaction. Thus, the complete
series of reaction is given by

+ –
NH2 N2Cl CN Exp. (a)
CH3 CH3 CH3
NaNO2 CuCN
∆
Conc HNO3 NO2
HCl, 0-4°C
SN reaction + H2SO4
(Diazotization) +
(A) (B)
+ N2 + CuCl
o-,p-directing
NO2
38. In the chemical reaction, [AIEEE 2010]
NH2 Sn/HCl
(Reduction of NO2)
NaNO2 HBF4 CH3 CH3

A B
HCl, 278 K
NH2
the compounds ‘A’ and ‘B’ respectively are +
(a) nitrobenzene and fluorobenzene
(b) phenol and benzene
(c) benzene diazonium chloride and NH2
fluorobenzene
NaNO2, HCl
(d) nitrobenzene and chlorobenzene diazotisation
Exp. (c) CH3 CH3

+
NH2 N2Cl
N NCl–
+
NaNO2 HBF4
HCl, 278 K
(Diazotization) +
N NCl–
(A)
+ CuBr, Heat
N2BF4
– F Sandmeyer’s reaction
CH3 CH3
∆ + N2 +BF3
+ HCl Br
+
Diazonium Aryl fluoride
fluoroborate (B)
(o-bromotoluene)
The reaction of diazonium chloride with Br
fluoroboric acid (HBF4 ) is called Balz-Schiemann (p-bromotoluene)
reaction.
40. Which one of the following is the strongest
39. Toluene is nitrated and the resulting base in aqueous solution ? [AIEEE 2007]
product is reduced with tin and (a) Trimethylamine (b) Aniline
hydrochloric acid. The product so obtained (c) Dimethylamine (d) Methylamine
is diazotised and then heated with cuprous
bromide. The reaction mixture so formed Exp. (c)
contains [AIEEE 2008] In aqueous solution, basicity order is
(a) mixture of o-and p-bromotoluenes Dimethylamine >methylamine
(b) mixture of o-and p-dibromobenzenes 2° 1°
> trimethylamine > aniline
(c) mixture of o-and p-bromoanilines 3°
(d) mixture of o-and m-bromotoluenes This order depends upon the inductive effect and
steric hinderance of alkyl groups.

41. In the chemical reaction, Exp. (d)

Basic nature of the compound is related to their
CH 3CH 2NH 2 + CHCl 3 + 3KOH → tendency to donate their lone pair of electrons
( A ) + (B ) + 3H 2O, more readily. − I effect [e − withdrawing] exerting
the compounds ( A ) and (B ) are respectively group decreases the basic strength while + I
(a) C2 H5CN and 3KCl [AIEEE 2007] effect [e − donating] exerting group increases the
basic strength of the compound.
(b) CH3CH2CONH2 and 3KCl
NH2
(c) C2 H5 NC and 3KCl
(d) C2 H5 NC and 3KCl
(a) NO2 group
Exp. (c) (electron withdrawing)
CH3 CH2 NH2 + CHCl 3 + 3kOH → decreases basic nature of aniline
( alc ) NO2
CH3 CH2  N →
== C + 3KCl + 3H2O O O
( A) ( B)
The above reaction is called carbylamine reaction (b) CH3C NH2 where, CH3C group is also
electron withdrawing
in which isocyanides or carbylamines are
produced.
:
(c) NH2 phenyl group is
42. Fluorobenzene (C 6H 5F) can be synthesized also electron withdrawing.
in the laboratory [AIEEE 2006] (d) Benzylamine (C 6H5CH2NH2 ) contains alkyl
(a) by heating phenol with HF and KF group linked to amine,  NH2 group. This
(b) from aniline by diazotisation followed by alkyl group is + I effect [e − donating] exerting
heating the diazonium salt with HBF4 group which increases the basicity of
(c) by direct fluorination of benzene with F2 gas benzylamine.
(d) by reacting bromobenzene with NaF solution Thus, most basic compound is benzylamine.
Exp. (b) 45. Reaction of cyclohexanone with

dimethylamine in the presence of catalytic
N2Cl –
+
NH2 amount of an acid forms a compound.
NaNO2, HCl
Water during the reaction is continuously
diazotisation removed. The compound formed is
generally known as [AIEEE 2005]
F
HBF4 (a) an amine (b) an imine
(c) an enamine (d) a Schiff ’s base
Exp. (c)
43. Which one of the following methods is CH3 CH3
neither meant for the synthesis nor for O + HN — HN
separation of amines ? [AIEEE 2005]
CH3 CH3
(a) Curtius reaction (b) Wurtz reaction Enamine
(c) Hofmann method (d) Hinsberg method
CH3
Exp. (b) — OH + H N
Wurtz reaction is used to prepare alkanes from CH3
alkyl halides. Enol
Dry ether
2R  X + 2Na → R  R + 2NaX 46. An organic compound having molecular
mass 60 is found to contain C = 20%,
44. Amongst the following the most basic
compound is [AIEEE 2005] H = 6.67% and N = 46.67% while rest is
(a) p -nitroaniline (b) acetanilide
oxygen. On heating, it gives NH 3 alongwith a
(c) aniline (d) benzylamine
solid residue. The solid residue gives violet

colour with alkaline copper sulphate I–

(b) NH CH3
solution. The compound is [AIEEE 2005]
I+
(a) CH3CH2CONH2 (b) (NH2 )2 CO
(c) CH3CONH2 (d) CH3 NCO
I–
(c) NH2
Exp. (b) CH3

Percentage Simple
Element Percentage (d) CH2 NH2
at. wt. Ratio
I+
C 20.0 20.0 1.66
= 1.66 =1 C 6H5 decreases electron density at N-atom due to
12 1.66 delocalisation of e − of NH2 with π e − of benzene.
H 6.67 6.67 6.67 Thus, basic nature is decreased.
= 6.67 =4
1 1.66 Hence, (d) is the strongest base.
N 46.67 46.67 3.33 48. The correct order of increasing basic nature
= 3.33 =2
14 1.66 for the bases NH 3 ,CH 3NH 2 and(CH 3 )2 NH is
O 26.66 26.66 1.66 (a) CH3 NH2 < NH3 < (CH3 )2 NH [AIEEE 2003]
= 1.66 =1
16 1.66 (b) (CH3 )2 NH < NH3 < CH3 NH2
Empirical formula =CH4N2O (c) NH3 < CH3 NH2 < (CH3 )2 NH
Empirical formula weight (d) CH3 NH2 < (CH3 )2 NH < NH3
= 12 + (4 × 1) + (2 × 14) + 16 = 60
Mole formula weight 60
Exp. (c)
∴ n= = =1
Emp formula weight 60 The basicity of an amine in aqueous solution
primarily depends upon the stability of the
∴ Molecular formula = CH4N2O ammonium cation or the conjugate acid formed
Given compound gives biuret test, thus given by accepting the proton from water.
compound is urea (NH2 )2 CO. +
∆ R NH2 + H2O 1 R NH3 + OH −
NH2CONH2 + HNHCONH2 →
[ammonium cation]
NH2CONHCONH2 + NH3 The stability of the ammonium cation depends upon
Biuret
(i) + I effect of alkyl groups
 as CuSO 4
↓ (ii) Extent of H-bonding with water molecules
Violet colour (iii) Steric effects of the alkyl groups
On the basis of above factors, the basic strength
47. Which of the following is the strongest base? of amine is as follows
[AIEEE 2004] (CH3 )2 NH >CH3 NH2 > NH3
(a) NH2 (b) NH3 (+ I effect of CH 3

group predominates )
CH3 49. On heating benzyl amine with chloroform
and ethanolic KOH, product obtained is
(c) NHCH3 (d) CH2NH2 [AIEEE 2002]
(a) benzyl alcohol (b) benzaldehyde
Exp. (d) (c) benzonitrile (d) benzyl isocyanide
CH3  [an electron releasing (+ I) group] Exp. (d)

increases electron density at N-atom, hence basic It is carbylamine reaction.
nature is increased. CH2NH2 CH2NC
CHCl3
(a) KOH,C2H5OH
NH2
Benzyl amine Benzyl isocyanide
I–
Carbylamine reaction (test for 1° amine)

19
Polymers and
Biomolecules
1. Maltose on treatment with dilute HCl gives 2. The structure of nylon-6 is
[JEE Main 2019, 8 April Shift-I] [JEE Main 2019, 8 April Shift-II]
(a) D-glucose and D-fructose O H
(b) D-fructose || |
(a) 
[ (CH2 ) 6  C  N 
]n
(c) D-galactose
(d) D-glucose O H
|| |
(b) 
[ C  (CH2 ) 5  N 
]n
Exp. (d)
O H
Maltose on treatment with dil. HCl gives D-glucose. || |
Hydrolysis of maltose yields two moles of (c) 
[ (CH2 ) 4  C  N 
]n
α- D-glucose. Thus, it is composed of two
O H
α-D-glucose units in which C-1 of one glucose unit (I) || |
is linked to C-4 of another glucose unit (II). The free (d) 
[ C(CH2 ) 6  N 
]n
aldehyde group can be produced at C-1 of second
glucose in solution and it shows reducing properties.
So, it is a reducing sugar. Exp. (b)
CH2OH CH2OH O
O O
H H H H H Polymerisation
H NH
OH H O OH H
OH OH
Caprolactum
H OH H OH
O O
CH2OH
O —C—NH—(CH2)5 —C—NH—(CH3)5—
H OH
Dil. HCl H
2 or
OH H H
OH O
H OH —NH—(CH2)5—C—
α-D-glucose n
Nylon-6

Polymers and Biomolecules 295
Nylon-6 is prepared by ring opening polymerisation of On hydrolysis with acids or enzyme, sucrose gives
caprolactum. It is heated about 533 K in an inert equimolar mixture of D-(+)-glucose and
atmospheric nitrogen about 4-5 hrs. Nylon-6 fibres are D-(–)-fructose.
tough, possessing high tensile strength, as well as HCl
elasticity and lustre. They are wrinkle proof and highly C 12H 22O11 + H 2O → C 6H12O 6 + C 6H12O 6
D -(+) - glucose D -(–)-fructose
resistant to abrasion and chemicals such as acids
and alkalis.
5. Which of the following compounds is a
3. Fructose and glucose can be distinguished constituent of the polymer
by [JEE Main 2019, 8 April Shift-II] O
(a) Fehling’s test (b) Barfoed’s test 
(c) Benedict’s test (d) Seliwanoff’s test [ HN —C — NH — CH 2—
— ]n ?
Exp. (d)
(a) N -methyl urea
Both fructose and glucose give following test positive.
(b) Methylamine
(i) Fehling’s test (red ppt. of Cu2O is obtained).
(c) Ammonia
(ii) Barfoed’s test (red ppt. of Cu2O is obtained)
(d) Formaldehyde
(iii) Benedict’s test (red ppt. of Cu2O is obtained)
Fehling’s solution : CuSO 4 + Na , K-tartrate Exp. (d)
(Rochelle salt) O
Barfoed’s reagent (CH 3COO)2Cu + CH 3COOH + H 2O ||
(7%) (1%) (92%) Monomer of [NH C NH CH 2 ]n is
Benedict’s solution : CuSO 4 + Na -citrate+ Na 2CO 3 formaldehyde. The polymer is also known as
Seliwanoff’s test is used to differentiate between ketose urea-formaldehyde resin. It is made from urea
and aldose. The reagent is a solution of resorcinol in (NH 2CONH 2 ) and formaldehyde (HCHO).
concentrated HCl. The reagent when heated along with Polymerisation
a sugar will produce furfural or hydroxy-methylfurfural, NH2CONH2 + HCHO →
Urea Formaldehyde
which further reacts to give red color. Ketose O
(fructose) reacts more quickly than aldose (glucose). ||
(NH C NH CH 2
)n
4. Which of the following statement is not true Urea -formaldehyde resin
about sucrose? [JEE Main 2019, 9 April Shift-I] It is used for making unbreakable cups and laminated
(a) It is also named as invert sugar. sheets.
(b) The glycosidic linkage is present between C1 of
α-glucose and C2 of β-fructose 6. The peptide that gives positive ceric
(c) It is a non-reducing sugar ammonium nitrate and carbylamine tests is
(d) On hydrolysis, it produces glucose and fructose [JEE Main 2019, 9 April Shift-II]
Exp. (b) (a) Lys-Asp (b) Ser-Lys
(c) Gln-Asp (d) Asp-Gln
Statement-(b) is not true for sucrose. It is linked through
a glycosidic linkage between C-1 of α-glucose and Exp. (b)
C-2 of β-fructose. Since, the reducing groups of
glucose and fructose are involved in glycosidic bond The peptide that gives positive cerric ammonium
formation, sucrose is a non-reducing sugar. nitrate and carbylamine tests is ser-lys. The structures
of serine and lysine are,
CH2OH
HO CH 2 C H  COOH
O |
H H HOH2C O
H H NH 2
α β Serine
OH H
HO Glycosidic H 2 N (CH 2 )4 C H  COOH
linkage H HO CH2OH |
H OH
NH 2
α-D-glucose OH H Lysine
β-D-fructose

7. Amylopectin is composed of Exp. (a)

Key Idea Chiral centre is also called stereo-centre or
(a) β-D-glucose, C 1-C 4 and C2-C6 linkages stereogenic center.
(b) α-D-glucose, C 1-C 4 and C2-C6 linkages
(c) β-D-glucose, C 1-C 4 and C1-C6 linkages Linear structure of glucose is as follows :
(d) α-D-glucose, C 1-C 4 and C1 -C6 linkages CHO
H OH
Exp. (d) H
HO
Amylopectin is the water-soluble component of starch. H OH
It is a branched-chain polymer of α-D-glucose. The
H OH
main chain consists of an α − 1, 4′- glycosidic linkages
between α - D - glucose units and the branches are CH2OH
connected to the main chain by Fischer formula
α - 16, ′- glycosidic linkages. Its structure can be
Number of stereo-centre (C* ) = 4.
represented as:
6
Cyclic structure of glucose are as follows :
4 CH2OH O
O 2
5 H
HO 1
3 OH α-1, 6′-glycosidic linkage (Branch)
O
6 6
4 CH2 O 4 CH2OH
O
5 2 5 2 H
H
HO HO 1
3 OH 3 OH O
O
α-1, 4′-glycosidic linkage (Chain) Haworth formula Number of stereo-centre ( C* ) in
Structure of Amylopectin
each anomer = 5.
8. Which of the following is a condensation 10. The correct match between Item-I and
polymer? [JEE Main 2019, 10 April Shift-I] Item-II is [JEE Main 2019, 10 April Shift-II]
(a) Nylon-6, 6 (b) Neoprene
(c) Teflon (d) Buna - S Item-I Item-II
Exp. (a) A. High density I. Peroxide catalyst

polythene
Nylon-6, 6 (an amide) is a condensation copolymer
B. Polyacrylonitrile II. Condensation at high
because it is obtained by condensation between
temperature and pressure
adipic acid and hexamethylenediamine.
O O C. Novolac III. Ziegler-Natta catalyst
H
nHO—C—(CH2)4—C—OH + nN—(CH2)6—NHH
D. Nylon-6 IV. Acid or base catalyst
H Hexamethylene –nH2O
Adipic acid
diamine Codes
O O A B C D A B C D
(a) III I IV II (b) IV II I III
——C—(CH2)4—C—NH—(CH2)6—NH—— (c) III V I III (d) III I II IV
1 mol n
nylon-6,6 Exp. (a)
Neoprene, teflon and buna-S are addition polymers.
[TiCl +(C H ) Al]
(A) nCH 2 ==CH 2 →
4 2 5 3

[ CH 2 
]n
9. Number of stereo-centers present in linear Ethylene
Ziegler -Natta catalyst
(III)
High density
polythene (HDPE)
and cyclic structures of glucose are CN
CN
respectively [JEE Main 2019, 10 April Shift-II] | O 22 − /O 2

(a) 4 and 5 (b) 4 and 4 (B) nCH 2 ==CH →  [ CH 2  CH 
]n
(Catalyst) Polyacrylonitrile
(c) 5 and 4 (d) 5 and 5 Acrylonitrile (I)
(PAN)

(C) OH OH
CH2OH 13. Which of the following statement is not true
sOH
+ HCHO Polymerisation/ about RNA? [JEE Main 2019, 12 April Shift-I]
Formaldehyde
Acid or H3Or (a) It controls the synthesis of protein
base catalyst
Phenol (IV) (b) It has always double stranded α-helix structure
(c) It usually does not replicate

OH OH
(d) It is present in the nucleus of the cell
CH2
Exp. (b)
n RNA does not have double stranded α-helix structure.
Novolac Helixes present in RNA are single-stranded but
(D) O sometimes they fold back on themselves to form a
NH double helix structure. RNA usually does not replicate.
550 K
O 20 atm —C—NH—(CH2)5— It is present in the nucleus of the cell. It controls the
–H2O Nylon-6 n synthesis of protein. RNA molecules are of three
Caprolactum (II) types, i.e. messenger’s RNA (m-RNA), ribosomal RNA
Thus, the correct match is as follows : (rRNA), transfer RNA (t -RNA).
(A) → (III), (B) → (I), (C) → (IV), (D) → (II)
14. Which of the given statements is incorrect
11. Which of the following is a thermosetting about glycogen? [JEE Main 2019, 12 April Shift-II]
polymer? [JEE Main 2019, 12 April Shift-I] (a) It is straight chain polymer similar to amylose
(a) Bakelite (b) Buna-N (b) Only α-linkages are present in the molecule
(c) Nylon-6 (d) PVC (c) It is present in animal cells
(d) It is present in some yeast and fungi
Exp. (a) Exp. (a)
Bakelite is a thermosetting polymer. These polymers Statement (a) is incorrect. Glycogen is not a straight
are cross-linked or heavily branched molecules which chain polymer similar to amylose. It is highly branched
on heating undergo extensive cross linking in moulds structure similar to amylopectin. It is known to be the
and become infusible. Once they get set, they cannot storage material of animals. It is found in liver,
be reshaped and reused. muscles and brain. It breaks down to glucose by the
action of enzymes when body needs a glucose. It is
12. Glucose and galactose are having identical also found in yeast and fungi.
configuration in all the positions except
15. The correct name of the following polymer is
position.
(a) C-3 (b) C-4 (c) C-2 (d) C-5 CH3 CH3
Exp. (b) n
Glucose and galactose are having identical (a) polyisobutane (b) polytert-butylene
configuration at all the positions except at C-4
position. Both of them are diastereomers that differ in (c) polyisoprene (d) polyisobutylene
configuration at only one chirality center. Hence, these Exp. (d)
are called epimers. Structures of glucose and
galactose are as follows: The correct name of the given polymer is
polyisobutylene. It’s monomer unit is isobutylene.
1 1
H—C==O H—C==O Reaction involved is as follows :
2 2 CH3
H OH H OH
3 3 CH3
HO H HO H Polymerisation
4 4 nCH2 C CH2 C
H OH C–4 HO H
CH3
H OH H OH CH3 n
Isobutylene
CH2OH CH2OH Polyisobutylene
D-glucose D-galactose The above reaction proceed via addition polymerisation.
Polymer is formed by the repeated addition of
monomer molecules possessing double bond.

16. The increasing order of pK a of the 17. The correct sequence of amino acids present
following amino acids in aqueous solution in the tripeptide given below is
is Gly, Asp, Lys, Arg
Me Me Me OH
(a) Asp < Gly < Arg < Lys H
(b) Arg < Lys < Gly < Asp N OH

H2N N C
(c) Gly < Asp < Arg < Lys H
(d) Asp < Gly < Lys < Arg OH
[JEE Main 2019, 9 Jan Shift-II] (a) Thr - Ser - Leu (b) Leu - Ser - Thr
Exp. (d) (c) Val - Ser - Thr (d) Thr - Ser - Val
Amino acid molecules can be represented as, [JEE Main 2019, 9 Jan Shift-II]
COOH Exp. (c)
R CH
NH2 Formation of the tripeptide (Val-Ser-Thr) can be shown
Nature of the ‘R’ group will determine the basicity as:
(hence, pK a) of an amino acid. Me Me Me OH
CH CH
‘R’ in the amino Nature Nature of the CH OH H HN C CH OH
amino acids C CH OH H HN C
group of R H 2N
+ More basic CH2
NH2 OH
(due to the
1.  (CH2)3 NH  C Basic presence of
NH2 Valine (Val) Serine (Ser) Threonine (Thr)
acetamidine
group) –2H2O
Me Me Me OH
(Arginine : Arg) CH CH
O Acidic Acidic CH NH C CH OH
2. CH2 C H2N C CH C
NH
O–
(Aspartic acid: Asp) CH2
OH
3. H (Glycine) : Gly Neutral Neutral
Val Ser Thr
+
4. ( CH2 )4  N H3 Basic Basic
(Lysine : Lys) 18. Which of the following tests cannot be used for
identifying amino acids ?
Acetamidine group present in arginine is (a) Barfoed test (b) Ninhydrin test
NH2 (c) Xanthoproteic test (d) Biuret test
C
NH [JEE Main 2019, 10 Jan Shift-II]
its self-protonation/deprotonation makes its Exp. (a)
conjugate acid very stable.
NH2 (i) Barfoed test is used for detecting the presence of
So, C is a strongly basic in nature. monosaccharides like glucose, fructose etc. Barfoed
NH reagents is Cu (II) acetate solution.
The resonating structure of acetamidine group is CHO COOH
H –
N H NH NH H OH H OH
C C C HO H HO H
+ + Cu2+ + 2H2O
NH NH2 NH2 H OH H OH
H OH (Cu (II)
H OH
The basicity order of given amino acids in aqueous acetale)
solution is as follows: CH2OH CH2OH
Asp < Gly < Lys < Arg (D-glucose) (D-gluconic acid)
Thus, order of pK a values is also, + Cu2O + 4H+
Asp < Gly < Lys < Arg (Red ppt.)
pK a value : (3) (6) (9.8) (10.8)

(ii) (Ninhydrin Test)

Violet 20. The polymer obtained from the following
Ninhydrin/ D
colouration
reaction is:
Amino acid (Xanthoprotic Test) Yellow (i) NaNO2 /H3O
+
(Protein) Conc. HNO3 colouration NH2

HOOC (ii) Polymerisation
(Biuret Test)
Violet O O
CuSO4 (aq)+NaOH
colouration H
(a) —C—(CH2)4—N— (b) —O—(CH2)4—C—
n n
19. Among the following compounds, which
one is found in RNA? H
O (c) —OC(CH2)4O— (d) —HNC(CH2)4—C—N—
O n n
CH3 [JEE Main 2019, 11 Jan Shift-I]
NH NH
(a) (b)
N O N O Exp. (c)
H
H Given amino acid on reaction with NaNO 2 / H 3O +
NH2 O gives diazotisation reaction which further evolves
 N 2 gas along with formation of carbocation. On
N N Me further reaction with water, it form HOOC (CH 2 ) 
(c) (d)
N N OH that undergoes polymerisation to give polymer.
O O
NaNO2/H3O+
H Me HOOC—(CH2)4—NH2 HOOC—(CH2)4—N2
(Diazotisation)
Aliphatic diazonium ion
[ JEE Main 2019, 11 Jan Shift-I] (Unstable)
–N2
+
Exp. (a) HOOC—(CH2)3—CH2
RNA contains, adenine (A), guanine (G), cytosine (C) –H –H2O
and uracil (U). In the given options, Polymerisation
C—(CH2)4—O H HOOC—(CH2)4—OH
OH OH
NH –H2O
(a) is uracil (present in RNA only)
H O—(CH2)4—C == O
-----O—(CH2)4—C—O—(CH2)4—C--- or —O—(CH2)4—C—
n
H 3C (An ester group) (Polymer)
NH
(b) is thymine (present in DNA only)
21. The correct match between Item I and Item II
is
NH2
Item I Item II
N A. Ester test P. Tyr
(c) is cytosine (present in both DNA and RNA)
B. Carbylamine test Q. Asp
C. Phthalein dye test R. Ser
S. Lys
N¾Me
(d) is not a pyrimidine base but a (a) A → Q; B → S; C → R
derivative of uracil. (b) A → R, B → Q; C → P
Me (c) A → R; B → S; C → Q
(d) A → Q; B → S; C → P

Exp. (d) (B) Molecule binding to the active site of enzyme

is called competitive inhibitor.
The correct match is :
(C) Molecule crucial for communication in the
A → (Q ); (B ) → (S ) (C ) → (P )
body is called receptor.
R ⇒ CH2—COOH C2H5OH/H2SO4/∆ (D) Molecule binding to the enzyme covalently is
Asp [Aspartic acid] called poison.

[Ester test] (A)
(Q)
Sweet smell Thus, the correct match is :
of ester
A →R, B →P, C →Q, D → S
R ⇒ (CH2)4—NH2 CHCl /alc.KOH
3
Lys [Lysine]
[Carbylamine test] (B)
OOC (S) 23. The homopolymer formed from
Foul smell
CH— R
of isocyanide 4-hydroxybutanoic acid is
H3N
General
formula of O, Conc. H2SO4/∆
amino acid (a) —OC(CH2)3—O— (b) —C(CH2)2C—
n n
R ⇒ ¾CH2 OH
Tyr [Tyrosine] [Phthalein dye test] (C)
(P) Resultant colourless (c) —C(CH2)3—O— (d) —C(CH2)2C—O—n
solution turns pink n
(A) Ester test confirms the presence of [JEE Main 2019, 11 Jan Shift-II]
COOH group.
(B) Carbylamine test confirms the presence of Exp. (c)
NH2 group (1°). On polymerisation, 4-hydroxy butanoic acid will
(C) Phthalein dye test confirms the presence of produce a condensation homopolymer by loss of H 2O
phenolic OH group. molecules.
22. The correct match between Item I and Item II

is HO—C—CH2CH2CH2—O H + HO —C—(CH2)3—O H
4-hydroxy butanoic acid
Item I Item II –H2O
A. Allosteric P. Molecule binding to the

effect active site of enzyme.
-----—C—(CH2)2CH2—O—C—(CH2)2CH2—O----
B. Competitive Q. Molecule crucial for Ester linkage
inhibitor communication in the body.
The homopolymer obtained can also be represented as
C. Receptor R. Molecule binding to a site O
other than the active site of 
enzyme. —
[ C — (CH 2 )3O —] n
D. Poison S. Molecule binding to the

enzyme covalently.
24. Among the following compounds, most basic
amino acid is
(a) A → P; B → R; C → S; D → Q (a) serine (b) asparagine
(b) A → P, B → R; C → Q; D → S (c) lysine (d) histidine
(c) A → R; B → P; C → S; D → Q
(d) A → R; B → P; C → Q; D → S
[JEE Main 2019, 11 Jan Shift-II] Exp. (c)
The most basic amino acid is lysine. There are only
Exp. (d) two basic amino acids (amino acids with two basic
(A) Molecule binding to a site other than the active nitrogen containing groups). These are lysine and
site of enzyme is called allosteric effect. arginine. Lysine have an ε-amino group. At

physiological pH, the groups are protonated as Exp. (c)

follows:
+ Nylon 6, 6 has following structure:
NH3 O
γ β
 O O 
δ
H3N
+ ý α
C O
s    
CH2CH2CH2CH2 CH  N (CH2 )6 N C (CH2 )4 C  

an ε-amino group    
 H H 
Asparagine is an acidic amino acid. It is the amide of  6 C-atoms 6 C-atoms n
aspartate. As it is a condensation polymer hence, each of its
Histidine is an imidazole substituted alanine. monomeric unit must contain 6 carbon atoms in them.
Serine contain alcohol group and is an HO-substituted Hence, a combination of adipic acid and
alanine. hexamethylene diamine is the correct answer. Both of
these units react as follows to form nylon-6, 6.
25. Poly-β-hydroxybutyrate-Co-β-hydroxyvalerate O
(PHBV) is a copolymer of ……
(a) 3-hydroxybutanoic acid and nH N (CH2)6 N H + OH C (CH2)4 C OH
2-hydroxypentanoic acid Adipic acid
H H –nH2O H
(b) 2-hydroxybutanoic acid and Hexamethylene O
3-hydroxypentanoic acid diamine
(c) 3-hydroxybutanoic acid and N (CH2)6 N C (CH2)4 C
4-hydroxypentanoic acid
(d) 3-hydroxybutanoic acid and H H O
n
3-hydroxypentanoic acid Nylon-6, 6
Exp. (d) 27. The correct structure of histidine in a
strongly acidic solution ( pH = 2 ) is
Poly-β-hydroxy butyrate Co-β-hydroxyvalerate (PHBV)
r s r
is a copolymer of 3-hydroxybutanoic acid and (b) H3N CH COOH
(a) H3N CH COO
3-hydroxypentanoic acid. It is used in speciality r r
packaging, orthopaedic devices and in controlled NH2 NH2
release of drugs. PHBV undergoes bacterial degradation
N N
in the environment. The reaction involved is as follows :
OH r s r
(c) H3N CH COO (d) H3N CH COOH

CH 3 CH  CH 2COOH + +
NH NH
3-hydroxybutanoic acid
OH NH
Nr
 H
CH 3CH 2 CHCH 2COOH →
3-hydroxypentanoic acid
 O CH 2CH 3  Exp. (d)
 
 
   Histidine has following structure in
 O CH  C H 2 C  O CH  CH 2 C 
  
H 2N CH C OH
 CH 3 O n
 
CH2 O
Lone pairs of
26. The two monomers for the synthesis of
both of these These lone pairs are
N
nylon 6, 6 are nitrogen are not free for donation as
freely available N H these are delocalised
(a) HOOC(CH2 )4 COOH, H2N(CH2 )4 NH2
for donation with-π bonds.
(b) HOOC(CH2 )6 COOH, H2N(CH2 )4 NH2
At highly acidic pH, i.e. 2 both the nitrogens with lone
(c) HOOC(CH2 )4 COOH, H2N(CH2 )6 NH2
pairs will accept one H + each and C OH will not
(d) HOOC(CH2 )6 COOH, H2N(CH2 )6 NH2 
[JEE Main 2019, 12 Jan Shift-II] O

loose its H + . Thus, the final structure of histidine at It is produced by decarboxylation of histidine having
pH = 2 will be following structure.
+ It is clearly visible from the above structure that
H 3N CH C OH histamine has two basic centres namely aliphatic amino
group and basic nitrogen of imidazole ring.
CH2 O
The aliphatic amino group has pK a around 9.4.

+ In blood with pH around 7.4 the aliphatic amino group
H N of histamine become protonated to give a single
NH charged cation as shown below
H
28. Glucose on prolonged heating with HI gives N +
NH3
[JEE Main 2018]
(a) n-hexane (b) 1-hexene N
(c) Hexanoic acid (d) 6-iodohexanal
30. The formation of which of the following
Exp. (a) polymers involves hydrolysis reaction?
HI is a strong reducing agent. It reduces both primary (a) Nylon-6 [JEE Main 2017 (Offline)]
and secondary alcoholic groups of glucose along with (b) Bakelite
the carbonyl group to produce n-hexane as
(c) Nylon-6, 6
CHO Carbonyl group CH3 (d) Terylene
Secondary HI
(CHOH)4 alcoholic
group ∆ (CH2)4 Exp. (a)
(Prolonged)
Primary Nylon-6 or perlon is prepared by polymerisation of
CH2OH CH3
alcoholic amino caproic acid at high temperature. Caprolactam
Glucose group n-hexane is first hydrolysed with water to form amino acid which
on heating undergoes polymerisation to give nylon-6.
29. The predominant form of histamine present in O
human blood is (pK a , Histidine = 6.0 ) O
NH Hydrolysis + –
[JEE Main 2018] H3N—(CH2)5—C—O
H H ∆ Polymerisation
N N r Caprolactam O
NH2 NH3
(a) (b)
r [ HN— (CH2)5—C —
]n
N N Nylon-6
H
H H
N N r 31. Which of the following compounds will
NH2 NH3 behave as a reducing sugar in an aqueous KOH
(c) (d)
r solution? [JEE Main 2017 (Offline)]
N N
H HOH2C O CH2OH HOH2C O CH2OH
(a) HO (b) HO
Exp. (d)
OCOCH3
Our blood is slightly basic in nature with pH range
from 7.35-7.4. OH OH
The structure of histamine is given below : HOH2C
Aliphatic HOH2C O CH2OH O CH2OCH3
amino group
H
N (c) HO (d) OH
Imidazole NH2
ring OCH3 OH
N OH OH
Basic nitrogen of imidazole ring

Exp. (a) O
Sugars that have an aldehyde, a ketone, a hemiacetal S C

Methionine
or a hemiketal group is able to reduce an oxidising H3C OH
agent. These sugars are classified as reducing sugars.
NH2
O CH2OH O
HOH2C HOH2C CH2OH

NH2
aq·KOH
HO –+ OH
OCOCH3 –CH3COOK O– N
Cytosine
OH OH
Hemiacetal O N
H
O 34. Which polymer is used in the manufacture of

HOH2C CH2OH
paints and lacquers? [JEE Main 2015]
HO (a) Bakelite (b) Glyptal
(c) Polypropene (d) Polyvinyl chloride
OH Exp. (b)
(α-hydroxyketone)
(a) Bakelite is used for making gears, protective
Hemiacetal can be easily reduced by oxidising agent coating and electrical fittings.
such as Tollen’s reagent.
(b) Glyptal is used in the manufacture of paints
O and lacquers.
HOH2C CH2OH
O
Tollen’s
positive silver
(c) PP is used in the manufacture of textile,
OH reagent packaging materials etc.
mirror test.
(d) Polyvinyl chloride (PVC) is used in the
OH manufacture of rain coats, hand bags, leather
(Reducing sugar) clothes etc.
32. Which of the following statements about low 35. Which of the vitamins given below is water
density polythene is false? soluble? [JEE Main 2015]
[JEE Main 2016 (Offline)] (a) Vitamin C (b) Vitamin D
(a) It is a poor conductor of electricity (c) Vitamin E (d) Vitamin K
(b) Its synthesis required dioxygen or a peroxide Exp. (a)
initiator as a catalyst
(c) It is used in the manufacture of buckets, dustbins Vitamin B and C are water soluble while vitamin A,D,E
etc. and K are fat soluble or water insoluble.
(d) Its synthesis requires high pressure 36. Which one is classified as a condensation
Exp. (c) polymer? [JEE Main 2014]
High density polythene is used in the manufacture of (a) Dacron (b) Neoprene
buckets, dustbins etc. (c) Teflon (d) Acrylonitrile
33. Thiol group is present in [JEE Main 2016 (Offline)] Exp. (a)
(a) cystine (b) cysteine Dacron is a condensation polymer of ethylene glycol
(c) methionine (d) cytosine and methyl terepthalate.
Exp. (b) MeO C C OMe + nHO CH2CH2OH

NH2
O O
Cystine HO S COOH (n -1) MeOH Polymerisation
C S
NH2 O C C OCH2 CH2
O
COOH
Cysteine
HS O O
Dacron n
NH2

37. Which one of the following bases is not present Exp. (c)
in DNA? [JEE Main 2014] NH2
(a) Quinoline (b) Adenine Glycine CH2 is α-amino acetic acid with no
(c) Cytosine (d) Thymine COOH
chiral carbon, thus optically inactive.

Exp. (a)
DNA contains four nitrogenous pyramidine bases, 42. The presence or absence of hydroxy group on
adenine, guanine, cytosine, thymine. While quinoline is which carbon atom of sugar differentiates RNA
an alkaloid, hence, it is not present in DNA. and DNA? [AIEEE 2011]
(a) 1st (b) 2nd
38. Synthesis of each molecule of glucose in
(c) 3rd (d) 4th
photosynthesis involves [JEE Main 2013]
(a) 18 molecules of ATP (b) 10 molecules of ATP Exp. (b)
(c) 8 molecules of ATP (d) 6 molecules of ATP
In RNA molecule, sugar moeity is β-D-ribose in which
Exp. (a) — OH group is present at 2nd carbon. Whereas in
DNA, it is β-D-2-deoxyribose in which OH group is
6CO 2 + 12NADPH + 18ATP → C 6H12O 6 absent at 2nd carbon.
+ 12NADP + 18 ADP 5 5 4
HOH2C O HOH2C O
OH OH
39. The species which can best serve as an initiator 4 1 4 1
H H H H
for the cationic polymerization is [AIEEE 2012] H H
3 2 H 3 2 H
(a) LiAlH 4 (b) HNO 3 (c) AlCl 3 (d) BaLi OH OH OH H
Exp. (c) β-D-ribose β-D-2-deoxyribose
Electron-deficient specie (Lewis acid) is used as an

initiator for cationic polymerization. 43. The change in the optical rotation of freshly
prepared solution of glucose is known as
40. Which of the following compounds can be [AIEEE 2011]
detected by Molisch’s test? [AIEEE 2012]
(a) tautomerism (b) racemization
(a) Nitro compounds (b) Sugars (c) specific rotation (d) mutarotation
(c) Amines (d) Primary alcohols
Exp. (d)
Exp. (b)
A spontaneous change in the specific rotation of a
Molisch’s test is used for the detection of solution of an optically active compound is called
carbohydrates. Add two drops of alcoholic solution of mutarotation.
α-naphthol to the carbohydrate solution under study. Hemiacetal forms of α- and β-D- glucose are stable in
Add conc. H 2SO 4 slowly by the side of the test tube. A solid state but in aqueous solution, there is opening of
the cyclic structure which gives solution of constant
violet ring is formed at the junction of the two liquids, if specific rotation.
carbohydrate is present.
41. Which one of the following statements is 44. Thermosetting polymer, bakelite is formed by
correct? [AIEEE 2012] the reaction of phenol with [AIEEE 2011]
(a) All amino acids except lysine are optically (a) CH 3CH 2CHO (b) CH 3CHO
active. (c) HCHO (d) HCOOH
(b) All amino acids are optically active. Exp. (c)

(c) All amino acids except glycine are optically Bakelite is a thermosetting polymer formed by the
condensation reaction of phenol with HCHO in the
active.
presence of conc. H 2SO 4 .
(d) All amino acids except glutamic acids are It is thus, a cross-linked polymer in which condensation
optically active. takes place at o- and p −positions.
Thus, HCHO is the correct option.

45. Biuret test is not given by [AIEEE 2010]

Exp. (c)
(a) carbohydrates (b) polypeptides Buna-N is actually abbreviated form, where Bu
represents 1,3-butadiene, na represents Na, sodium
(c) urea (d) proteins
and N represents nitrile (acrylonitrile).
Exp. (a) Thus, buna-N is a copolymer of 1,3-butadiene and
Biuret test is characteristically given by the compound acrylonitrile usually polymerise in the presence of
O sodium.

having —C — NH — functional group. 49. Bakelite is obtained from phenol by reacting
with [AIEEE 2008]
46. The polymer containing strong intermolecular
(a) (CH 2OH)2 (b) CH 3CHO
forces e.g., hydrogen bonding, is [AIEEE 2010]
(c) CH 3COCH 3 (d) HCHO
(a) teflon (b) nylon 6 6
(c) polystyrene (d) natural rubber Exp. (d)
Bakelite is obtained from phenol by reacting with HCHO
Exp. (b) in the acidic or alkaline medium.
Nylon-6 6 contains strong intermolecular forces like
O 50. α-D(+)-glucose and β-D-(+)-glucose are
 (a) conformers [AIEEE 2008]
hydrogen bonds that are formed between — C —NH
(b) epimers
group of successive chains. (c) anomers
(d) enantiomers
47. The two functional groups present in a typical
carbohydrate are [AIEEE 2009] Exp. (c)
(a) —OH and —COOH
α-D(+) glucose and β-D(+) glucose are anomers of
(b) —CHO and —COOH glucose.
(c) C == O and —OH
CH2OH CH2OH
(d) —OH and —CHO
O O
H H H H H OH
Exp. (c, d)
Carbohydrates are optically active polyhydroxy HO OH H OH HO OH H H
aldehyde or polyhydroxy ketones.
C == O, OH are the functional groups of typical H OH H OH
ketose while —CH ==O, OH are the functional groups α-D-glucose β-D-glucose
of typical aldose.
48. Buna-N synthetic rubber is a copolymer of 51. The secondary structure of a protein refers to
[AIEEE 2009] [AIEEE 2007]
Cl (a) α-helical backbone
 (b) hydrophobic interactions
(a) H 2C == CH —C == CH 2 and (c) sequence of α-amino acids
H 2C == CH — CH == CH 2 (d) fixed configuration of the polypeptide backbone
(b) H 2C == CH — CH == CH 2 and
H 5C 6 — CH == CH 2
Exp. (a)
Primary structure involves sequence of α-amino acids
(c) H 2C == CH — CN and H 2C == CH — CH == CH 2 in a polypeptide chain.
(d) H 2C == CH — CN and H 2C — C == CH 2 Secondary structure involves α-helical and β-pleated
 sheet like structures.
CH 3

52. The term anomers of glucose refers to Exp. (a)

(a) isomers of glucose that differ in configurations at Synthesis of RNA/DNA from phosphoric acid, ribose
carbons one and four (C-1 and C-4 and cytosine is given below. Thus, ester linkages are at
(b) a mixture of (D)-glucose and (L)-glucose C 5′ and C 1′ of sugar molecule.
(c) enantiomers of glucose Dehydration
(d) isomers of glucose that differ in configuration at OH

carbon one (C – 1) [AIEEE 2006] 5′ NH2
HOCH2
O OH
O P OH
Exp. (d) + 1′ 5 4 N
4 H H + 3
Anomers of glucose are cyclic diastereomers (epimers) OH 3 2 12
6
differing in configuration of the hydroxyl group at C-1, H H N O
existing in two forms α and β, respectively. OH OH H
53. The pyrimidine bases present in DNA are NH2
[AIEEE 2006]
OH 5 4
3N
(a) cytosine and adenine (b) cytosine and guanine 5' 6 12
(c) cytosine and thymine (d) cytosine and uracil O P O CH2 N O
–2H2O O
Exp. (c) OH 4' H H 1'
In DNA, cytosine and thymine are pyrimidine bases. 3' 2'

H H
H
OH OH
C
57. Identify the correct statement regarding
N N
enzymes. [AIEEE 2004]
HC CH (a) Enzymes are specific biological catalysts that can
normally function at very high temperatures (T~
CH 1000 K)
Pyrimidine base (b) Enzymes are normally heterogeneous catalysts
that are very specific in their action
54. Which of the following is fully fluorinated (c) Enzymes are specific biological catalysts that
polymer? [AIEEE 2005] cannot be poisoned
(a) PVC (b) Thiokol (d) Enzymes are specific biological catalysts that
possess well defined active sites
(c) Teflon (d) Neoprene
Exp. (d)
Exp. (c)
Normal optimum temperature of enzymes is between
Teflon is 
[ CF2 CF2 ]n .
25°C to 40°C. Hence (a) is false. Enzymes are normally
55. Which of the following is a polyamide? homogeneous catalysts that can be poisoned.
(a) Bakelite (b) Terylene Thus, (b) and (c) are also false. Enzymes have well defined
(c) Nylon-6 6 (d) Teflon [AIEEE 2005] active sites and their actions are specific in nature.
Exp. (c) 58. Insulin production and its action in human

Nylon-6 6 is a polyamide of hexamethylene diamine body are responsible for the level of diabetes.
(CH 2 )6(NH 2 )2 and adipic acid (CH 2 )4 (COOH)2. This compound belongs to which of the
(Each reactant has six-carbon chain, hence trade code following categories ? [AIEEE 2004]
6, 6 is used.) (a) A coenzyme
(b) A hormone
56. In both DNA and RNA, heterocylic base and
(c) An enzyme
phosphate ester linkages are at [AIEEE 2005]
(d) An antibiotic
(a) C 5′ and C 1′ respectively of the sugar molecule
(b) C ′1 and C ′5 respectively of the sugar molecule Exp. (b)
(c) C ′2 and C 5′ respectively of the sugar molecule Insulin is a hormone built up of two polypeptide chains.
(d) C ′5 and C 2′ respectively of the sugar molecule

59. Which base is present in RNA but not in DNA? 62. Complete hydrolysis of cellulose gives
[AIEEE 2004] (a) D-fructose (b) D-ribose
(a) Uracil (b) Cytosine (c) D-glucose (d) L-glucose
(c) Guanine (d) Thymine [AIEEE 2003]
Exp. (a) Uracil is present in RNA but not in DNA. Exp. (c)
Partial hydrolysis of cellulose gives the disaccharide
60. The reason for double helical structure of DNA cellobiose (C 12H 22O11 ). Cellobiose resembles maltose
is operation of [AIEEE 2003] (which on acid catalysed hydrolysis yields two molar
(a) van der Waals’ forces equivalents of D-Glucose) in every respect except one :
the configuration of its glycosidic linkage.
(b) dipole-dipole interaction
(c) hydrogen bonding 63. Monomers are converted to polymer by
(d) electrostatic attractions (a) hydrolysis of monomers [AIEEE 2002]
Exp. (c) (b) condensation reaction between monomers
(c) protonation of monomers
Hydrogen bonding is involved as a molecular force in
the DNA molecule.
Watson and Crick observed the purine- pyrimidine type Exp. (b)
of hydrogen bonding (instead of purine-purine and
pyrimidine-pyrimidine type). Condensation is the process of aggregation of more
than one molecule without loosing any atom or group
61. Nylon threads are made up of [AIEEE 2003] (sometimes smaller group or atoms H 2O, R OH etc
are released).
(a) polyvinyl polymer
nCH 2 == CH 2 → CH 2 (CH 2 CH 2 ) CH 2 
(b) polyester polymer
(Monomer) Polymer
(c) polyamide polymer
(d) polyethylene polymer 64. A substance forms Zwitter ion. It can have
Exp. (c) functional groups [AIEEE 2002]
(a)  NH 2 , COOH (b)  NH 2 ,  SO 3H
Nylon threads are made up of polyamide, some (c) Both (a) and (b) (d) None of these
common are
O Exp. (c)

Nylon 6 : H 2N ( CH 2 
) 5 C OH ; Monomer For the formation of Zwitter ion, basic part and acidic
part both should be present in a molecule.
Polymer
O O 65. RNA contains [AIEEE 2002]
  (a) ribose sugar and thymine
HN  ( CH 2 )5 C NH  ( CH 2 )5  C NH 
(b) ribose sugar and uracil
O
 (c) deoxyribose sugar and uracil
Nylon 6 6 : HO  C (CH 2 )
4 COOH
(d) deoxyribose sugar and thymine
and H 2N 
( CH 2 )6 NH 2; Copolymer Exp. (b)
O O  RNA, Ribonucleic acid.
   

 C ( CH 2 )4 C NH ( CH 2 )6  NH  Sugar present in RNA is D (–) ribose. It consists of
  cytosine and uracil as pyrimidine and guanine and
adenine as purine bases.

20
Analytical Chemistry
and Chemistry
in Everyday Life
1. An organic compound X showing the m-cresol on reaction with 10% NaOH forms
following solubility profile is 3-methyl sodiumphenoxide ion.
[JEE Main 2019, 8 April Shift-I] OH O–Na+
Water
Insoluble
10% NaOH
X
5% HCl
Insoluble CH3 CH3
10% NaOH It does not react with H2O, 5% HCl and 10%
Soluble
NaHCO 3 .
10% NaHCO3 Oleic acid (C18H34O 2 ) is soluble in 10% NaOH
Insoluble
and 10% NaHCO 3 due to the presence of
(a) o -toluidine (b) oleic acid COOH group.
(c) m-cresol (d) benzamide O

Exp. (c) Benzamide (C 6H5C NH2 ) is insoluble in 5%
HCl, 10% NaOH and 10% NaHCO 3 due to the
m-cresol is the organic compound that shows the
presence CONH2 group. o-toluidine is
following solubility profile.
soluble in 5%. HCl due to presence of basic
Water group ( NH2 ) attached to ring.
Insoluble
CH3
5% HCl
2. The organic compound that gives following
Insoluble qualitative analysis is
10% NaOH [JEE Main 2019, 9 April Shift I]
Soluble
m-cresol
OH Test Inference
10% NaHCO3 (i) Dil. HCl Insoluble
Insoluble
(ii) NaOH solution Soluble
(iii) Br2 /water Decolourisation

Analytical Chemistry and Chemistry in Everyday Life 309
NH2 OH
(a) (b)
pH pH
NH2 OH
(c) (d)
V(mL) V(mL)
(C) (D)
Exp. (b) (a) (D) (b) (A) (c) (B) (d) (C)
Phenol (ArOH) is insoluble in dil. HCl and readily Exp. (b)
soluble in NaOH solution. It reacts with Br2 /water
to give 2, 4, 6-tribromophenol. It readily The graph that shows the correct change of pH
decolourises the yellow colour of Br2 water. of the titration mixture in the experiment is
Reactions involved are as follows :
OH
Dil. HCl
pH
· no reaction
Phenol
(Acidic in nature) V(mL)
– +
OH ONa In this case, both the titrants are completely
ionised.
+ −
· NaOH HCl + NaOH - Na Cl + H O 2
⊕
È
Phenol Sodium
As H is added to a basic solution, [OH ]
(Acidic in nature) phenoxide decreases and [H+ ] increases. Therefore, pH
goes on decreasing. As the equivalence point is
OH OH
reached, [OHÈ ] is rapidly reduced. After this point
Br Br [OH È] decreases rapidly and pH of the solution
Br2 Water remains fairly constant. Thus, there is an inflexion
· point at the equivalence point.
Phenol The difference in the volume of NaOH solution
Br between the end point and the equivalence point
White ppts. is not significant for most of the commonly used
(2, 4, 6-tribromophenol)
indicators as there is a large change in the pH
value around the equivalence point. Most of
3. In an acid-base titration, 0.1 M HCl solution them change their colour across this pH change.
was added to the NaOH solution of
unknown strength. Which of the following 4. Noradrenaline is a/an
correctly shows the change of pH of the
(a) antidepressant (c) antihistamine
titration mixture in this experiment?
[JEE Main 2019, 9 April Shift-II] (c) neurotransmitter (d) antacid
Exp. (c)
Noradrenaline is one of the example of
pH pH
neurotransmitters. It plays a major role in mood
changes. If the level of noradrenaline is low for
some reason, then signal-sending activity
V(mL) V(mL) becomes low and the person suffers from
(A ) (B) depression.

O
5. Which one of the following is likely to give a
precipitate with AgNO3 solution? (C) H2N S N
H N
(a) CH2 == CH  Cl (b) CCl 4 O
(c) CHCl 3 (d) (CH3 )3 CCl Primary Sulphapyridine
amine (–NH2) CHCl3 + KOH (alc.)

Foul smell
(Carbylamine
Exp. (d) test) (P) of isocyanide
(CH3 )3 CCl gives a precipitate with AgNO 3 O
H H CH3
solution because it forms stable carbocation. S
(D) R C NH
(i.e. tertiary) that readily combines with AgNO 3 to CH3
give precipitates of AgCl. N COOH
CH3 O
H
 + Penicillin
CH3 C  Cl + AgNO 3 → (CH3 )3 C + AgCl NaHCO3(aq)
Becomes soluble
 (White (Sodium
with effervescence
ppts. ) hydrogen
CH3 carbonate) of CO2 gas
(Q)
CH2 == CH Cl forms unstable carbocation.
Hence, it does not readily react with AgNO 3 . Thus, the correct match is:
A → R; B → S; C → P; D → Q
6. The correct match between Item-I and
Item-II is 7. The correct match between item ‘I’ and item
‘II’ is
Item I (Drug) Item II (Test)
Item ‘I’ Item ‘II’
A. Chloroxylenol P. Carbylamine test
(Compound) (Reagent)
B. Norethindrone Q. Sodium hydrogen
(A) Lysine (P) 1-naphthol
carbonate test
(B) Furfural (Q) Ninhydrin
C. Sulphapyridine R. Ferric chloride test
(C) Benzyl alcohol (R) KMnO 4
D. Penicillin S. Bayer’s test
(D) Styrene (S) Ceric ammonium
(a) A→ R ; B→ P ; C→ S ; D→ Q nitrate
(b) A→ R ; B→ S ; C→ P ; D→ Q Codes
(c) A→ Q ; B→ P ; C→ S ; D→ R A B C D A B C D
(d) A→ Q ; B→ S ; C→ P ; D→ R (a) Q R S P (b) R P Q S
[ JEE Main 2019, 9 Jan Shift-I] (c) Q P S R (d) Q P R S
Exp. (b)
Phenolic Exp. (c)
OH –OH group
FeCl3 (A) → Q; B → (P) ; C → (S), D → (R)
(Ferric chloride)
(A) Violet colouration (A) Lysine (R=–(CH2)4–NH2)
(R) NH2
CH3 Ninhydrin test (B)
H 3C R CH Violet
COOH O
Cl colouration
OH
Chloroxylenol (Dettol)
(Ninhydrin),
OH boil
OH
H 3C C≡≡CH O
H OH
H Dil. KMnO4/5°C/OH –
Pink colour of
(Baeyer’s test)
(B) KMnO4 gets (B)
H H
(S) CHO +
discharged O
O (Furfural)
Norethindrone CH2SO4
D Violet colouration
C C Molisch Test (P)
(Double bond) (Molisch reagent)

CH2OH Ceric ammonium

nitrate (s) [CAN] required to titrate 30 mL of 0.2 M aqueous
(C) NaOH solution?
50% CH3COOH CHO (a) 75 mL (b) 25 mL
(Benzyl alcohol)
(c) 12.5 mL (d) 50 mL
(Benzaldehydel)
–
dil. KMnO4/OH /Cold (R) Exp. (b)
(D)
(Pink) OH The reaction of HCl with Na 2CO 3 is as follows:
(Styrene)
OH 2HCl + Na 2CO 3 → 2NaCl + H2O + CO 2
We know that, Meq of HCl = Meq of Na 2CO 3
H 25 30
H
H × 1 × MHCl = × 0.1 × 2
1000 1000
+Mn2+(Colourless) 30 × 0.2 6
MHCl = = M
25 25
8. The correct match between item (I) and The reaction of HCl with NaOH is as follows:
item (II) is NaOH + HCl → NaCl + H2O
Also, M eq of HCl = M eq of NaOH
Item - I Item - II
6 V 30
(A) Norethindrone (P) Antibiotic × 1× = × 0.2 × 1
25 1000 1000
(B) Ofloxacin (Q) Antifertility V = 25 mL
(C) Equanil (R) Hypertension
(S) Analgesics 10. Taj Mahal is being slowly disfigured and
discoloured. This is primarily due to
(a) (A) → (Q); (B) → (R); (C) → (S)
(a) water pollution (b) soil pollution
(b) (A) → (Q); (B) → (P); (C) → (R)
(c) global warming (d) acid rain
(c) (A) → (R); (B) → (P); (C) → (S)
(d) (A) → (R); (B) → (P); (C) → (R)
[JEE Main 2019, 11 Jan Shift-I] Exp. (d)
Exp. (b) Acid rain (pH = 3.5 − 5.6) constitutes strong
acids like HNO 3 , H2SO 4 and H2SO 3 which slowly
The correct match is: react with marble (CaCO 3 ) of Taj Mahal and
A → (Q), B → (P), C → (R) make it disfigured and discoloured. Here, CaCO 3
(A) Norethindrone It is an antifertility drug(Q ) (marble) gets dissolved in acids.
containing synthetic progesterone derivative. 2 H ⊕ ( aq )
[Other similar drug, is ethinylestradiol (novestrol)]. CaCO 3 (s ) → Ca 2 + (aq ) + H2O(l ) + CO 2 (g )↑
(Acid rain)
(B) Ofloxacin It is an antibiotic (P),
i.e produced wholly or partly by chemical 11. 50 mL of 0.5 M oxalic acid is needed to
synthesis with low concentration of
neutralise 25 mL of sodium hydroxide
microorganism.[Some other similar drugs :
Penicillin, chloramphenicol, salvarsan etc.] solution. The amount of NaOH in 50 mL of
(C) Equanil (meprobamate) It is a mild the given sodium hydroxide solution is
tranquilizer for relieving hypertension. It relieve (a) 40 g (b) 80 g (c) 20 g (d) 10 g
anxiety, stress, excitement by inducing a [ JEE Main 2019, 12 Jan Shift-I]
sense of well being.
(Other similar drug is chlordiazepoxide.) Exp. (*)
The reaction takes place as follows,
9. 25 mL of the given HCl solution requires H2C 2O 4 + 2NaOH → Na 2C 2O 4 + 2H2O
30 mL of 0.1 M sodium carbonate solution. Now, 50 mL of 0.5 M H2C 2O 4 is needed to
What is the volume of this HCl solution neutralize 25 mL of NaOH.

∴ Meq of H2C 2O 4 = Meq of NaOH H

CH3
50 × 0.5 × 2 = 25 × MNaOH × 1 N
N
MNaOH = 2M
N S C
Number of moles
Now, molarity = N NHCN
Volume of solution (in L)
H
Weight / molecular mass Cimetidine
=
Volume of solution (in L) CH (NO2)
w 1000
2 = NaOH × Me2N S C
40 50 O N NHMe
2 × 40 × 50 H
wNaOH = = 4g Ranitidine
1000
Phenelzine is a tranquilizer, not an antacid.
Thus, (*) none option is correct.
H
12. Which of the following is an anionic N NH2
detergent? [JEE Main 2016 (Offline)]

(a) Sodium lauryl sulphate
(b) Cetyltrimethyl ammonium bromide
(c) Glyceryl oleate 14. For the estimation of nitrogen, 1.4 g of an
(d) Sodium stearate organic compound was digested by
Kjeldahl’s method and the evolved
Exp. (a) ammonia was absorbed in 60 mL of M /10
Sodium lauryl sulphate sulphuric acid. The unreacted acid required
[(CH3 (CH2 )10 CH2OSO −3Na + )] = Anionic detergent 20 mL of M /10 sodium hydroxide for the
Cetyltrimethyl ammonium bromide complete neutralization. The percentage of
+ nitrogen in the compound is [JEE Main 2014]
 CH3  (a) 6% (b) 10%
  
CH (CH ) N  CH  Br − = Cationic (c) 3% (d) 5%
 3 2 15

3

 CH3  Exp. (b)
 
detergent Mass of an organic compound (OC ) = 1.4 g
Glyceryl oleate [(C17 H32COO)3 C 3H5 ] Suppose x m mole of N-atom is present in organic
compound. Thus,
= Non-ionic detergent
Kjeldahl’s
Sodium stearate[C17H35COO −Na + ] = Anionic soap Organic compound → NH 3
method x m mole
13. Which of the following compounds is not an M
antacid? [JEE Main 2015] Initial m mol of H2SO 4 = 60 × = 6 mmol
10
(a) Aluminium hydroxide M
mmoles of NaOH required by H2SO 4 = 20 ×
(b) Cimetidine 10
(c) Phenelzine = 2 mmol
(d) Ranitidine Involved reactions are
Exp. (c) 2NH3 + H2SO 4 → (NH4 )2 SO 4

 6 mmol 
 Initially taken 
Aluminium hydroxide Al (OH)3 , cimetidine and
ranitidine are antacids while phenelzine is not. H2SO 4 + 2NaOH → Na 2SO 4 + 2H2O
2 mmol reacted

Hence, 1 mmole of H2SO 4 reacted with NaOH. 14

Mass of N contained in NH3 = 8.5 mg ×
⇒ mmoles of H2SO 4 reacted from first equation 17
= 6−1 = 7 mg
= 5 mmoles Thus, % of N present in OC =
7
× 100
⇒ mmoles of NH3 in first equation = 2 × 5 29.5

= 10 mmoles = 237
. %
⇒ mmoles of N atoms in the organic compound 16. How many EDTA (ethylenediamine
= 10 m moles tetraacetic acid) molecules are required to
⇒ mass of N = 10 × 10−3 × 14 make an octahedral complex with a Ca 2+
= 0.14 g ion? [AIEEE 2006]
(a) Six (b) Three
Mass of N in OC
% of N in OC = × 100 (c) One (d) Two
Total mass of OC
0.14 Exp. (c)
∴ % of N = × 100
1.4
EDTA (Ethylenediamine tetraacetic acid)
= 10%
−
OOCCH2 CH2COO −
15. 29.5 mg of an organic compound containing N CH2 CH2  N
•• ••
nitrogen was digested according to −
OOCCH2 CH2COO −
Kjeldahl’s method and the evolved
It is hexadentate (6 electron pairs).
ammonia was absorbed in 20 mL of 0.1 M
That’s why for octahedral complex, only one EDTA
HCl solution. The excess of the acid required
is required.
15 ML of 0.1M NaOH solution for complete
neutralization. The percentage of nitrogen 17. Which one of the following types of drugs
in the compound is [AIEEE 2010] reduces fever ? [AIEEE 2005]
(a) 59.0 (b) 47.4 (a) Tranquiliser (b) Antibiotic
(c) 23.7 (d) 29.5 (c) Antipyretic (d) Analgesic
Exp. (c) Exp. (c)
Mass of organic compound = 29.5 mg Antipyretic drugs reduce fever. Analgesic relieve
mmoles of HCl = 20 × 0.1= 2 mmoles in pain, antibiotics act against bacterial infections
mmoles of NaOH = 15 × 0.1= 1.5 mmole while tranquilisers are used against mental
disorders.
Involved reactions are
NH3 + HCl → NH4Cl 18. Coordination compounds have great
(2 mmoles
initially taken) importance in biological systems. In this
HCl + NaOH → NaCl + H2O context, which of the following statements is
(Lewis acid ) (1.5 mmoles incorrect ? [AIEEE 2004]
initially taken) (a) Chlorophyll is green pigment in plant and
From the above equation, it is clear that contain calcium
mmoles of HCl reacted with NaOH = 2 − 15
. (b) Haemoglobin is the red pigment of blood and
= 0.5 mmol contains iron
m moles of NH3 reacted in first equation with HCl (c) Cyanocobalamin is vitamin B12 and contains
= 0.5 × 17 mg cobalt
(d) Carboxypeptidase-A is an enzyme and
Mass of NH3 = 0.5 × 17 mg = 8.5 mg
contains zinc

Exp. (a) (c) precipitate of Cr(OH)3 and Fe(OH)3 as

obtained in (b) are treated with conc. HCl
Chlorophyll contains Mg, hence (a) is incorrect
statement. when only Fe(OH)3 dissolves
(d) both (b) and (c)
19. The compound formed in the positive test

for nitrogen with the Lassaigne solution of
Exp. (b)
an organic compound is [AIEEE 2004] If Fe 3+ and Cr 3+ both are present, then very first
(a) Fe4 [Fe(CN)6 ]3 (b) Na 3 [Fe(CN)6 ] solid ammonium chloride and ammonium
hydroxide is added slowly till the solution smells of
(c) Fe(CN)3 (d) Na 4 [Fe(CN)5 NOS]
ammonia. Fe 3+ and Cr 3+ precipitates in the
Exp. (a) hydroxide form.
For identification, precipitate is treated with NaOH
If nitrogen is present in organic compound, then and Br2 water, yellow colouration confirms Cr 3+
sodium extract contains NaCN. ion.
Fuse
Na + C + N → NaCN 2NaOH + Br2 → NaBrO + NaBr + H2O
FeSO 4 + 6NaCN → Na 4 [Fe(CN)6 ] NaBrO → NaBr + [O]
(A)
+ Na 2SO 4 2Cr(OH)3 + 4NaOH + 3[O] → 2Na 2CrO 4
A changes to Prussian blue Fe 4 [Fe(CN)6 ]3 on + 5H2O
reaction with FeCl 3 . Solution is acidified and treated with lead acetate
solution.
4FeCl 3 + 3Na 4 [Fe(CN)6 ] →
Na 2CrO 4 + Pb(CH3COO)2 → PbCrO 4
Fe 4 [Fe(CN)6 ]3 + 12NaCl (Yellow ppt)
+ 2CH3COONa
20. Which of the following could act as a 22. Compound A given below is [AIEEE 2002]
propellant for rockets ? [AIEEE 2003] OCOCH3
(a) Liquid hydrogen + liquid nitrogen COOH
(b) Liquid oxygen + liquid argon
(c) Liquid hydrogen + liquid oxygen
(d) Liquid nitrogen + liquid oxygen A
(a) antiseptic (b) antibiotic
Exp. (c)
(c) analgesic (d) pesticide
Liquid hydrogen and liquid oxygen are good fuels.
Exp. (c)
21. If Fe 3+ and Cr 3+ both are present in
O
group III of qualitative analysis, then
distinction can be made by [AIEEE 2002]
O  C  CH3
(a) addition of NH4OH in the presence of NH4Cl
when only Fe(OH)3 is precipitated COOH
(b) addition of NH4OH in presence of NH4Cl when
Cr(OH)3 and Fe(OH)3 both are precipitated A
and on adding Br2 water and NaOH, Cr(OH)3 o-acetyl salicylic acid
dissolves aspirin (Analgesic)

Practice Set 1
Instructions
This test consists of 30 questions to be completed in 3 hrs.
Each question is allotted 4 marks for correct response.
1 marks will be deducted for indicating incorrect response of each question. No deduction from the total
score will be made if no response is indicated for an item in the answer sheet.
There is only one correct response for each question. Filling up more than one response in any question will
be treated as wrong response and marks for wrong response will be deducted according as per instructions.
1. An alkene, having molecular formula C 8H12 , 4. On the basis of molecular orbital theory, which
on ozonolysis yields glyoxal and one of the following statements is correct?
2, 2-dimethyl butane-1, 4-dial. The (a) O 2 is diamagnetic and N 2 is paramagnetic
structure of alkene is (b) N 2 is less stable than O 2
CH3 CH3 (c) He2 is stable and has bond order 1
(a) (b) (d)O 2 contains two unpaired electrons one each
CH3
in π* 2p x and π* 2p y orbitals
H3C
5. The following compound is used as
CH3 O
H3C O  C  CH3
(c) (d) H3C
COOH
(a) hypnotic (b) antiseptic
2. When equal volumes of the following
(c) analgesic
solutions are mixed, precipitation of AgCl
(d) an anti-inflammatory compound
(K sp = 1.8 × 10−10 ) will occur only with
O–
(a)10−4 M Ag + and10−4 MCl −
(b)10−5 M Ag + and10−5 M Cl − 6. The IUPAC name of is
−6 + −6 −
(c)10 M Ag and10 M Cl
(d)10 −10 +
M Ag and10 −10
M Cl − (a) methoxy-3-ethyl pentane
2−
(b) 2-ethyl-2-methoxy pentane
3. Amongst Ni(CO)4 , [Ni(CN)4 ] and NiCl 2−
4 (c) 3-ethyl-3-methoxy pentane
(a) Ni(CO)4 and NiCl 24 − are diamagnetic but (d) 3-methoxy-3-ethyl pentane
[Ni(CN)4 ]2 − is paramagnetic
7. Conductivity of 0.01 M NaCl solution is
(b) Ni(CO)4 and [Ni(CN)4 ]2 − are diamagnetic but 0.00147 Ω −1 cm −1. What happens to this
NiCl 24 − is paramagnetic
conductivity, if extra 100 mL of H 2O will be
(c) NiCl 24 − and [Ni(CN)4 ]2 − are diamagnetic but added to the above solution?
Ni(CO)4 is paramagnetic (a) Increases (b) Decreases
(d) Ni(CO)4 is diamagnetic but NiCl 24 − and (c) Remains constant
[Ni(CN)4 ]2 − are paramagnetic (d) First increases than decreases
Note All the Practice Sets (1-5) available for free online practice see detailed instructions back side of the Title.

COOH
8. The product formed when phthalimide is
treated with a mixture of Br2 and strong CH2 C CH3
NaOH solution is
(d) OH
(a) aniline (b) phthalamide
(c) phthalic acid (d) anthranilic acid

13. A solid AB has NaCl structure. If the radius
9. The correct order of mobility of alkali metal of cation A + is 110 pm, the maximum value
ions in aqueous solution is of the radius of the anion B − is
(a) Na + > K + > Rb+ > Li +
(a) 240.5 pm (b) 410.6 pm
(b) Rb+ > K + > Na + > Li +
(c) 315 pm (d) 265.7 pm
(c) Li + > Na + > K + > Rb+
(d) K + > Rb+ > Na + > Li + 14. A 5% by weight solution of cane sugar in
water has freezing point of −2 °C. The
10. The gas which has both oxidising as well as freezing point of 5% by weight solution of
reducing properties is glucose in water, if freezing point of pure
(a) CO (b) SO 2 (c) H2 S (d) PH3 water is 0°C is
(a) 3.8 K (b) 269.2 K (c) 273 K (d) 4.8 K
11. Which of the following sets of quantum
numbers represent the highest stability of an 15. At 20°C and 1.00 atm partial pressure of
atom? hydrogen, 18 mL of hydrogen, measured at
(a) n = 4, l = 1, m = 0, s = + 1 / 2 STP, dissolves in 1 L of water. If water at 20°C
(b) n = 4, l = 0,m = 0, s = + 1 / 2 is exposed to a gaseous mixture having a
(c) n = 4, l = 2 , m =1, s = + 1 / 2 total pressure of 1400 torr (excluding the
(d) n = 3, l = 1, m = 0, s = + 1 / 2 vapour pressure of water) and containing
68.5% by volume, then the volume of H 2
12. In a set of reactions, acetic acid yielded a measured at STP, which will dissolve in 1 L of
product D. water is
SOCl 2 (a) 23 mL (b) 12 mL (c) 18 mL (d) 121 mL
CH 3COOH → A   → B
Benzene
Anhy. AlCl 3 CH 3ClCH CH 3
HCN H2O 16. The compound C == C
→ C → D H CH 3
The structure of D would be will exhibit
(a) geometrical isomerism
OH (b) optical isomerism
(c) conformational isomerism
CH2 C CH3
(d) position isomerism
(a)
CN 17. Standard entropies of X 2 ,Y 2 and XY 3 are
OH 60, 40 and 50 JK −1 mol −1, respectively. For
1 3
the reaction, X 2 + Y 2 → XY 3 ,
C COOH 2 2
(b) ∆H = −30 kJ mol −1 to be at equilibrium, the
CH3 temperature should be
(a) 500 K (b) 750 K (c) 1000 K (d) 1250 K
CN
18. In the reaction ofKMnO4 with an oxalate in
C CH3
acidic medium, MnO4 is reduced to
(c)
OH
Mn 2 + and C 2O2–
4 is oxidised to CO 2 . Hence,
50 mL of 0.04 M KMnO4 is equivalent to

Practice Set 1 317
(a) 100 mL of 0.1 M H2C2O 4 24. The freezing point of equimolar solutions of
(b) 50 mL of 0.2 M H2C2O 4 urea, potassium ferricyanide, potassium
(c) 50 mL of 0.1 M H2C2O 4 ferrocyanide and barium chloride will be in
the order
(d) 25 mL of 0.1 M H2C2O 4 (a) potassium ferrocyanide > potassium
ferricyanide > barium chloride > urea

19. Consider the reaction X + Y → products. If (b) urea > barium chloride > potassium
the initial concentration of X is increased by ferricyanide > potassium ferrocyanide
four times, keeping the concentration of Y (c) urea > potassium ferrocyanide > barium
constant, the rate of reaction increases four chloride > potassium ferricyanide
times. When the concentrations of both X (d) potassium ferricyanide > potassium
ferrocyanide > barium chloride > urea
and Y becomes four times of their original
values, the rate of reaction becomes sixteen 25. Which of the following reactions is given by
times of its original value. The observed rate only primary amines?
law is (a) Reaction with HONO
(a) k [X ]2 [Y ]2 (b) k [X ][Y ]2 (b) Reaction with chloroform and alc. KOH
(c) k [X ][Y ] (d) k [X ]2 [Y ] (c) Reaction with acetyl chloride
(d) Reaction with Grignard reagent
20. Given that, C + O2 →
 CO2 ; ∆H ° = − x kJ
26. Hydrolysis of one mole of
2CO + O2 →
 2CO2 ; ∆H ° = − y kJ peroxodisulphuric acid produces
(a) two moles of sulphuric acid
The enthalpy of formation of CO will be
2x − y y − 2x (b) two moles of sulphuric acid and one mole of
(a) (b) (c) 2x − y (d) y = 2 x hydrogen peroxide
2 2
(c) one mole of sulphuric acid and one mole of
peroxomonosulphuric acid
21. What is the correct relationship between the
(d) one mole of sulphuric acid, one mole of
pHs of isomolar solutions of sodium oxide peroxomonosulphuric acid and one mole of
( pH1 ), sodium sulphide (pH 2 ), sodium hydrogen peroxide
selenide ( pH 3 ) and sodium telluride (pH 4 ) ?
(a) pH1 > pH2 ≈ pH3 > pH4 27. The reaction,
(b) pH1 < pH2 < pH3 < pH4 Cl C2H5
(c) pH1 < pH2 < pH3 ≈ pH4
(d) pH1 > pH2 > pH3 > pH4 Na metal
+ C2H5Cl
Dry ether
22. Which of the following statements is
incorrect ? is called
(a) Transition metals have high enthalpy of (a) Wurtz reaction (b) Friedel-Crafts reaction
atomisation (c) Fittig reaction (d) Wurtz-Fittig reaction
(b) Sc forms no coloured ions
(c) Transition metals never show very low 28. In the preparation of p-nitro acetanilide
oxidation state such as 0 and +1 from aniline, nitration is not done directly
(d) The chemical properties of lanthanoids are by nitrating mixture (a mixture of conc.
quite similar to each other H 2SO4 and conc. HNO3) because
(a) on nitration it gives o-nitro acetanilide
23. When FeCl3 is dissolved in water it causes (b) it gives a mixture of o-and p-nitro aniline
(a) a decrease in the H+ ions concentration (c) — NH2 group gets oxidised
(b) a decrease in OH− ions concentration (d) it forms a mixture of o-and p-nitro acetanilide
(c) a decrease in pH
(d) an increase in pH

o (a) 2.40 M (b) 2.66 M

29. If E cell of an electrochemical cell is
(c) 0.1 M (d) 3.01 M
0.086 volt. The value of x for the cell
Ag / AgNO3 (0.0093 M)|| AgNO3 (x M)| Ag will 30. If pH of 0.0001 M NaOH solution will be
be (a) 4 (b) 12 (c) 2 (d) 10
Answers
1. (b) 2. (a) 3. (b) 4. (d) 5. (c) 6. (c) 7. (a) 8. (d) 9. (b) 10. (b)
11. (d) 12. (b) 13. (d) 14. (b) 15. (a) 16. (b) 17. (b) 18. (c) 19. (c) 20. (b)
21. (d) 22. (c) 23. (c) 24. (b) 25. (b) 26. (c) 27. (d) 28. (c) 29. (b) 30. (d)
Solutions
1. Cyclic alkenes on ozonolysis generally yields [Ni(CN)4 ]2− are diamagnetic. While Cl − is a weak
glyoxal. Thus, the compound, C 8H12 must be an field ligand, hence NiCl 2−
4 is paramagnetic.
alkene.
4. O 2 (16) = σ1s 2 , σ* 1s 2 , σ2 s 2 , σ* 2 s 2 ,
CH3 H
σ2 pz2 , π2 p2x ≈ π2 py2 , π* 2 p1x ≈ π* 2 p1y
CH3 C C O O C H O 2 contains two unpaired electrons one each in
+ π* 2 px and π* 2 py orbitals, hence paramagnetic.
CH2 C O O C H
Glyoxal 5. o-acetylsalicylic acid is an analgesic.
H
2,2-dimethyl butane-1,4-dial
5
4
H3 C CH 6. 3 O
C CH H3 C 1 2
H3 C or
H3 C 3-ethyl-3-methoxy pentane
CH2 CH
CH (C8H12) 7. On dilution, number of ions or concentration of
solute increases. Hence, conductivity of NaCl
2. AgCl is precipitated only when solution increases.
[Ag + ] [Cl − ] > Ksp O
On mixing equal volumes of two solutions, C
concentration becomes halved.
∆
10−4 8. NH + Br2 + 4NaOH
In case of (a), [Ag + ] = M
2 C
10−4
[Cl − ] = M
2 O
Phthalimide
10−8
[Ag + ] [Cl − ] = = 2 .5 × 10−9 > Ksp O
2
OH
3. Ni (28) = [Ar] 3d 8 , 4s 2 C
Ni 2+ = [Ar] 3d 8 + 2NaBr + Na 2 CO 3 + H 2O
2+ NH2
Ni and Ni both have two unpaired electrons. CO
and CN− are strong field ligands and thus, unpaired Anthranilic acid
electrons get paired. Hence, Ni(CO)4 and

Practice Set 1 319
9. Hydration enthalpies of alkali metal ions decreases 14. For sugar, ∆T = 0 − (−2 ) = 2, w = 5 g
with the increase in ionic radii as we move down the
W = 100 − 5 = 95 g
group.
Therefore, smaller is the mass of hydrated species K f × w × 1000
∆T =
higher is the ionic mobility in the aqueous solution. m×W
Thus, the order for ionic mobility of ions is K f × 5 × 1000

2= ...(i)
Rb+ > K+ > Na + > Li+ 342 × 95
10. The oxidation number of sulphur varies from −2 to K f × 5 × 1000
For glucose, ∆T = ...(ii)
+6. In SO 2 , the oxidation state of sulphur is +4. 180 × 95
Thus, oxidation number may increase or decrease. From Eqs. (i) and (ii)
So, it can behave as both oxidising agent as well as
∆T = 3.8 K
reducing agent.
Thus, freezing point for glucose solution is
11. Lower the value of (n + l ) for an orbital, the lower is its
= 273 − 3.8 = 269.2 K
energy. If two orbitals have the same (n + l ) value,
the orbital with lower value of n has the lower energy 15. p H 2 =(1400 t orr) (0.685)
i .e., highest stability.
959
Set (d) has the lower value of n, thus has highest = 959 torr = atm
760
stability.
SOCl2 = 1.26 atm
12. CH3COOH CH3COCl According to Henry’s law,
(A) Amount of gas absorbed ∝ p
C CH3 V 1.26 atm
Hence, =
Benzene HCN 18 mL 1 atm
Anhy. AlCl3 O V = 23 mL
(B) H3C CH CH3 *
16. The compound | C ==C contains

CN COOH Cl
CH3
CH3 CH3 H
C +
C
H *
one chiral carbon (C) atom, so it is optically active
OH OH and exhibits optical isomerism.
(C ) (D) 17. For the reaction.
1 3
13. For NaCl type structure, X 2 + Y2 3 XY3
2 2
rc
= 0.414 to 0.732 ∴∆H = − 30 kJ = −30 × 103 kJ /mol -1
ra
rc Since, ∆H° = T∆S °
If = 0.414 ∆H°reac
ra ∴ T=
∆S °reac
110
ra
= 0.414, ra = 265.7 pm ∆S ° for the reaction is ∆S ° = ΣSoP − ΣS R
 1 
∆S ° = (S ° XY3 ) −   S ° X 2  +  S ° Y2  
3
If
rc
= 0.732 ∴
ra  2  2 
 1 
= 50 −   × 60 +  × 40 
110 3
= 0.732
ra  2  2 
ra = 150.3 pm = 50 − (30 + 60) = −40 JK −1 mol −1

−30 × 103 kJ mol −1
Hence, the maximum value of ra is 265.7 pm. ∴ T° = = 750 K
−40 JK −1 mol −1

18. Equivalent mass of MnO –4 = molar mass Greater the number of ions, lower will be the freezing
7–2 point of the compound. Thus, the correct order is
molar mass K 4 [Fe(CN)6 ] < K 3 [Fe(CN)6 ] < BaCl 2 <Urea
=
5 5 ions 4 ions 3 ions No ions
molar mass
Equivalent mass of C 2O 4 =2–
2(4 − 3) 25. Carbylamine reaction is given by only primary

molar mass amines.
=
2 RNH2 +CHCl 3 + 3 alc.KOH →
Milliequivalent of KMnO 4 = 50 × 5 × 0.04 = 10 RNC + 3KCl + H2O
and H2C 2O 4 = 50 × 2 × 0.1 = 10 26. H2S2O 8 + H2O → H2SO 5 + H2SO 4
19. On increasing [ X ] four times, the rate of the reaction Peroxodi Peroxomono Sulphuric
sulphuric acid sulphuric acid acid
becomes four times, hence the order of the reaction (1 mol) (1 mol)
(1 mol)
with respect to X is one.
Rate ∝ [ X ]1. Cl C2H5
But the rate becomes sixteen times, on increasing
the concentrations of both X and Y four times.
Hence the order is two with respect to X and Y. Na
27. + C2H5Cl
dry ether
Thus, the correct rate law is
Rate = k [ X ] [Y ] This reaction is known as Wurtz-Fittig reaction.
20. C + O 2 → CO 2 ; ∆H° = − x kJ ...(i)
28. The nitration of aniline is difficult to carry out with
2CO + O 2 → 2CO 2 ; ∆H° = − y kJ ...(ii) nitrating mixture, since NH2 group get oxidised
Divide Eq. (ii) by 2 because heat of formation is which is not required. So, the amino group is first
calculated for one mole of CO. protected by acylation to form acetanilide which is
1 y then nitrated to give p-nitro acetanilide as a major
CO + O 2 → CO 2 ; ∆H° = − kJ ...(iii)
2 2 product.
On subtracting Eq. (iii) from (i), we get 0.0591 C 2
29. E= log
1 n C1
C + O 2 → CO;
2 0.0591 x
y y − 2x 0.086 = log
∆H° = − x = kJ 1 0.0093
2 2 0.086 x
= log
21. The acidic strength increases from Na 2O to Na 2 Te 0.0591 0.0093
and greater the acidic strength of a solution, lesser x = 28.7 × 0.0093 = 2.66 M
will be its pH. Thus, 30. NaOH → Na + + OH–
pH ofNa 2O >pH ofNa 2S >pH ofNa 2Se > pH of
[OH− ] = [NaOH] = 0.0001 M
Na 2 Te
= 1 × 10−4 g/L
pH1 > pH2 > pH3 > pH4 Kw
[H+ ] =
22. Sometimes transition metals also show very low [OH− ]
oxidation states such as 0 and +1. 1 × 10−14
= = 1 × 10−10
23. FeCl 3 + 3H2O → 3HCl + Fe(OH)3 1 × 10−4
Strong acid Weak base pH = − log [H+ ]
Thus, pH decreases. = − log[1 × 10−10 ] = 10
24. Depression in freezing point is a colligative property,

so it depend upon the number of molecules or ions.

Practice Set 2
Instructions
For instructions refer to Practice Set 1.
(a)1s 2 , 2 s 2 , 2p 6 , 3s 2 , 3p 6 , 3d 3 , 4s 2
1. Addition of common salt to a sample of
water will (b)1s 2 , 2 s 2 , 2p 6 , 3s 2 , 3p 6 , 3d 1
(a) increase its freezing point and boiling point (c)1s 2 , 2 s 2 , 2p 6 , 3s 2 , 3p 6 , 3d 3
both (d)1s 2 , 2 s 2 , 2p 6 , 3s 2 , 3p 6 , 3d 2
(b) decrease its freezing point and increase the
boiling point
6. The final product C obtained in the
(c) increase its freezing point and decrease the
following sequence of reactions
boiling point
(d) decrease both the boiling and the freezing
points
2. When copper pyrites is roasted in excess of

air, a mixture of CuO + FeO is formed. FeO is
present as impurity. This can be removed as
slag during reduction of CuO. The flux
added to form slag is
(a) CaO, which is a basic flux
(b) SiO 2 , which is a basic flux
(c) Limestone, which is a basic flux CH3 CH3
(d) SiO 2 , which is an acidic flux
(a) (b)
3. The correct name for the complex ion
+
[Co(en)2Cl(ONO)] is Br Br Br
(a) cobaltdiethylenediaminechloronitrate OH
(b) chloro(ethyldiamine)nitritocobalt (III) CH3 CH3
(c) chloronitritodiethyldiaminecobaltate (III)
Br PO2H
(d) chlorobis(ethylenediamine)nitritocobalt (III)
(c) (d)
4. From 392 mg of H 2SO4 , 1.204 × 1021
Br
molecules are removed. The number of
NO2 NO2
moles of H 2SO4 left are
(a) 2.0 × 10−3 (b)1.2 × 10−3 7. The conductivity of 0.0100 M acetic acid
(c) 4.0 × 10−3 (d)1.5 × 10−3 solution, at infinite dilution and 25°C is
390.7 cm 2/Ω eq, the equivalent conductivity
5. A compound of vanadium has a magnetic of this solution is (K a = 1.8 × 10−5 )
moment of 1.73 BM. The electronic
(a) 25 cm 2 Ω eq (b)15 cm 2 Ω eq
configuration of the vanadium ion in this
compound is ( V = 23). (c)16 cm Ω eq2
(d) 20 cm 2 Ω eq

Alkyl C—O bond

8. 15. O
18 +
H3O
CH3CH2C  O  CH2CH3
Acyl C—O bond O
(a) ethyl methyl p -amino benzoic acid CH3CH2C—OH + CH3CH2OH

(b) p -carboxylic-N-methyl-N-ethyl aniline Select the correct statement.
(c) 4-(ethyl methyl amine) benzoic acid (a) Alkyl C—O bond breaks and O18 is contained
(d) None of the above in acid
(b) Alkyl C—O bond breaks and O18 is contained
9. Which part of amino acid molecule is linked in alcohol
through hydrogen bond in the secondary (c) Acyl C—O bond breaks and O18 is contained in
structure of proteins? alcohol
(a) COO R group (b) NHCH3 group (d) Acyl C—O bond breaks and O18 is contained in
(c) C  NH group (d) —OH group acid
||
O 16. The hybridisation in both CH 4 and NH 3 is
sp 3 , yet CH 4 is tetrahedral and NH 3 is of
10. The solubility of AgCl in water at 25°C is pyramidal shape because
1.79 × 10−3 g/L. The K sp of AgCl at 25°C is (a) it contains three single bonds and no lone pair
(a)1.68 × 10−12 (b)1.55 × 10−10 (b) it contains three single bonds and one lone pair
(c)12 .4 × 10−8 (d)1.73 × 10−14 (c) the number of surrounding atoms is three
(d) nitrogen is more electronegative than carbon
11. Which of the following has been arranged in 17. Mark out the correct nucleophilicity order in
the order of increasing covalent character? DMF.
(a) KCl < CaCl 2 < AlCl 3 < SnCl 4 (a) CH3s > OHs > NHs2 > F s > Is
(b) SnCl 4 < AlCl 3 < CaCl 2 < KCl (b) CHs3 > OHs > NHs2 > Is > F s
(c) AlCl 3 < CaCl 2 < KCl < SnCl 4 (c) Is > F s > OHs > NHs2 > CH3s
(d) CaCl 2 < SnCl 4 < KCl < AlCl 3 (d) CHs3 > NHs2 > OHs > F s > Is
12. The compound with highest boiling point is 18. Which of the following will not give
(a) n-heptane Lassaigne’s test for nitrogen?
(b) 2, 2- dimethyl pentane (a) NH2  NH2 (b) C6 H5 N == NC6 H5
(c) 2-methyl hexane (c) CH3CONH2 (d) CH3C ≡≡N
(d) iso-heptane 19. Compound ( A ) C 4H 8Cl 2 is hydrolysed to
13. Some solid NH 4HS is placed in a flask compound B , C 4H 8O which gives an oxime
and a negative Tollen’s test. What is the
containing 0.5 atm of NH 3. The pressure of
structure of ( A ) ?
NH 3 when equilibrium is reached, would be
(K p = 0.11) (a) CH3CH2 CH  CH2Cl
(a) 0.325 atm (b) 0.165 atm (b) ClCH2 |CH2  CH2  CH2Cl
Cl
(c) 0.5 atm (d) 0.665 atm Cl
|
(c) CH3  C  CH2CH3
14. For a reaction A + B → Product, the rate is |
given as k [ A ]1/ 3 [B ]2. The units of its rate Cl
constant are (d) CH3  CH2  CH2 CH3
| |
(a) mol −2 L2 s−1 (b) mol L−1 s−1 Cl Cl
−4/3 4/3 −1
(c) mol L s (d) mol −2/3 L2/3 s−1

Practice Set 2 323
20. Identify the product ( D ) in the following 26. Consider the following equation, which
sequence of reactions represents a reaction in the extraction of
NaNO KMnO chromium from its ore
CH 3CH 2NH 2 →
2
A →
4
B 2Fe 2O3 ⋅ Cr2O3 + 4Na 2CO3 + 3O2 →
HCl
(i) SOCl 2 Br2 2Fe 2O3 + 4Na 2CrO4 + 4CO2

→ C → D
(ii) NH 3 NaOH
Which one of the following statements
(a) ethanamide (b) methyl amine about the oxidation states of the substances
(c) methyl alcohol (d) ethyl amine is correct?
(a) The iron has been reduced from +3 to +2 state
21. Which of the following about wave function (b) The chromium has been oxidised from + 3 to
ψ, is not correct? + 6 state
(a) ψ may be a real valued wave function
(c) The carbon has been oxidised from +2 to +4
(b) ψmay be in some cases be a complex function state
(c) ψ has a mathematical significance only
(d) There is no change in the oxidation state of the
(d) ψ is proportional to the probability of finding substances in the reaction
an electron
22. By heating which of the following nitrogen 27. The vapour pressure of a pure liquid A is
70 torr at 27°C. It forms an ideal solution
dioxide cannot be obtained?
(a) KNO 3 (b) Pb(NO 3 )2
with another liquid B.The mole fraction of B
(c) Cu(NO 3 )2 (d) AgNO 3 is 0.2 and total vapour pressure of the
solution is 84 torr at 27 ° C. The vapour
23. Lanthanoids and actinoids both have a pressure of pure liquid B at 27°C is
tendency to form complexes. In which of (a) 14 torr (b) 56 torr
these, this tendency is greater? (c) 140 torr (d) 70 torr
(a) Lanthanoids
(b) Actinoids 28. 20 mL of 0.2 M NaOH is added to 50 mL of
(c) Both have equal tendency 0.2 M acetic acid. The pH of this solution
(d) Actinoids does not form complex after mixing is (K a = 1.8 × 10−5 )
(a) 4.5 (b) 2.3
24. Which of the following orders regarding (c) 3.8 (d) 4
bond length is correct?
(a) O −2 > O 2 > O +2 (b) O −2 < O 2 < O 2+ 29. In the reaction,
(c) O −2 > O 2 < O +2 (d) O −2 < O 2 > O 2+
2 Ag + + Cd → 2 Ag + Cd 2+ ,
25. The molar heat of formation of NH 4 NO 3 ( g ) °
the E Ag and E ° Cd 2+ / Cd are + 0.80 and
+
is −367.57 kJ and those of N 2O( g ), H 2O(l ) are /Ag
81.46 and 285.8 kJ, respectively at 25°C and −0.40 volts, respectively. If the
1 atm. The change in internal energy for concentration of Cd 2+ is taken 0.10 M rather
the reaction than 1M, then the total emf becomes
NH 4 NO 3(s ) → N 2O( g ) + 2H 2O(l ) is (a) more positive
(b) less positive
(a) −122.60 kJ (b) −125.07 kJ (c) remain same
(c) −120. 20 kJ (d) −123 kJ (d) decreases to negative

30. Four samples of acids and bases are taken Now for each sample enthalpy of
for an experiment neutralisation is calculated. Now the result
shows that
(I) 100 mL of 1 M NaOH and 100 mL of
(a) enthalpy of neutralisation calculated in each
1 M HCI
case is found same
(II) 100 mL of 2 M KOH and 100 mL of 1 M

(b) in case (I) and (IV), the value of enthalpy of
H 2 SO4 neutralisation is same
(III) 100 mL of 1 M CH 3COOH and 100 mL of (c) in case (I), (II) and (IV), the value of enthalpy
1 M NaOH calculated is same
(IV) 100 mL of 0.5 M KOH and 100 mL of 0.5 M (d) the value of enthalpy calculated is different for
HNO3 each sample
Answers
1. (b) 2. (d) 3. (d) 4. (a) 5. (b) 6. (b) 7. (c) 8. (c) 9. (c) 10. (b)
11. (a) 12. (a) 13. (d) 14. (c) 15. (c) 16. (b) 17. (d) 18. (a) 19. (c) 20. (b)
21. (d) 22. (a) 23. (b) 24. (a) 25. (b) 26. (b) 27. (c) 28. (a) 29. (a) 30. (c)
Solutions
1. Addition of solute decreases the freezing point and On solving, we get n = 1
increases the boiling point. Thus, V contains only one unpaired electron and its
electronic configuration is
2. SiO 2 is added as a flux as it is acidic in nature and V(23) = 1s 2 , 2 s 2 , 2 p6 , 3s 2 , 3 p6 , 3d 3 , 4s 2
reacts with basic FeO to form FeSiO 3 . This FeSiO 3
is removed as an impurity. V 4 + = 1s 2 , 2 s 2 , 2 p6 , 3s 2 , 3 p6 , 3d 1
3. The correct name is

chlorobis (ethylenediamine) nitritocobalt (III).
6.
4. Mass of H 2 SO 4 = 392 mg = 0.392 g
0.392
Number of moles of H2SO 4 = = 0.004
98
Number of moles removed from the solution
Here, n = number of moles
N = Number of molecules
N0 = Avogadro’s number
N 1.204 × 1021 molecules Br
n= = = 0.002
N0 6.02 × 1023 molecules
Number of moles of H2SO 4 left
[H3O+ ] [CH3COO − ]
−3 7. K a = = 1.8 × 10−5
= 0.004 − 0.002 = 2.0 × 10 [CH3COOH]
5. Magnetic moment (µ ) = n (n + 2 ) x = [H3O+ ] = [CH3COO − ]

CH3COOH = 0.0100 − x
. =
173 n (n + 2 )

Practice Set 2 325
x2 . = (0.5 + x) × x
011
Ka =
0.0100 − x x = 0165
.
x2 Q 0.0100 >>> x  p NH 3 = 0.5 + 0.165 = 0.665 atm
1.8 × 10−5 = ∴ 0.0100 − x = 0100
0.010  . 
14. Rate = k [ A]1/ 3 [B]2
x2 = 1.8 × 10−7
 conc.  = k [conc.]7/ 3
x = 4.2 × 10−4  time 
λ 4.2 × 10−4 k = conc.−4/ 3 t −1
=
λ∞ 1.0 × 10−2 = mol −4/ 3L4/ 3s −1
λ
= 4.2 × 10−2 O
390.7  18
λ ≈ 16 cm2 Ω eq
15. CH3CH2 C O CH2CH3 + H OH →
O
 18
8. CH3CH2 C OH + CH3CH2 OH
16. In NH3 , there are three single bonds and one lone
pair of electrons.
N

9. Proteins have C NH2 linkage. H

|| H H
O
Due to the presence of the lone pair, lone pair-bond
10. Solubility of AgCl in water pair repulsion increases which results in the
distorted geometry of the molecule, NH 3 .
. × 10−3 g/L
= 179
1.79 × 10−3 17. In the aprotic solvent DMF (dimethyl formamide),
= mol/L nucleophilicity follows the order of basicity. Hence,
143.5
the order of nucleophilicity is
−5
= 1.247 × 10 mol/L CHs3 > NHs2 > OHs > Fs > Is
−
ForQ AgCl 3 Ag + Cl +
S S 18. Hydrazine (NH2  NH2 ) do not respond to
Ksp = S × S = S 2 = (1.247 × 10−5 )2 Lassaigne’s test because it does not contain any
= 1.55 × 10−10 mol 2L−2 carbon atom and hence, NaCN is not formed.
19. Since, B does not give Tollen’s test, thus it is a

11. According to Fajan’s rule, ketone.
Covalent character ∝ charge on cation or anion Cl O
Thus, the correct order is | 2H 2O
||
H3C  C  CH2CH3 → H3C C CH2CH3
K+ < Ca 2+ < Al 3+ < Sn4+ |
− H 2O
(C 4 H 8O)
KCl < CaCl 2 < AlCl 3 < SnCl 4 Cl B
(C 4 H 8Cl 2 )
12. Boiling point increases gradually with increase in H3C
molecular weight. With branching, the surface area C==O +H2NOH →
decreases and therefore, the boiling point H3CH2C – H 2O
decreases. H3C
NH 3 + H 2S C==NOH
13. NH 4HS (s) a CH3CH2
Initially 1 0.5 0 (oxime)
At equilibrium 1 ( 0.5 + x ) x H3C
C==O + Tollen’s reagent →
Since, solid concentration remains constant, hence H3C H2C
pNH 4 HS = 1
No reaction
K p = p NH 3 × p H 2S

NaNO +3 +3 +4
20. CH3CH2NH2 →
2 KMnO 4
CH3CH2OH → 26. 2Fe 2 O 3 ⋅ Cr 2O 3 + 4Na 2CO 3 + 3O 2 →
HCl (A) +3 +6 +4
(i) SOCl2 2Fe 2 O 3 + 4Na 2 CrO 4 + 4CO 2
CH3COOH →
(ii) NH
CH3CONH2
3 The oxidation state of chromium increases from +3
( B) (C )
to +6.
Br
→
2
CH3NH2
NaOH
Methyl amine 27. pB = ptotal − pA
( D) ptotal = 84 torr
pA = X A × p°A
21. ψ2 is proportional to the probability of finding an
electron. = (1 − 0.2 ) × 70
= 56torr
22. KNO 3 → KNO 2 + O 2 pB = 84 − 56
Other gives oxides and NO 2 gas. = 28 torr
p 28
23. Actinoids have a much greater tendency to form p° B = B =
X B 0.2
complexes than lanthanoids.
This is because actinoids show a large number of = 140 torr
oxidation states due to a small energy gap between
28. NaOH + CH3COOH → CH3COONa + H2O
5f, 6d and 7s subshells. Hence, all their electrons
can take part in complex formation. mmol 20 × 0.2 50 × 0.2 0 0
added =4 = 10
24. O 2−
(17 ) = σ1s , σ 1s , σ2 s , σ 2 s ,
2 * 2 2 * 2
mmol after 0 6 4 4
σ2 pz2 , π2 p2x ≈ π2 py2 , π* 2 p2x ≈ π* 2 p1y
reaction
Nb − Na 10 − 7 3
BO = = = = 1. 5 ∴ [CH3COOH] =
6
;
2 2 2 70
In O 2 (16), bond order is 2. 4
[CH3COONa] =
In O +2 (15), bond order is 2.5. 70
1 4/70
Bond order ∝ ∴ pH = − log 1.8 × 10−5 + log
Bond length 6/70
Thus, correct order is pH = 4.56
O −2 > O 2 > O+2
29. Ecell = E ° + E°
Cd /Cd 2 + Ag + / Ag
25. NH4NO 3 (s ) → N2O(g ) + 2H2O(l )
= 0.40 + 0.80
∆H Reaction = ∆H Products − ∆H Reactants = 1.2 V
= ∆H N 2O + 2 × ∆H H 2O − ∆H NH 4 NO 3 0.059 [Ag+ ]2
Ecell = E °cell + log
= 81.46 + 2 (−285.8) − (−367.57 ) 2 [Cd 2+ ]
∆H = − 122 .560 kJ If [Cd 2+ ] is 0.10 M in place of 1 M, then Ecell will be
∆H = ∆E + ∆nRT more positive.
− 122560 = ∆E + 1 × 8.314 × 298 30. As in cases (I), (II) and (IV), the acids and bases
∆E = − 125037 J taken are strong and the enthalpy of neutralisation of
all strong acids with strong bases is same,
= −125 .037 kJ i.e., – 57.3 kJ.

Practice Set 3
Instructions
1. ∧°eq . for BaCl 2 , H 2 SO 4 and HCl are 7. Which of the following will undergo
x1 , x 2 and x 3 S cm eq 1 −1
respectively. If dehydration fast?
OH
conductivity of saturated BaSO 4 solution is y S
cm −1 , then K sp for BaSO 4 is (a) OH (b)
6 2 9 3
10 y 10 y
(a) (b)
2( x 1 + x 2 − 2 x 3 ) 8( x 1 + x 2 − 2 x 3 )3
(c) OH (d)
10 3 y 10 6 y 2 OH
(c) (d)
2( x 1 + x 2 − 2 x 3 ) 4( x 1 + x 2 − 2 x 3 ) 2
H
2. In which of the following, glycol is an 8. The alcohol, having molecular formulaC 4H 9OH,
important constituent? when shaken with a mixture of anhydrous ZnCl 2
(a) Acrilan (b) Teflon (c) Dacron (d) Bakelite and conc. HCl give an oil layer product after five
3. The halide that is not hydrolysed is minutes. The alcohol is
(a) SiCl 4 (b) SnCl 4 (a) H 3C  (CH 2 )3 OH
(c) PbCl 4 (d) CCl 4 (b) (CH 3 )2CHCH 2 OH
(c) (CH 3 )3C OH
4. Chemical substances used to cure mental (d) H 3C CH(OH)CH 2 CH 3
diseases are called
(a) tranquilizers (b) antihistamines 9. How many moles of MgIn 2 S 4 can be produced
(c) analgesics (d) antimicrobials when 1.00 g of magnesium (at. mass = 24), 1.00
g of indium (atomic mass = 114.8)and 1.00 g of
5. Consider the reactions,
K1
sulphur (atomic mass = 32) react?
(i) CO( g ) + H 2O( g )
aCO (g ) + H (g ) 2 2 (a) 6.74 × 10 −4 (b) 3.1 × 10 −2
K2 (c) 4.17 × 10 −2 (d) 8.7 × 10 −3
(ii) CH ( g ) + H O( g ) aCO( g ) + 3H ( g )
4 2 2
K3 10. If the cell-edge length for CsCl is 0.4123 nm
(iii) CH ( g ) + 2H O( g ) aCO ( g ) + 4H ( g )
4 2 2 2 and the ionic radius of a Cl − ion is 0.181 nm,
Which of the following is correct ? then the ionic radius of a Cs + ion is
(a) K 3 = K 1/K 2 (b) K 3 = K 12/K 23 (a) 0.176 nm (b) 0.231 nm
(c) 0.352 nm (d) 0.116 nm
(c) K 3 = K 1 ⋅ K 2 (d) K 3 = K 1 ⋅ K 2
11. NH3 has a net dipole moment while dipole
6. An ideal solution of benzene and toluene boils moment of BF3 is zero, this is because
at 1 atmospheric pressure at 90°C. At 90°C , (a) fluorine is more electronegative than nitrogen
benzene has a vapour pressure of 1022 mm (b) boron is more electronegative than nitrogen
and toluene has a vapour pressure of 406 mm. (c) NH 3 is not a planar molecule while BF3 is a planar
The mole fraction of benzene in the solution is molecule
(a) 0.284 (b) 0.364 (d) NH 3 is a planar molecule while BF3 is not a planar
(c) 0.574 (d) 0.475 molecule

12. For the first order reactionTav (average life),T50 19. Which of the following statements is correct?
andT75 in the increasing order are (a) Fe 2+ gives brown colour with ammonium
(a) T 50 < T av < T 75 (b) T 50 < T 75 < T av thiocyanate
(c) T av < T 50 < T 75 (d) T av = T 50 < T 75 (b) Fe 2+ gives blue precipitate with potassium
ferricyanide
13. Which of the following hasd 2sp 3 hybridisation ? (c) Fe 2+ gives brown colour with potassium
(a) [CoF6 ] 3 + (b) [Fe(CN)6 ] 3− ferricyanide
2+ (d) Fe 2+ gives red colour with potassium
(c) [Co(H 2O)6 ] (d) [PtCl 4 ] 2−
ferrocyanide
14. Which of the following is not involved in the 20. An electron in H-atom in its ground state
formation of photochemical smog? absorbs 1.50 times as much as energy as the
(a) NO (b) O 3 (c) C x H y (d) SO 2 minimum required for its escape (13.6 eV)
15. In a set of reactions, ethylbenzene yilded a from the atom. Thus, KE given to emitted
product D. electron is
CH2CH3 (a) 13.6 eV (b) 20.4 eV (c) 34.0 eV (d) 6.8 eV
A
KMnO4
B
Br2
C
C2H5OH
D
21. One gram sample of heptane, C 7H16 is burned
KOH FeCl3 H+ in excess of oxygen in a bomb calorimeter.
D should be The temperature of the calorimeter rises from
COOC2H5 290 K to 298 K. If heat capacity of the
COOH calorimeter is 7 kJ/K, the enthalpy of
combustion of heptane is
(a) (b) (a) 5472 kJ/mol (b) 5234 kJ/mol
OC2H5 Br (c) 5400 kJ/mol (d) 5600 kJ/mol
Br 22. Sulphur is converted into Na 2 S in Lassaigne
CH2 CH COOC2H5
fusion test. Na 2 S can be detected by
(c) (d) (I) (CH 3COO)2 Pb (II) CH 3COOH
Br
Br (III) Na 2 [Fe(CN)5 NO]
COOC2H5 Correct codes are
(a) (I), (II) (b) (I), (III)
16. 0.0005 mole of strong electrolyte, Ca(OH)2 is (c) (III) only (d) (I), (II), (III) all
dissolved to form 100 mL of a saturated
aqueous solution. The pH of this solution is 23. The osmotic pressure will be lowest for
(a) 12 (b) 11.7 (c) 9.78 (d) 3.3 (a) 0.10 M sodium nitrate
(b) 0.08 M barium nitrate
17. Bromine is added to cold dilute aqueous solution (c) 0.06 M sodium sulphate
of sodium hydroxide. The mixture is boiled. (d) 0.10 M sucrose
Which of the following statements is not true?
(a) During the reaction bromine is present in four
24. Copper sulphate reacts with KCN solution to
different oxidation states form
(b) The greatest difference between the various (a) Cu(CN) (b) Cu(CN)2
oxidation states of bromine is 5 (c) K 3[Cu(CN)4 ] (d) K 4 [Cu(CN)6 ]
(c) On acidification of the final mixture, bromine is
formed 25. The degree of hydrolysis in hydrolic
(d) Disproportionation of bromine occurs during the equilibrium
reaction A −(aq ) + H 2O (l ) a HA (aq ) + OH (aq ) −
18. The correct order of increasing N N bond at salt concentration 0.0001 M is

stability of N 22 − , N 2 , N 2⊕ , N 2− is (K a = 1.0 × 10 −6 )
(a) N 22− > N 2 > N s2 > N ⊕ (b) N 2 > N 2⊕ = N s2 > N 22− (a)1 × 10 −2 (b)1 × 10 −3
2
−4
(c) 5 × 10 (d)1 × 10 −6
(c) N 2− > N s = N ⊕ > N
2 2 2 2 (d) N 2− > N > N s = N ⊕
2 2 2 2

Practice Set 3 329
26. An aqueous solution of colourless metal (a) E = − 0.36 +

0.059
log 2 × 10 −2
sulphate M gives a white precipitate with 2
NH 4OH. This was soluble in excess of NH 4OH. (b) E = − 0.36 −
0.059
log 50
On passing H 2 S through this solution a white 2
ppt. is formed. The metal M in the salt is
0.059
(c) E = + 0.36 − log 2 × 10 −2
(a) Ca (b) Ba (c) Al (d) Zn 2
0.059
27. In order to obtain (CH 3 )3 CCl, which set of (d) E = − 0.36 + log 50
2
reactants is most suitable ?
(a) (CH 3 )3CBr + HCl 29. Which electrolyte is most effective in causing
(b) (CH 3 )2C === CH 2 + HCl coagulation of ferric hydroxide sol?
(c) (CH 3 )2C === CH 2 + Cl 2 (a) KBr (b) K 2SO 4
(d) (CH 3 )2CO + CH 3OH (c) K 2CrO 4 (d) K 3[Fe(CN)6 ]
28. The emf of the following cell 30. Which of the following is not an electrophilic
Zn| Zn 2+ (0.004) || Cd 2+ (0.2) | Cd is given by reagent?
[E °( Zn 2+ /Zn ) = − 0 .763 V (a) NO 2+ (b) BF3
and E °( Cd 2+ /Cd ) = − 0 .403 V ] (c) SO 3 (d) R  OH
Answers
1. (d) 2. (c) 3. (d) 4. (a) 5. (c) 6. (c) 7. (a) 8. (d) 9. (d) 10. (a)
11. (c) 12. (a) 13. (b) 14. (d) 15. (b) 16. (a) 17. (c) 18. (b) 19. (b) 20. (b)
21. (d) 22. (b) 23. (d) 24. (c) 25. (a) 26. (d) 27. (b) 28. (c) 29. (d) 30. (d)
Solutions
1. ∧°eq (BaSO 4 ) = ∧°eq (BaCl 2 ) + ∧° (H 2SO 4 ) − 2 ∧°eq (HCl ) 4. Tranquilizers are the chemical substances, used to
cure mental disease. They reduce anxiety and induce
= x1 + x2 − 2 x3
sleep e. g ., barbituric acid.
1000 × K
∧°eq (BaSO 4 ) = [CO 2 ] [H 2 ] [CO] [H 2 ]3
Normality (Solubility in g eq L−1 ) 5. K1 = , K2 =
[CO] [H 2O] [CH 4 ] [H 2O]
1000 × y
∴Solubility in g eq L−1 = [CO 2 ] [H 2 ]4
x1 + x2 − 2 x3 K3 =
1000 y [CH 4 ] [H 2O]2
Solubility in mol L −1 =
2( x1 + x2 − 2 x3 ) K1 × K 2 = K 3
2+ 2− 6. p° B X B + p°T XT = ptotal
BaSO4 a Ba
S
+ SO4
S
1022 X B + 406 (1 − X B ) = 1 atm
Ksp = ( s )2
2 = 760 mm Hg [Q X B + XT = 1]
 1000 y  10 6 y 6
=  = On solving, X B = 0.574
 2( x1 + x2 − 2 x3 ) 
2
4( x1 + x2 − 2 x3 )2
7. Dehydration reactions of alcohols leads to the
2. Dacron (terylene) is a polymer of ethylene glycol and formation of carbocations as is more stable than
terephthalic acid. secondary and primary, thus, tertiary alcohol would
undergo dehyderation fast.
3. Since carbon has no d-orbital, hence it cannot extend
its coordination number beyond four, thus its halides 8. Secondary alcohol, on reaction with anhydrous ZnCl 2
are not attacked (hydrolysed) by water. and conc. HCl (Lucas reagent) gives an oil layer
product after five minutes.

Lucas reagent
H 3C  CH(OH)  CH 2CH 3 → oil layer 13. Fe 3 + : [Ar] 3 d 5, 4s, 4 p
s −alcohol
Fe3+ : [Ar]
product (turbidity) after 5 min.
9. Mg + 2In + 4S → MgIn2S 4 [Fe (CN)6 ]3– × × × × × ×

Initial moles of d2 s p3
2 3
1 d sp and 1 unpaired electron
Mg = = 0 . 0417
24
1 14. Photochemical smog comprises O 3, NO, acrolein,
In = = 8 .71 × 10 −3
114 . 8 formaldehyde and peroxyacyl nitrate (PAN). These are
prepared as follows
1
S= = 0 . 032 NO 2( g )  hv
→ NO( g ) + O( g )
32
O( g ) + O 2( g ) → O 3( g )
Amongst the following, In possesses smaller number of
moles in comparison to Mg and S. Thus, it will react NO( g ) + O 3( g ) → NO 2( g ) + O 2( g )
completely in the reaction. This suggests that In will be 3CH 4 + 2O 3 → 3HCHO + 3H 2O
the limiting reagent.
Hence, 8 .71 × 10 −3 moles of Mg In2S 4 would be COOH
produced in the reaction. CH2CH3
Br2 / FeCl3
KMnO4
10. CsCl has a bcc lattice, so 15. KOH E+sustitution
d = a 3 [here d is diagonal] [oxidation] (B) [–COOH is
(A)
= 0.4123 × 3 = 0 .7141 nm [benzoic acid] m-directing]
d 07141
.
r + + rCl − = = = 0.3571 nm COOC2H5
Cs
2 2 COOH
r + + 0 .181 = 0.3571 nm
Cs C2H5OH/H +
r + = 0 .176 nm
Cs
[Esterification]
11. Due to the presence of a lone pair of electron on Br Br
nitrogen atom ofNH 3, its structure is non-planar. Hence, (D) [C]
it possesses a net dipole moment. 16. Concentration of Ca(OH)2
While the structure of BF3 is trigonal planar (lie in one 0.0005 × 1000
= = 0.005 mol L−1
plane) thus, net dipole moment of BF3 is zero. 100
µ1
µ4 µ3 F Ca(OH)2 Ca 2+ + 2OH −
a
[µ1+µ2+µ3]
µ1 µ 3 F B (µ1+µ2) Initially 1 2
N
H µ2 0.005 0.005 × 2 = 0.01
H
µ F pOH = − log [OH − ] = − log [0.01] = 2
H 2 µ has = 0 Since, (µ1+µ2)=– µ0
∴µ has = 0 pH = 14 − 2 = 12
Reduction
12. For first order reaction 17.
0.693
T50 = 0 –1 +1 +5
k ∆
Br2 + NaOH NaBr + NaBrO + NaBrO 3
Tav = 1.44 × T50
2 .303 100 Oxidation
T75 = log
k 100 − 75
Oxidation, difference of 5 (greatest)
2.303 2 × 0.693
= log 4 =
k k 18. N 22− (16) : σ 1s 2, σ* 1s 2, σ 2 s 2, σ* 2 s 2 ,
[Q T75 = 2T50]
σ 2 pz2, π2 px2 ≈ π2 py2, π* 2 p1x ≈ π* 2 p1y
Hence, T50 < Tav < T75
Nb − Na 10 − 6
Bond order = = =2
2 2

Practice Set 3 331
In N 2 (14) bond order = 3 10 −8 = 0.0001 h2 [Q (1 − h) ≈ 1]

In N −2 (15) bond order = 2 .5 10 −4 = h2
In N 2+ (13) bond order = 2 .5 h = 10 −2
bond order ∝ stability
26. All the given metals form white ppt. withNH 4OH but only
⊕ 2−
Thus, N 2 > N 2 = Ns
2 > N2 ppt. of Zn is soluble in excess ofNH 4OH and on passing
19. The blue precipitate of Fe 2+ ions with potassium H 2S it gives white ppt. of ZnS, so the metal is Zn and
ferricyanide is due to the formation of Turnbull’s blue m reactions takes place as follows
II III
complex, K Fe [ Fe (CN)6 ] Zn 2+ + 2NH 4OH → Zn(OH)2 ↓ + 2NH+4
II III White ppt.
Fe 2+ + K 3 [Fe (CN)6 ] → K Fe[Fe(CN)6 ] + 2K+ Zn(OH)2 + 2NH 4OH → (NH 4 )2 ZnO 2 + 2H 2O
Potassium Turnbull’s blue
ferricyanide Soluble
20. Energy in ground state = 13 . 6 eV (NH 4 )2 ZnO 2 + H 2S → ZnS ↓ + 2NH 4OH

White ppt
Energy absorbed = 1. 5 × 13 . 6 = 20 . 4 eV
27. Alkenes undergo Markownikoff addition when attacked
Energy in higher level = 34 . 0 eV
by acid HCl. During addition of HCl, alkenes forms a
Energy emitted = 34 . 0 − 13 . 6 = 20 . 4 eV carbocation as an intermediate through the addition of
21. Rise in temperature = 298 − 290 K = 8K H + ion on less substituted C-atom.
Thus, the carbocation so formed undergoes a
Heat given to the calorimeter
nucleophilic attack by Cl − on a more substitutecd
= Heat capacity × ∆T C-atom.
= 7 × 8 = 56 kJ (CH3)2 C CH2
Molar mass of heptane (C 7 H16 ) = 100 + +
H
1 g of heptane gives = 56 kJ (CH3)2 C CH3
[Addition on less
100 g of heptane gives = 56 × 100 = 5600 kJ/mol substituted C-atom]
(carbocation)
–
22. Na 2S + Na 2[Fe(CN)5NO] → Na 4 [Fe(CN)5NOS] Cl
(CH3)2 C CH3
Deep violet
[SN attack on
CH 3COOH PbS ↓ Cl
Na 2S + (CH 3COO)2Pb     → Black ppt. carbocation]
+ 2CH 3COONa 0.059 [oxidised state]

28. E = E °cell − log
n [reduced state]
23. Osmotic pressure is colligative property, thus, it n = number of electrons taken part in the reaction
depends upon the number of moles of solute. Smaller
=2
the number of moles of solute, lower is the osmotic
0 .059 0.004
pressure. E = [E °Zn / Zn 2 + + E ° 2+ ]− log
Cd /Cd
Hence, osmotic pressure will be lowest for sucrose, 2 0 .2
since it is non-electrolyte. 0.059 1
= [0 .763 − 0.403] − log
2 50
24. CuSO 4 + 2KCN → Cu(CN)2 + K 2SO 4
0.059
(Unstable) = 0.36 − log 2 × 10 −2
2
2Cu(CN)2 → Cu2(CN)2 + (CN)2
29. Ferric hydroxide is a positive sol, thus coagulated by
Cu2(CN)2 + 6KCN → 2K 3[Cu(CN)4 ] negative ions (like Br − , SO 24− , CrO 24− and [Fe(CN)6 ]3− ).
K 10 −14
25. Kh = w = = 10 −8 More is the valency of negative ion, more is the
Ka 10 −6 coagulating power.
A − + H 2O a HA + OH − • •
30. R — OH is not electrophilic because oxygen has two
••
[HA ] [OH − ]
Kh = − lone pair of electrons and hence it is nucleophilic in
[A ] nature.
( 0.0001 × h) ( 0.0001 × h)
Kh =
0.0001 (1 − h)

Practice Set 4
Instructions
. 1. If 195 mg/mL of K ⊕ ions are present in human 7. Which of the following is most likely structure
blood, then its molarity is of CrCl 3 ⋅ 6H 2O, if 1/3 of total chlorine of the
(a) 4 M (b) 3 M (c) 2 M (d) 5 M compound is precipitated by adding AgNO3 to
its aqueous solution?
2. When sulphur in the form of S8 is heated at 900 (a) CrCl 3 ⋅ 6H 2O
K, the initial pressure of 1 atm falls by 29% at (b) [Cr(H 2O)3Cl 3 ] (H 2O)3
equilibrium. This is because of conversion of (c) [CrCl 2(H 2O)4 ] Cl ⋅ 2H 2O
some S 8 into S 2. The value of equilibrium (d) [CrCl ⋅ (H 2O)5 ] Cl 2 ⋅ H 2O
constant for this reaction is
(a) 2.55 (b) 9.9 × 10 −3 (c)11 × 10 −2 (d) 1.89 8. Which of the following statements is incorrect?
(a) The first ionisation potential of Al is less than
3. Phosphine (PH 3 ) is a hydride of nitrogen the first ionisation potential of Mg
family. The structure for phosphine molecule (b) The first ionisation potential of Na is less than
in the vapour phase is the first ionisation potential of Mg
H (c) The second ionisation potential of Mg is greater
H
than the second ionisation potential of Na
(a) P 120° 90° (d) The third ionisation potential of Mg is greater
(b) H P H
:
H H than the third ionisation potential of Al

:
P P 9. If the heat of a reaction at constant volume

(c) H H (d) H H exceeds that at constant pressure and at 25°C
<109° 109°
H H by 1785 cal, then the value of K p/K c for this
reaction is
4. Among the 0.1 M solution of A, B andC , boiling (a) 68.3 × 10 −4 (b) 6.8 ×10 −5
point is the highest for C. While vapour (c) 6.4 ×10 −9 (d) 6.35
pressure is the highest for B. Then, their
correct order of freezing point will be 10. The first order 50% decomposition of
(a) A > B > C (b) B < A > C (c) A < B > C (d) B < A < C hydrogen peroxide is completed in 360 min at
380°C. The energy of activation for this
5. The electron identified by quantum number n
reaction is 200 kJ mol −1 . The time required for
and l.
its 75% decomposition at 450°C will be
(i) n = 5 , l = 0 (ii) n = 3 , l = 2
(a) 20.34 min (b) 25.5 min
(iii) n = 4 , l = 0 (iv) n = 2 , l = 0
(c) 12 min (d) 180 min
can be placed in order of increasing energy
from lowest to highest as 11. Three faraday of electricity was passed
(a) (iv) < (iii) < (ii) < (i) (b) (iii) < (iv) < (ii) < (i) through aq CrCl 3 , aq CuSO4 and molten NaCl
(c) (ii) < (i) < (iv) < (iii) (d) (iii) < (iv) < (i) < (ii) taken in three different electrolytic cell. The
amount of Cr, Cu and Na deposited at the
6. SnO + HCl →
 X + H 2O
cathode will be in the ratio of
C 6H 5 NO2 + 6HCl + X →
 Y + Z + H 2O (a) 1mole : 2 mole : 3 mole
Identify X andY in the above reactions. (b) 1 mole : 3 mole : 2 mole
(a) SnCl 2 , SnCl 4 (b) SnCl 4 , C 6 H 5NH 2 (c) 1 mole : 1.5 mole : 3 mole
(d) 1.5 mole : 2 mole : 3 mole
(c) C 6 H 5NH 2 , SnCl 2 (d) SnCl 2 , C 6 H 5NH 2

Practice Set 4 333
12. The product of the reaction of p-xylene with 18. Which of the following carbocations is the most
NBS is stable?
(a) o , o ′- dibromo-p- xylene CH3 CH3
(b) o- bromo-p- xylene
(c) o , m- dibromo-p- xylene r
(d) α , α ′- dibromo-p- xylene (a) (b)

r
13. Which of the following compounds is
colourless? H Y Y H
(a) Na 2[CuCl 4 ] (b) Na 2[CdCl 4 ]
CH3 CH3
(c) K 4 [Fe(CN)6 ] (d) K 3[Fe(CN)6 ]
14. A white crystalline compound (A) swells up r r

on heating and gives violet colour flame on (c) H (d) H
burning. Its aqueous solution gives white
ppt with BaCl 2 . It gives white gelatinous ppt Y Y
with NH 4Cl and excess of NH 4OH which
dissolves in NaOH but reappears on boiling 19. AgCl and NaCl are colourless. NaBr and NaI are
with conc NH 4Cl .(A) is also colourless but AgBr and AgI are coloured.
(a) Na 2 B4O 7 ⋅ 10H 2O This is due to
(b) CaOCl 2 (a) Ag + polarises Br − and I−
(c) K 2SO 4 ⋅ Al 2(SO 4 )3 ⋅ 24H 2O
(d) CuSO 4 ⋅ 5H 2O (b) Ag + has unpaired d-orbital
(c) Ag + depolarises Br − and I−
15. The equilibrium constant for the reaction
Sn (s ) + 2 Cu 2 + (aq ) Sn 2 + (aq )+ 2Cu + (aq )
a
at 25°C is (Given, E °Sn 2+/Sn = − 0.14 V, 20. A hydrocarbon having molecular formula C 7H12
E °Cu 2+/Cu + = 0.15 V ) (A), on ozonolysis gives a compound (B ) which
undergoes aldol condensation giving 1-acetyl
(a) 3.25 × 10 4 (b) 6.48 × 10 −9 cyclopentene. The structure of compound A is
(c) 6.51 × 10 9 (d) 4.38 × 10 −7
CH3 CH3 CH3 CH3
16. Identify the compound ‘C’ in the following
sequence of reactions
AlCl (a) (b) (c) (d)
C 6H 6 + CH 2 == CHCH 2CH 2Cl →
3
A
(i) BH 3/THF
→ B →
HF
C
(ii) H 2O 2, OH − ∆ 21. Enthalpy change for the reaction
4H ( g ) → 2H 2 ( g ) is − 869.6 kJ. The
(a) (b) dissociation energy of H  H bond is
(a) + 217. 4 kJ (b) – 434.8 kJ
(c) –869.6 kJ (d) + 434.8 kJ
(c) (d)
22. During the preparation of acetanilide from
aniline a small amount of zinc is added to the
reaction mixture because
17. Among the following species, identify the (a) zinc induces the precipitation
isostructural pairs
(b) zinc prevents the reduction of aniline during the
NH 3 , ClO3− , NO3− , SF5⊕ , PCl 5 and BF3 reaction
(a) (NH 3 , ClO 3− ) and (SF5+ , PCl 5 ) (c) zinc reduces the coloured impurities in the
aniline and also prevents its oxidation during
(b) (ClO −3 , NO 3− ) and (NH 3 , PCl 5 )
the reaction
(c) (BF3 , NO 3− ) and (SF5+ , PCl 5 ) (d) zinc forms a white crystalline complex with
aniline
(d) (BF3 , NH 3 ) and (SF5⊕ , PCl 5 )

23. Consider the following reaction occurring in 27. An element (X ) forms compounds of the
an automobile, formula XCl 3 , X 2O5 and Ca 3X 2, but does not
2C 8H18 ( g ) + 25 O2 ( g ) → 16 CO2 ( g ) form XCl 5 . Which of the following is the
+ 18H 2O( g ) element X?
the sign of ∆H , ∆S and ∆G would be
(a) B (b) Al (c) N (d) P

(a) –ve, +ve, –ve (b) +ve, –ve, +ve
28. Which of the following will undergo nitration
(c) –ve, +ve, +ve (d) +ve, +ve, –ve slow than benzene ?
NH2
24. The molal freezing point constant for water
1.86 °C/M. Therefore, the freezing point of 0.1 m
NaCl solution in water is expected to be in °C (a) (b)
(a) − 1.86 (b) − 0.186
(c) − 0.372 (d) + 0.372
CI NHCOCH3
25. When 1L of a saturated solution of PbCl 2 is
evaporated to dryness, the residue is found to
(c) (d)
weight 4.5 g. The K sp for the solution is
(a)1.7 × 10 −3 (b)1.69 × 10 −5
(c)1.5 × 10 −3 (d)1.5 × 10 −5 29. p-toluidine and benzyl amine can be
distinguished by
26. What are the four quantum numbers of the (a) Sandmeyer’s reaction (b) Dye test
19th electron in scandium (at. no. 21)? (c) Molisch test (d) Gattermann reaction
1
(a) n = 4,l = 0,m = 0,m s = − 30. Phenolphthalein is an indicator for acid-base
2
titration, it exists as
1
(b) n = 4,l = 0,m = 0,m s = + (a) benzenoid form in acid and quinonoid form in
2 basic solution
1 (b) quinonoid form in acid and benzenoid form in
(c) n = 4,l = 0,m = 1,m s = +
2 basic solution
1 (c) quinonoid form in both
(d) n = 4,l = 1,m = −1,m s = +
2 (d) benzenoid form in both
Answers
1. (d) 2. (a) 3. (c) 4. (c) 5. (a) 6. (d) 7. (c) 8. (c) 9. (b) 10. (a)
11. (c) 12. (d) 13. (b) 14. (c) 15. (c) 16. (d) 17. (c) 18. (b) 19. (a) 20. (d)
21. (b) 22. (c) 23. (a) 24. (c) 25. (b) 26. (b) 27. (c) 28. (c) 29. (b) 30. (a)
Solutions
1. K ⊕ = 195 mg = 195 × 10 −3g 10 3 mL [or 1 L] blood will contain
195 × 10 −3 × 10 3
weight 195 × 10 −3 = = 5M
Number of moles = = 39
molecular weight 39
[Q loss of electron does not affect the atomic weight, 2. S 8( g ) a 4 S 2( g )
so atomic weight of K ⊕ is taken as 39] Initially 1 atm 0
195 × 10 −3 At equilibrium 1 −
29
0.29 × 4
1 mL blood contains = moles 100
39
= 0.71 atm = 1.16 atm

Practice Set 4 335
[ pS 2 ]4 [1.16]4 . × 10−3 = 0.0681 min−1

k2 = 35. 366 × 192
Equilibrium constant ( K p ) = =
[ pS 8 ] 0.71 For 75% decomposition at 450°C
= 2 .55 atm3 2. 303  a 
k= log10  
 a − x
:
3. P t
H H 2. 303 100
<109° 0. 0681 = log10 ⇒ t = 20.34 min
H t 25
The correct structure for PH 3 is
The bond angle is less than 109° due to the presence of 11. Since charge on Cr 3+ , Cu2+ , Na + is 3, 2, 1,
lone pair of electron. respectively.
1 1
1 So, one faraday will deposit , , 1 equivalent of ions.
4. Freezing point ∝ ∝ vapour pressure 3 2
boiling point 3 3
Hence, three faraday will deposit = , , 3
Thus, correct order is B > A > C i .e., A < B > C 3 2
5. Greater the value of ( n + l ), greater is the energy of CH3 CH2Br
orbital and for same value of ( n + l ), greater the n,
greater is the energy of orbital. NBS
12.
Thus, (iv) < (iii) < (ii) < (i)
6. SnO + HCl → SnCl 2 + H 2O

X CH3 CH2Br
(p-xylene) αα
, '-dibromo-p-xylene
C 6H 5NO 2 + 6HCl +SnCl 2 → C 6H 5NH 2 13. The outershell electronic configuration of Cu2 + , Fe 2 +
X Y
+ SnCl 4 + H 2O and Fe 3 + are 3 d 9, 3 d 6, 3 d 5 respectively i .e., they
Z contain 1, 4 and 5 unpaired electrons, thus coloured.
7. In CrCl 3 ⋅ 6H 2O total number of chlorine atoms = 3 But in Cd 2 + the outer shell is completely filled ( 3 d 10 ), so
Total chlorine precipitated it is colourless.
1 1
= of total chlorine in CrCl 3 ⋅ 6H 2O = × 3 = 1 14. K gives violet colour flame on burning SO 2− 4 gives white
3 3
ppt with BaCl 2 and Al gives white gelatinous ppt of
Only one atom of chlorine is precipitated by AgNO 3, so Al(OH)3 with NH 4Cl and NH 4OH (excess). Thus, the
the structure of complex will be[CrCl 2(H 2O)4 ] Cl ⋅ 2H 2O. compound contains K+ , SO 2− 3+
4 and Al and its formula
8. A large amount of energy is required to release one is K 2SO 4 ⋅ Al 2(SO 4 )3 ⋅ 24H 2O (double salt, give
electron from the outermost shell of Na + ion (due to properties of all constituents).
stable configuration) as compared to Mg + ion, thus
15. Sn( s ) + 2 Cu2 + ( aq ) a Sn2 + ( aq ) + 2 Cu + ( aq )
second ionisation potential of Na is greater than the
second ionisation potential of Mg. ° = E°
Ecell + E° = 0.14 + 0.15 = 0.29 V
Sn/Sn 2+ Cu 2+ /Cu+
9. ∆H = ∆E + ∆nRT or q p = q V + ∆nRT 0.0591
E °cell = log Keq
q p − q V = ∆nRT n
−1785 0.29 =
0.0591
∆n = ≈ −3 log Keq
2 × 298 2
Kp 0.29 × 2
= (RT )∆n = (0.0821 × 298)−3 = 6.8 × 10−5 log Keq = = 9. 814 ⇒ Keq = 6.51 × 109
Kc 0.0591
0.693
10. Rate constant at 380°C ( k1 ) = = 1.92 × 10 −3min−1
360 16.
We know that
k2 Ea  T2 − T1 
log =  
k1 2 .303 R  T1T2 
k2 200 × 10 3  723 − 653 
log = ×  = 1.548
k1 2 .303 × 8 .314  653 × 723 
k2
= 35.366
k1

22. During acetylating of aniline, zinc not only prevents the

oxidation of amine during heating but also reduces
coloured impurities if formed during heating.
23. For all combustion reactions ∆H is negative. As the
number of gaseous molecules increases, entropy also

increases i .e., +ve. For a spontaneous process ∆G
must be negative.
24. ∆T = i ⋅ K f × m = 2 × 1.86 × 0 .1 = 0 .372
Freezing point of solution = 0° C − 0.372 ° C
= −0.372 ° C
4.5
25. Solubility of PbCl 2 = 4.5 gL−1 = mol L−1
278
17. In both BF3 and NO −3 the number of bond pair of
PbCl 2 a Pb 2+ + 2Cl −
electrons are 3 and lone pair of electrons is zero, thus x 2x
3
they are isostructural.  4.5 
Ksp = 4 x3 = 4 ×  . × 10 −5
 = 169
As  278 
–
F O 26. Scandium has atomic number 21
B N
[Ar] ¼¿ ¼
2
F F O O 4s 3d 1
Trigonal planar
19th electron goes into 4s
Similarly in SF5⊕ and PCl 5, five bonds are formed, thus 1
∴ n = 4, l = 0, m = 0, m s = +
both have trigonal bipyramidal geometry. 2
18. In the given carbocations, carbocation (b) is the most 27. The element is N, which forms NCl 3, N 2O 5, Ca 3N 2 but
stable, as it is conjugated in nature and hence not NCl 5.
resonance stabilized.
28. It is because Cl atom deactivates the ring. In rest of the
19. Ag + polarises Br − and I − , thus AgBr and AgI are examples, the attached atoms activates the ring.
coloured. NH2 contains amino group directly attached to
20. 1-acetyl cyclopentene contains seven carbon atoms, it benzene ring, thus undergo diazotisation
means that ozonolysis has not resulted in the loss of reaction and give red dye. In benzyl amine
carbon atoms. So, it must be a cyclic alkene. 29. (C 6H 5CH 2NH 2 ) the amino group is not
CH3 directly attached to benzene ring, hence it
will not undergo diazotisation reaction.
CH3
CH3COCH2CH2CH2CH2CHO p-toluidine
O3 / H2O
(B) 30. Phenolphthalein is colourless in acid solution
(A ) (benzenoid form) and pink in alkali (basic) solution
O Aldol (quinonoid form).
condensation O
CH3 C OH OH OH
COCH3
C HO
CH2 H
CH
C C
CH2 CH2 OH–
1-acetyl cyclopentene O A +
(B) H
C COO–
21. 2 H 2 ( g ) → 4 H ( g ), ∆H = +869. 6 kJ
O
869. 6
or H 2 ( g ) → 2 H ( g ), ∆H = = 434. 8 kJ Colourless (acid medium) Red (alkaline medium)
2 benzenoid form quinonoid form

Practice Set 5
Instructions
1. Of the following acids 6. Relative lowering of vapour pressure of an

I. Hypophosphorous acid aqueous glucose dilute solution is found to be
II. Orthophosphorous acid 0.018. Hence, elevation in boiling point
III. Caro’s acid is (Given, that 1 molal aqueous urea solution
IV. Glycine boils at 00.054°C at 1 atm pressure).
(a) I, II monobasic; III dibasic acid and IV (a) 0.018° (b) 0.18° (c) 0.54° (d) 0.03°
amphoteric O OH
(b) II monobasic; I, III dibasic acid and IV O O
amphoteric 7.
(c) I monobasic; II, III dibasic acid and IV HO OH
amphoteric
(d) I, II, III dibasic acids and IV amphoteric IUPAC name of the compound is
(a) 2-carboxylic pentane-1, 5-dioic acid
2. Cationic addition polymerisation (b) propane-1, 2, 3-tricarboxylic acid
reaction initiated by an acid is maximum (c) iso-butane-1, 2, 3-tricarboxylic acid
in (d) butane-1, 2, 3-tricarboxylic acid
CH3 CH3
| | 8. When a certain conductivity cell was filled with
(a) H3C C  CH3 (b) CH3 C ==CH2
| 0.01 M solution of KCl, it had a resistance of
CH3 160 ohm at 25°C and when filled with 0.005 M
(c) CH3CH== CH2 (d) CH2 == CH2 NaOH, it had a resistance of 190 ohm. If specific
resistance of KCl solution is 700 ohm-cm, specific
3. Magnetic moments of Cr (Z = 24), Mn conductance (ohm −1cm −1 ) of NaOH solution is
(Z = 25) and Fe (Z = 26) are x , y and z (a) 0.00180 (b) 0.00170
respectively. Hence, (c) 0.00130 (d) 0.00120
(a) x = y = z (b) x = z < y
(c) x < y < z (d) x > y > z 9. The atomic radius of transition series decreases
very slightly as compared to that in
4. Which of the following pairs of metals is representative series. This is due to
purified by van Arkel method? (a) shielding effect (b) penetrating effect
(a) Zr and Ti (b) Ga and In (c) compton effect (d) inert pair effect
(c) Ni and Fe (d) Ag and Au
10. Arrange the following compounds in
5. Which reagent can be used to identify decreasing order of basicity
nickel ion? I. Ethylamine
(a) Resorcinol II. 2-amino ethanol
(b) Dimethyl glyoxime III. 3-amino-1-propanol
(c) Diphenyl benzidine (a) I > II > III (b) III > I > II
(d) Potassium ferrocyanide (c) III < I > II (d) I < II > III

11. 16 g of an ideal gas SOx occupies 5.6 L at STP. 18. Which of the following does not illustrate
The value of x for this gas is the anomalous properties of Li?
(a) 1 (b) 2 (a) The m.p. and b.p. of Li are comparatively high
(c) 3 (d) 4 (b) Li forms a nitride Li 3 N unlike group I metals
(c) Li is much softer than the other I group metals

12. 1 g of hydrogen and 112 g of nitrogen are (d) LiNO 3 on decomposition produces its oxide
enclosed in two separate containers each of unlike group I metals
volume 5 L at 27°C. If the pressure of
hydrogen is 1 atm, then the pressure of 19. If for a reaction A → B , ∆H = −10 kJ mol −1
nitrogen would be and E α = 50 kJ mol −1 , then the energy of
(a) 12 atm (b) 4 atm
activation for reaction B → A will be
(c) 8 atm (d) 16 atm
(a) 40 kJ mol −1 (b) 50 kJ mol −1
13. A buffer solution contains 100 mL of 0.01 M (c) −50 kJ mol −1 (d) 60 kJ mol −1
CH 3COOH and 200 mL of 0.02 M
CH 3COONa. 700 mL of water is added to this
20. NaAlH 4 reduces an ester into HCHO and
solution. pH before and after dilution are (CH 3 )2CHOH. Thus, ester is
( pK a = 4 .74) (a) HCOOCH(CH3 )2 (b) (CH3 )2 CHCOOCH3
(a) 5.04, 5.04 (b) 5.04, 0.504 (c) HCOOCH2CH2CH3 (d) CH3CH2COOCH3
(c) 5.34, 0.534 (d) 5.34, 5.34
21. For the following cell reaction
14. Following is the concentration cell in which Pb (s) + Hg 2SO4 (s ) aPbSO (s) + 2Hg(l )
4
electrode is reversible with respect to anion E °cell = 0.92 V
Pt(Cl 2 )|Cl − (C1 )||Cl − (C 2 )|Pt(Cl 2 ) −8
K sp (PbSO4 ) = 2 × 10 ,
1 bar 1 bar
The cell reaction is spontaneous if K sp (Hg 2SO4 ) = 1 × 10−6
(a) C1 > C 2 (b) C1 < C 2
(c) C1 = C 2 (d) C1 = 0 Hence, E cell is
(a) 0.92 V (b) 0.89 V
15. The complex showing a spin-only magnetic (c) 1.04 V (d) 0.95 V
moment of 2.82 BM is
(a) [Ni Cl 4 ] 2 − (b) [Ni (CN) 4 ] 2 − 22. What is the repeating unit in nucleic acids?
(a) Monosaccharides (b) Amino acids
(c) Ni (CO 4 ) (d) Ni (PPh 3 ) 4
(c) Nucleotides (d) Nucleosides
16. A laboratory reagent imparts green colour to
the flame. On heating with solid K 2Cr2O 7
23. Reduction of a metal oxide by excess carbon
at high temperature is a method for the
and conc. H 2SO4 it evolves an orange red
commercial preparation of some metals.
gas. Identify the reagent.
This method can be successfully applied in
(a) CaCl 2
the case of
(b) BaCl 2 (a) BeO and Al 2O 3 (b) ZnO and Fe2O 3
(c) CuCl 2 (c) CaO and Cr2O 3 (d) BaO and U3O 8
24. Elevation in boiling point of an aqueous urea
17. van’t Hoff factors are x, y and z in case of solution is 0.52 ° (K b = 0.52 ° mol −1kg). Hence,
association, ionisation and no change, mole fraction of urea in this solution is
respectively. Their increasing order is (a) 0.982 (b) 0.0567
(a) x < y < z (b) x = y = z (c) 0.943 (d) 0.018
(c) y < x < z (d) x < z < y

Practice Set 5 339
25. A 100 mL sample is removed from water solution 29. Analysis of chlorophyll shows that it
saturated with CaSO4 at 25°C. The water is contains 2.68 per cent magnesium.
completely evaporated from the sample and a How many atoms of magnesium does
deposit of 0.24 g CaSO4 is obtained. The K sp of 1.00 g of chlorophyll contain?
CaSO4 at 25°C is
(a) 6.72 ×1020 atoms

(a) 3.114 × 10−4 (b) 1.76 × 10−3 (b) 6.02 ×1023 atoms
(c) 2.32 × 10−4 (d) 3.24 × 10−6
(c) 6.72 ×1040 atoms
(d) 6.02 ×1021 atoms
26. Silver metal crystallises in a cubic closed packed
arrangement with the edge of the unit cell having ( CH )CCl
2 3 Cl /FeCl HBr
a length a = 407 pm. What is the radius of silver 30. Anisole →
3
→ → X.
AlCl 3 ∆
atom?
The product X in the above series of
(a) 148 pm (b) 140.8 pm
reaction is
(c) 143.9 pm (d) 149.3 pm
OCH3 Br
27. In a transition series, as the atomic number Br Cl
increases, paramagnetism (a) (b)
(a) increases gradually
(b) decreases gradually
C(CH3)3 C(CH3)3
(c) first increases to a maximum and then decreases
(d) first decreases to a minimum and then increases Br OH
Br Cl
28. Which of the following pairs of liquid form an
emulsion? (c) (d)
(a) H2O and C2 H5OH
(b) C2 H5OH and C2 H5OC2 H5 C(CH3)3 C(CH3)3
(c) Water and coconut oil
(d) Coconut oil and NaOH
Answers
1. (c) 2. (b) 3. (d) 4. (a) 5. (b) 6. (c) 7. (b) 8. (d) 9. (a) 10. (c)
11. (b) 12. (c) 13. (b) 14. (a) 15. (a) 16. (b) 17. (d) 18. (c) 19. (d) 20. (a)
21. (d) 22. (c) 23. (b) 24. (d) 25. (a) 26. (c) 27. (c) 28. (c) 29. (a) 30. (d)

Solutions
O
1. Fe (26) = 1s 2 ,2s 2,2p 6,3s 2,3p 6,4s 2,3d 6
P 3d 6
(I) H O H
H Replaceable
hydrogen Four unpaired electrons
(Hypophosphorous acid)
(Monobasic acid) Magnetic moment (µ ) = n (n + 2 )
O where, n = number of unpaired electrons.
Greater the number of unpaired electrons, greater
P will be the magnetic moment. Thus, Cr > Mn > Fe.
( x) (y) (z)
(II) H O O H
4. Zr and Ti form unstable iodides, hance, purified by
Replaceable H Replaceable van Arkel method.
hydrogen hydrogen
(Orthophosphorous acid) 5. Nickel salt reacts with dimethyl glyoxime in the
(Dibasic acid) presence of NH4OH to give scarlet red ppt of nickel
O dimethyl glyoxime.
H3C  C ==NOH
(III) H O S O O H 2  + NiCl2 + 2NH4OH
H3C  C ==NOH
OH O
O 
Replaceable Replaceable
hydrogen
(Caro’s acid)
hydrogen
H3C  C ==NOH N== C  CH3
(Dibasic acid)
 

Ni

O H3C  C ==NOH N== C  CH3

(IV) CH2 C O H O OH
Nickel dimethyl glyoxime

NH2
Replaceable (Scarlet red ppt)
hydrogen
Can accept (Glycine) + 2NH4Cl + 2H2O
a proton (Amphoteric)
6. ∆Tb for urea solution = 0.54° = K f × molality
2. Vinylic monomers containing electron releasing 0.54°
Kf =
groups favour cationic addition polymerisation. As 1
the number of electron releasing group = 0.54° kg mol −1
(  CH3 ,  C 2H5 etc.,) increases, the ability to
∆p wM
undergo cationic polymerisation also increases. =
p° mW
3. Cr (24) = 1s 2 ,2s 2,2p 6,3s 2,3p 6,4s 1,3d 5 w ∆p
4s 3d5 =
mW p° M
0.018
=
Six unpaired electrons 18
1000 K f w
Mn (25) = 1s ,2s ,2p ,3s ,3p 6,4s 2,3d 5
2 2 6 2 ∆Tb (glucose) =
mW
5
3d
1000 × 0.54 × 0.018
=
18
Five unpaired electrons = 0.54°

Practice Set 5 341
O OH
7. 13. pH (before dilution)
O O [salt]
= pK a + log
[acid]
2
HO 3 OH 200 × 0.02
1 = 4.74 + log
100 × 0.01
Propane-1, 2, 3-tricarboxylic acid

= 4.74 + log 4
resistance
8. Cell constant = = 5.34
specific resistance
Dilution has no effect on pH of buffer solution, hence
160 ohm
= pH (after dilution) = 5.34
700 ohm - cm
= 0.228 cm−1
14. Pt(Cl 2 )|Cl − (C1 )||Cl − (C 2 )|Pt(Cl 2 )
1 atm 1 atm
Q Cell constant for every cell is fixed. Thus,
0.0591 C
specific conductance of NaOH Ecell = log 1
1 1 C2
= × cell constant
resistance of NaOH Thus, cell reaction is spontaneous when
1 C1 > C 2
κ= × 0.228
190
15. Magnetic moment is given by
= 0.00120 ohm−1cm−1
µ = n(n + 2 )
9. In transition elements, as the atomic number 2.82 = n(n + 2 )
increases, the atomic radius decreases slightly (2.82 )2 = n(n + 2 )
because of screening effect by inner ‘d ’ orbitals.
7.9524 = n2 + 2 ⇒ n = 2
10. The electron withdrawing inductive effect of —OH Ni 28 = 3d 8 4s 2
group decreases the electron density on nitrogen,
Ni2+=3d 8=
thus lowering the basicity of amines. This effect
diminishes with distance from the amino group. 2 unpaired e–
Thus,
The two unpaired electrons will remain unpaired
ethylamine > 3-amino-1-propanol > 2-amino
only in the presence of weak ligand, Cl − .
ethanol
16. Ba 2+ ion imparts green colour to the flame and Cl –
11. 1 mole of the gas at STP = 22 .4 L ion forms chromyl chloride (which is orange red in
5.6 L at STP = 16 g colour) when treated with K 2Cr2O 7 and conc. H2SO 4 .
Thus, the reagent is
16 × 22 .4
Hence, 22.4 L at STP = = 64 g Ba 2+ + 2Cl – → BaCl 2
5.6
Thus, molecular mass of gas = 64 g 2BaCl 2 + K 2Cr2O 7 + 3H2SO 4 → K 2SO 4
Given, gas is SO 2 32 + 16 x = 64 + 2BaSO 4 + 2CrO 2Cl 2 + 3H2O
x=2 Chromyl chloride
(Orange red gas)
Thus, gas is SO 2 .
12. Number of moles of hydrogen (nH ) = 1 mole 17. In case of ionisation i > 1
2
112 For no change i = 0
Number of moles of nitrogen (nN ) = = 4 mol For association i < 1
28
pH V nH RT Thus, ionisation > no change > association
= (y) ( z) ( x)
pN V nN RT
1
=
1 18. In I group all the metals are soft because of weak
pN 2 × 4 metallic bonding and this softness increases down
the group.
pN = 8 atm

19. ∆H ( A → B) = −10 kJ exothermic reaction 25. 100 mL of saturated CaSO 4 solution has 0.24 g of
Activated CaSO 4
state Thus, solubility of CaSO 4 = 2.4 gL−1
2 .4
50kJ = mol L−1 = 0.01765
136
K sp = S 2 = (0.01765)2 = 3114
. × 10−4
A
∆H 26. r = a = 407 = 143.9 pm
B 2 2 2 2
27. Paramagnetism depends upon the number of

∴ ∆H (B → A) = 10 kJ
unpaired electrons. As the atomic number increases
Ea ( A → activated state) = 50 kJ in a transition series, the number of unpaired
∴ Ea (B → activated state) = 50 + 10 = 60 kJ electrons first increases, then decreases, so also
the paramagnetism.
NaAlH
20. HCOOCH(CH3 )2 →
4
HCHO + (CH3 )2 CHOH
28. Oils are chemically esters, hence forms emulsion
with water.
2+ Ksp (PbSO 4 ) 2 × 10−8
21. Q = [Pb 2+ ] = =
[Hg 2 ] Ksp (Hg 2SO 4 ) 1 × 10−6 29. 1 g of chlorophyll has
. × 2.68
100
−2
= 2 × 10 = 0 .14 = g of Mg
100
0.059 2.68 1
Ecell = E °cell − log 0.14 = 100
. × × mol of Mg
2 100 24
= 0.92 − 0.0295 log 0.14 = 0.95 V 2.68
= × 6. 02 × 1023 atoms of mg
2400
22. Nucleic acid is a polymer of nucleotides.
= 6.72 × 1020 atoms
23. Least active metals have the most positive standard OCH3 OCH3
reduction potentials and are the easiest to reduce,
e. g .,
(Ch3)3CCl, AlCl3 Cl2 / FeCl3
Blast furnace 30.
Fe 2O 3 + 3C → 2Fe + 3CO (Fe alkylation) +
E substitution,
1200 °C Anisole methoxy group is a
ZnO + C → Zn + CO
C(CH3)3 stronger o, p directing
PbO + C → Pb + CO group than C(CH3)3
OH OCH3
24. ∆Tb = m × K b Cl Cl
HBr, ∆
0.52 = m × 0.52
Molality (m) = 1mol kg −1; Moles of urea = 1 [Cleavage
Ph OCH3
1000
Moles of H2O = = 55.55 C(CH3)3
(ethers)bond]
C(CH3)3
18
(X)
1
Xurea = = 0.018
56. 5

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